Proceedings - Toz Konfrensı

6th INTERNATIONAL POWDER METALLURGY CONFERENCE & EXHIBITION
6. ULUSLARARASI TOZ METALURJS KONFERANSI ve SERGS

APPLICATIONS
www.turkishpm.org

Development of PM in China
Authors: Michael Godin, Bahar Bayar, Fenling Han
Abstract
The continuous economic growth in China has an immense impact on the development of Chinese PM.
Widely known advantages such as low production cost are complemented by the increasing quality of
Chinese powders, PM parts and PM equipment.
The international trend towards production localization in the automotive sector is accompanied by political pressure from Chinese government, which aims to have 50% local content in cars sold in China.
2009 Chinese car production reached 13 million, surpassing the US as the largest auto market in the
world. Other industries such as medical, computer and telecommunication increasingly make use of
Chinese PM.
The development of Chinese PM raises concerns among western PM competitors, however most PM
companies in China have a relatively low technological level and arent able to meet the highest standards of foreign customers. Therefore the interest to purchase foreign PM equipment and technologies
offer various opportunities to foreign counterparts.
Overview
Abstract
1. History of PM in China
2. Automotive market in China 3.
3. PM in China - Market Data 4.
4. PM producers in China
Changsha Xunda Powder Metallurgy
NBTM New Materials Group
Shanghai Automotive Powder Metallurgy
5. PM equipment

Sintering Furnaces - Ningbo Dongfang Heating Equipment

Compacting Presses - Nanjing Eastern Precision Machinery (EPM)
Atomization - Changsha Easy Fashion Industry
HIP & CIP - Beijing Isostatic Pressing Technology Engineering Center (IPTEC)
6. Iron and Copper Powder in China

7. MIM in China
8. PM education in China
9. Trends and Development of the Chinese PM industry
10. References
1. History of PM in China
The PM industry in China started in the 1950s. One of the first enterprises to produce PM components
such as bearings was the company Shanghai Automotive Powder Metallurgy Co., Ltd. After Chinas
opening policy starting 1979 the development of PM in China accelerated due to the many opportunities

to supply PM components to emerging automotive, motorbike, electronics and furniture industries. As of

the beginning of the 21st century, the automotive industry in China continues to develop at an accelerated speed, increasingly driving the growth of Chinas PM. Counting Powder, Mold, PM equipment and
component manufactures
in China, there are approximately 2000 PM enterprises in China.
2. Automotive Market in China
The Chinese automotive market has been constantly growing for the last 20 years. In 2010 more than
18 264 700 vehicles were manufactured in China, making the Peoples Republic of China to the largest
automotive producer in the world. 2010 the industry showed an increase of 32.44% compared to 2009.
The output of passenger vehicles was 13 897 100. The quantity of automotive PM parts reached 18
456T in 2010, an increase of 9.8% compared to 2009. The amount of PM structural parts reached 116
835T, sinter parts were 12 509T. The PM industry in China is largely concentrated in eastern coastal regions, where most PM producers are located. However due to rising labor costs many enterprises have
started to move further inland where labor costs are still much less.
It can be predicted that China will continue to be a large and growing automotive market surpassing
20m cars in 2011. With an increasing amount of global automakers setting up their manufacturing plants
further inland in China, the PM industry will certainty continue growth in the next years. Currently only
3% of Chinese population have a driving license. Therefore there is a tremendous potential for the
automotive industry to further expand production and increase its sales in China. The PM industry in
China will benefit from the current 5 years plan of the Chinese Communist Party, which oblige automotive producers to localize at least 50% of their automotive components. The governmental requirement
forces automotive producers to source their PM components locally and refrain from importing them
into China.
Volkswagen and General Motors in China
Currently the VW and GM Groups are the most successful automotive corporations in China. Combined
the two companies have produced more than 3m vehicles in their manufacturing facilities across China
in 2010. VW and GM both entered the Chinese market in the early
1980s and have established various joint ventures with local partners. Their business models allowed
them to profit from the low production costs in China and substantially grow their business in cooperation with their partners.
3. PM in China - Market Data
Total PM Sales in 2010 reached 300m USD. A growth of 42% compared to 2009. PM in China is not as
closely related to the automotive market as it is in Europe or the US. Only 42% of all PM produced components in China are automotive components. Another 20% of PM parts components for the motorbike
industry. More than 30% of all produced PM parts are supplied to non automotive related industries such
as electronics, household, tools and others.
Chinas PM total output surpassed Japan in 2009, reaching 137 146T in 2010. The output of the largest
12 PM producers in China was more than 83 000T in 2009. Chinas PM is currently Asias largest PM
market.
Largest PM producers in Mainland China (Sales):
1. Ningbo NBTM
2. Yanzhou Porite
3. Haian Yingqiu
4. Chongqing Huafu
5. Shanghai Automotive (SAIC)
Chinas PM producers are not entirely focused on automotive products. Only five of the twelve largest
PM producers have more than 75% of their components produced for the automotive industry in 2009.
On average Chinese PM producers supplying 42% of its components to the automotive and 20% to the
motorbike industry.

4. PM producers in China
To show a general overview about the Chinese PM producers three PM producers will be presented.
According to output in tons in 2009, the largest Chinese PM producer, Ningbo NBTM (#1 in China),
Shanghai SAIC Group (#8 in China) Changshu Xunda (#20 in China) are briefly presented.
NBTM New Materials Group Co., Ltd.
NBTM is a first listed foreign-controlled company in China, which
emerged from Ningbo Tongmuo Powder Metallurgy Co., Ltd. The company is registered with the capital of 30m USD. The Mutsumi Special
Alloy Industry Co., Ltd. from Japan holds 33.34% of its shares. The
Group has seven production sites all over China, employing more than 3000 people. The companies
headquarter is in Ningbo, Zhejiang Province, approximately two hours south of Shanghai. Among others NBTM supplies to BorgWarner, ZF, Magna, GM, BYD. Only 42% of the companys production are
automotive components.
NBTM is the largest producer of sintered structural components in China. NBTMs annual production
capacity is more than 40 000T. In 2010 the annual sales reached 170m USD. The sintered components
manufactured by NBTM are used in automobile, motorcycle, refrigerator and air-conditioner compressors and power-tools. NTMB is exporting around 10% of its production to the US, Japan and Europe.
Shanghai Automotive Powder Metallurgy Co., Ltd. (SAIC)
SAIC is the oldest PM producer in China and is a completely government owned
enterprise. The company has been manufacturing PM components since the 1960s
and is currently the main PM supplier of GM and VW in Shanghai. Among others clients, the company
is supplying KIA, FAW and a few foreign clients. With 5000T annual production capacity and 34m USD
sales in 2010 the company belongs to largest PM producers in China.
Changshu Xunda Powder Metallurgy Co., Ltd.
Changshu Xunda is located 2 hours from Shanghai, in Changshu City, Jiangsu Province.
The company was founded in 1992 and is privately owned. Xunda employs 250 people
and has assets of 4m USD. The production facility covers an area of 20,000m2. Xunda
was ISO9001- 2000 certificated in 2001 and TS16949 & ISO14001 certificated in 2008.
Currently the production at Xunda, amounts 4m parts per month. The company produces products such
as gears and clutches in quantities of 500 000 and more pcs per year. Xunda has a full equipment park,
including more than 50 compacting presses ranging from 5T-500T, sizing presses, sintering furnaces,
after treatment equipment, mold making and machining equipment. In addition, Xunda has a lab with
all functions for 3D, precision air flow and strength testing. Xunda has also necessary equipment for
metallographic, material flow and hardness testing. And the heat treatment workshop is equipped with
an imported IPSEN furnace.
5. PM Equipment in China
Currently foreign PM equipment has less than 10% of the total market share in China. The main reason
is for the low market share is the high price of the foreign equipment and the long lead-times for spare
parts. In general Chinese PM Equipment costs approximately 30% of what foreign PM equipment costs.
In terms of quality, a difference remains between foreign and Chinese PM equipment, however there is a
rapid increase of the quality of Chinese PM Machinery. In addition most of the PM components produced
in China are rather simple and do not require highly sophisticated high precision equipment.
Isostatic Pressing Technology & Engineering Center (IPTEC)
IPTEC is the department of the China Iron & Steel Research Institute Group (CISRI) specialized in R&D
and production of isostatic pressing equipment. IPTEC has begun its R&D work and production of cold
isostatic presses (CIP) in 1956 and hot isostatic press (HIP) in 1972. In 1991, it developed its first sinter
hot isostatic press furnace (Sinter-HIP or SIP). It has been provided nearly two hundred of CIP, HIP and
Sinter-HIP furnaces for more than 100 customers in China and abroad. IPTECs equipments is widely
used in the molding, sintering and densification of high-temperature, titanium-aluminum and carbide alloys, high performance ceramics, powder metallurgy and composite materials.

The company currently currently has 40 employees in its production site in Hebei, 2h from Bejing. The
companies HQ is in Beijing, where 13 staff are involved in the companys operations and R&D. Annually
IPTEC has the capacity to produce 20 Sintering HIP, 10 CIP and 5 HIP furnaces. The production time
for a sintering HIP is around 18 months, the cycle for a SIP takes 10 months.
Examples are:
IPTECs Sintering HIP (exported to South Korea in 2010):
Size:
Temp:
Max. Load:
5 MPa Argon:
620x460x1700
1520C
1500kg
1400 C 8 C
IPTECs HIP (Installed for a Chinese customer in 2009):

Chamber size:
Temp:
Max. Load:
1 5 0 Mp a:
1250x2500mm
1400 C
10T
Argon Gas
Nanjing East Precision Machinery Co., Ltd (EPM)

EPM was established in 1995. EPM is a privately owned enterprise that specialized in the manufacturing & development of powder forming technology, forming equipment, tool adapters and peripheral
equipment. It provided thousands of automatic dry powder compacting presses for magnetic materials,
special ceramic, PM, hard metals and carbon production.
Currently the Nanjing based company has 250 staff and produced 200 presses in 2010. Among its clients are Miba, Ames, Tigra and Porite.
Ninbo Dongfang Heating Equipment Co., Ltd.
Ningbo Dongfang is the largest producer of heating equipment in China. With over 150 employees
the company has produced more than 100 sintering furnaces in 2010, reaching more than 10m USD
in sales last year. Some of the companys clients are the Hawk Corp, FJ Automotive Denmark, Porite,
SAIC and NBTM.
The company is constantly expanding its product range and developed its first MIM batch furnace in
2010. One of its recently sold sintering furnaces for a US client was a 1150C furnace with only 2C of
temperature difference at maximum operating temperature. With a production capacity of 240kg/hour
the furnace was built for up to 500g automotive and magnet component production.
Changsha Easy Fashion Equipment Co., Ltd.
Easy Fashion is a Changsha based company specializes in atomization equipment, vacuum and smelting furnaces. With over 80 staff (6 R&D) the company manufactured 30 Vacuum and 6 atomization units
for Chinese and foreign clients in 2010.
6. Powder Production in China
Iron and Copper Powder
Ferrous Powder production in China has been growing annually by 20% for the last 10 year, reaching
180 000T or approximately 85% of the US production in 2010. Copper powder in China has already
surpassed the US production, reaching 30 000T in 2010.

The Chinese government has implemented a 25% export tariff on metal powder made in China. The
current government restriction leads to market changes in China, making more high quality powder used
in China. The tariff on powder exports leads to an increase of quality of finished components since good
powder is being used domestically in China.
Iron Powder
Currently there are 28 ferrous powder producers in China, of which the seven largest have a market
share of 63%. The total output of ferrous powder in China has reached 295 000T in 2010 (Water Atomized 105 000T & reduced powder 186 000T).
Large Fe Atomized Powder producers in China
1. Laigang
2. Angang
3. Jiande
Large Fe Reduced Powder Producers in China
1. Laigang 2.
2. Wugang
3. Beipiao
4. Magang
Chinese powder is 50% cheaper than foreign powder. Therefore foreign powder is being replaced by
many components manufacturers with domestic powder.
Copper Powder
In 1960 only 40T of electrolytic Cu powder was produced in China. In 2009 the production of electrolytic
powder reached 20 500T. The total production of Cu powder in China has reached 40 500T.
Largest Cu powder producers in China
Beijing GRIPM
Chongqing Huahao
Hengshui Runze
Cu powder produced in China:
50% Electrolytic
33% Atomized
10% Copper Coating, others
7% Reduced
7. Metal Injection Molding (MIM) in China
Metal Injection Molding is a rather small industry in Chinese PM market, which started commercial application in the early 1990s. With increasing foreign direct investment into China, Chinese MIM experienced a high technological improvement and product innovation in recent years.
MIM sales in China in 2010 reached 55m USD. Compared to the sales in Asia of 450m USD, the MIM
market in China is still rather small, however continues to develop at an high speed pace. Currently
there are 70 MIM producers in China, of which most are located around eastern Chinese manufacturing hubs such as Beijing, Shanghai and Guangzhou with most companies located in the provinces of
Jiangsu, Zhejiang and Guangdong.
Most commonly used materials in Chinese MIM are 17-4PH, 316L and FeNi alloys. MIM in China is
strongly focused on computer and communication components and only few companies in China are
manufacturing medical equipment and automotive components. Most of the 70 MIM producers in China
are manufacturing their own feedstock and using predominantly domestic equipment.

Trends of MIM in China

The MIM industry in China is growing rapidly where an increasing number of MIM and MIM powder
newcomers can be seen. Due to high price foreign of MIM powder & feedstock foreign powder is being
replaced with domestic Chinese one.
An increasing use of cemented carbides, W & tool steels can be observed. Even though the MIM industry in China is already 20 years old, the domestic demand has not yet started and the majority of MIM
enterprises highly depend on exports. However with an increasing awareness for the MIM technology,
a demand for MIM products in China is expected shortly.
Due to rapidly rising labor and material costs Chinese MIM is rapidly moving from very low automation
to semi automated production, with an increasing number of robotics and computer programmed machines instead of manual labor. For that purpose Chinese MIM companies are heavily investing into the
purchase or own development of MIM equipment.
8. PM education in China
There are four leading universities with a PM core engineering major in China. The leading PM University is the Changsha Central South University. Other universities with a PM Major are Hefei Industrial,
Beijing Tech and Guangzhou Industrial. There are six leading PM R&D institutes in China. Powder
Metallurgical R&D institutes only accept PM master graduates. In 2010, there were over 500 graduates
with a PM major in China. The PM graduates are the main drive force behind the rapid development of
Chinas PM industry.
9. Trends in Chinese PM Industry
Most Chinese PM factories use domestic equipment and do not export their production. However a
quick quality improvement of Chinese equipment can be seen, since the producers are forced to meet
the requirements of foreign PM end users who engage in manufacturing and assembling in China and
require the highest component quality.
An increasing number of PM factories in China start to import foreign equipment to replace domestic
one. Regarding the powder, foreign powder is replaced with domestic one, mainly due to a much lower
price comparable quality. Chinas PM has gained increasing competitiveness in the world. As a result,
an increasing demand for training and education has become necessary.

THE PRACTICAL ANALYSIS OF FABRICATION OF A

COPPER PART BY METAL INJECTION MOLDING
Asghar SAFARIAN*, Karen ABRINIA ** and Amir Hossein BEHRAVESH ***
* Islamic Azad University, Maragheh Branch, Iran, asgharsafarian@iau-maragheh.ac.ir
Tehran University, Faculty of Engineering, Department of Mechanical Engineering, Tehran,
Iran, cabrinia@ut.ac.ir
***
Tarbiat Modares University, Faculty of Engineering, Department of Mechanical Engineering, Tehran, Iran,
amirhb@modares.ac.ir
**
ABSTRACT
In the present work the application of MIM to metal matrix composites comprising of Copper powders is presented.
The processing steps are discussed and a suitable set of powder loading, mixing procedure, molding condition
and debinding/sintering schedule has been established. A defect-free cylindrical part was successfully produced
and finally the effects of injection temperature, density and debinding/sintering atmosphere were studied. Also the
possibility of manual mixing of powder/binder and direct injection of that mixture without having prepared granules
has experimented.
Keywords: Metal Matrix Composites, Copper Powders, Debinding, Sintering, Powder Loading.
1. INTRODUCTION
The Metal Injection Molding (MIM) process is a combination of powder metallurgy and plastic injection molding
technologies. The process has been developed from the injection molding approach used for manufacturing of
plastic parts, but the technology for MIM is more complicated than that of plastic injection molding, which arises from
the need to remove the binder and to strengthen the part. The MIM process comprises of four main steps: mixing,
injection molding, debinding and sintering as illustrated in figure 1 [1].
Figure 1. Schematic diagram of MIM process.

In MIM process the most important thing is the technical information of these four steps which are different for
various materials. Therefore for each material some experiments should be done to get technical and applicable
data. That is what this study has tried to do for copper material which is very important in producing parts in different
sectors such as telecommunication, electricity, etc.
2. EXPERIMENTAL PROCEDURE
2.1. Material
Copper gas-atomized powders (code No. 19190, Ghatran Shimi Co., Iran) with spherical shape and average
particle size smaller than 15 m have been used in order to prepare the feedstock. The binder used in this work
is composite of 36% PP (fiber-free, Bandare Emam Petrochemical, IRAN), 60% paraffin wax (PW) and 4% stearic
acid (SA). Powder loading for this work is 94 wt.% copper and 6 wt.% binder.
In order to prepare the feedstock a manual mixing method has been used. For this purpose, at first step all PW
was melted and copper powders were added step by step. After this step other components were added based on
schedule shown in table 1.
The heating equipment was a normal gas burner with a controllable gas dial in a way that feedstock temperature
could be measured by a laser thermometer. In this step the used mixture was a fork shape manual one with rotation
of 200 rpm.
Table 1. Steps of feedstock manual mixing.
Steps
1
2
3
4
5
Temperature
65 C
65 C
65 C
65 C
Cooling until 24 C
Time of Mixing
..
15 min
25 min
15 min
20 min
Materials to be Added
100% PW
50% Copper Powder
50% Copper Powder
100% PP and SA
..
As the temperature was around the wax melting point, the only phenomenon happened in mixing step was powder
wetting by melted wax and therefore having powder and polymer stuck to each other what made a homogenous
physical feedstock not in granule form but in loose form of mixing which could easily fed into injection machine
hopper.
2.2. Molding
In this work a cylindrical part has been chosen as sample and one cavity mold with direct sprue has been designed
and made based on dimensions shown in Figure 2 (all dimensions are in mm). The prepared feedstock was injected
into the mold on a normal plastic injection machine (HAIDA HDX, 50 gr) with 7.5 MPa pressure and in two different
temperatures, 165C and 185C of feedstock temperature which was again measured by laser gun thermometer.
The injection process done in this situation and density measurement have proven that injection, with 165C results
in homogenous and dense parts, while with 185C, parts with low density were fabricated which could not be
debound and sintered to reach defect-free parts. The reason of this phenomenon will be discussed in following
sections.
Figure 2. Geometry of sample.
10

2.3. Debinding/Sintering
Thermal debinding was used to extract the binder inside the green parts. In this step different green parts regarding
their density from 5.5 to 7 g/cm3 were debound and so the effect of density on process and schedule of debinding
was determined. These densities are measured simply by weighting green parts and dividing them by part volume
((20)24). Table 2 shows the debinding steps done in a tube furnace with -0.5 bar vaccum and circulatory
system.
Table 2. Debinding steps.
Steps
1
2
3
Heating Rate (C/min)

0.5
1
2
Debinding Temperature (C)

100
250
500
Debinding Holding Time (min)

30
30
15
After debinding the same furnace was used to get the brown parts sintered and these parts get directly into sintering
step from debinding. Sintering step was started from 500C and in fact it continued from the debinding step. Table
3 illustrates this step in detail.
Table 3. Sintering steps.
steps
1(debinding last step)
2
Heating Rate
(C/min)
Sintering Temperature
(C)
500
980
Sintering Holding Time

(min)
60
The total time needed for debinding and sintering is 550 min and 120 min respectfully. After these steps defect-free
parts were fabricated from brown parts and the best result was reached from the green parts with density near 7 g/
cm3. Figure 3 shows the whole diagram of debinding/sintering in one graph. Figure 4 illustrates the sintered defectfree part regarding the final part density, mechanical properties like hardness and tensile, with total volumetrical
shrinkage of 13% which was measered by measuring the sintered part dimension and its weight.
3. RESULTS AND DISCUSSION
3.1. Influence of Injection Temperature
As it was explained before injection process was carried out in two temperatures, 165C and 185C. In 185C
because of high temperature, there is a low viscosity of feedstock mainly about binder, and therefore possibility of
separation of binder/powder under injection pressure increases and so the percentage of defected parts with low
density arises. Also separation phenomenon shown in Figure 5 is a concern that will definitely affect the debinding
and sintering steps. This separation was happened during the experiments and because the pictures of these
parts were not clear, this phenomenon is shown in schematic form. Differences among movements behavior of
components in feedstock especially between powder and binder cause some problems in molding process and it
gets worse when temperature gets high and viscosity drops dramatically.
Figure 3. The graph of debinding/sintering.
11
Figure 4. Sintered part.

Therefore temperature should be near polymer melting point which causes optimum viscosity that makes the
feedstock flow and get molded better and prevents the separation of powder and binder. In this study temperature
of 165C near the melting point of PP is optimum injection temperature that results in homogenous parts.
Another point to be considered is the difference between pure polymer and the present feedstock (powder/binder
suspension). Because of having the powder as metallic particles inside the feedstock, the machine barrel transfers
heat more easily and also there is interior friction that generates more heat inside the feedstock. Therefore the
injection temperature of pure polymer and this feedstock could not be equal. Therefore it seems that the lower
injection temperatures for this feedstock could have better injection results compared to pure PP.
Figure 5. Schematic shape showing the separation phenomenon in an injected part.

3.2. Influence of Green Part Density
Although a considerable amount of research has been focused on the relationship between the density and the
strength of sintered metal components [2-11], most of the investigations have not included both the low-density and
the high-density powder compacts. In the present work samples with density of 5.5 to 7 g/cm3 were debound and
sintered in order to study its effect on process. Low density samples have higher amount of binder and therefore there
is not adequate compact of metallic particles. Consequently these samples will collapse in debinding stage and that
is what happened for samples with density under 6.5 g/cm3. Although samples with higher density (around 6.5 g/
cm3) were debound without losing their shape, the result of sintering and strength of these parts was not satisfying
(for example after sintering some parts with this density could crumbled easily). Figure 6 shows micrographs of
these parts. As it is shown in figure 6 there are some gray places that show the presence of porosity.
3.3. Influence of Debinding/Sintering Atmosphere
In this section the effect of furnace atmosphere were studied. Three different mediums were applied on samples in
order not to get them oxidized:, vacuum, Nitrogen and Argon gases. The mechanical properties of sintered metals
depend strongly on the porosity, inclusions, oxygen content and other metallurgical variables [12].
In this stage because of high temperature metallic samples could get oxidized easily. Therefore a -0.5 bar vacuum
air atmosphere was applied on samples during debinding/sintering stage. However the result was not satisfying
and all samples were oxidized which could be seen by color changes and very low strength that caused parts
crumbling by hand pressure. The reason could be the low degree of vacuum, but because of lack of efficient
vacuum equipment high degree of vacuum was not applied.
Second medium was Nitrogen that was applied on samples. Nitrogen could not prevent samples oxidation completely
and the sintered parts showed inappropriate mechanical properties which observed by some tests like tensile test.
The reason was the degree of gas purity and its flow rate of 50 cc/min that was not enough for this experiment.
(a)
(b)
Figure 6. Micrographs of sintered parts (x1000),

a) green part density: 6.5 g/cm3 and b) green part density: 7 g/cm3.
12

Finally the last medium was studied and Argon was used with high purity and flow rate around 80 cc/min. Among
all these atmospheres Argon had the best result and sintered parts in third atmosphere got to reach the desired
mechanical properties compared to copper parts produced by other processes rather than MIM. It also should be
mentioned that in order to get the best result samples were located on graphite powders which got oxidized rapidly
and so could prevent metallic samples oxidation. Also it should be mentioned that the graphite powders were only
used in the last medium.
3.4. Influence of Feedstock Direct injection instead of prepared Granules
Making granules could expose some extra expense on metal injection molding. In this study an effort has been
done to examine the possibility of direct injection of feedstock with manual mixing (explained in section 2.1) not in
granule shape. The experiment has proven that in first stage of injection process, all injected parts (in this study
first ten parts) have low density and are not homogenous. While after some injection it turns to get better with high
quality. The reason could be the difference between movement behavior of binder and powder that makes them to
separate. After this separation, under applied pressure by screw, binder flows easily and fills the mold. Therefore
injected parts at first stage after starting point of injection have low density. However there is a slow flow for
powders. In other words, powders have gradually flow forward and gathered in front zone of barrel and get ready
to be injected to the cavity of mold. In this stage (after ten to fifteen parts) injected samples will have high density.
This phenomenon could happen periodically and there will be a combination parts with low and high density which
could heavily affect the production stability. As it mentioned before injection process have been done with normal
plastic machine with its normal screw that definitely could affect all process specially injection of feedstock without
granules. Although there is no absolute number of low density or high density parts based on which a injection
parameters could be set. Changes and optimization in screw design could cause the process and have different
results.
4. CONCLUSION
After various experiments done in this study, finally a defect-free part with total volumetrically shrinkage of 13% was
produced and all data needed for mixing, injection, debinding and sintering has determined. Also study of injection
temperature pointed out that injection temperature should be near polymer melting point and the more temperature
rises, the less samples density gets. With low density there is debinding and sintering problems. Even if there are
some samples with density near ideal densities, the sintered part shows inappropriate mechanical properties. In this
study the least density should be 7 g/cm3. Debinding and sintering stage have special concerns among which the
medium could be very important if the material is sensitive to oxygen, especially in high temperatures. For copper
samples debinding and sintering could be successful in Argon atmosphere with flow rate around 80cc/min.
REFERENCES
1. B.O. Rhee, Processing Behavior of Powder/Binder Mixtures in Powder Injection Molding-Binder Separation
and Quick Freezing, Doctor of Philosophy Thesis, Rensselaer Polytechnic Institute, School of Mechanical
Engineering, Troy, NY, USA, 1992.
2. A. Salak, V. Miskovic, E. Dudrova, E. Rudnayova, Powder Metall. Int. 6 (3) (1974) 128.
3. N.A. Fleck, R.A. Smith, Powder Metall. 24 (1981) 121-125.
4. V.T. Troshchenko, Sov. Powder Metall. Met. Ceram. 2 (1963) 179-184.
5. H.E. Exner, D. Pohl, Powder Metall. Int. 10 (1978) 193-199.
6. A. Bose, JOM 47 (8) (1995) 24-30.
7. G.F. Bocchini, Int. J. Powder Metall. 22 (3) (1986) 185-202.
8. A. Bose, J.J. Valencia, J. Spirko, R. Schmees, Advances in powder Metallurgy and Particulate Materials,
vol. 3, MIPIF, 1997, pp. 18099-18112.
9. G.F Bocchini, Int. J. Powder Metall. 22 (3) (1986) 185-202.
10. J.J. Valencia, T.J. McCabe, H. Dong, Advances in powder Metallurgy and Particulate Materials, vol. 2,
MIPIF, 1995, pp. 6205-6214.
11. T.J. Griffiths, R. Davies, M.B. Bassett, Powder metal. 22 (1979) 119-123.
12. R. Haynes, The Mechanical Behavior of Sintered Metals, Freund Pub., London, 1981.
13

THE PROCESSING OF Ni-RICH TiNi FOAMS WITH Mg SPACE HOLDER

TECNIQUE AND IN-VIVO EVALUATION AS GRAFT MATERIAL
G.pek NAKA*, B.Bertan ARPAK**, akir BOR***
*Middle East Technical University, Department of Metallurgical and Materials Engineering, 06800, Ankara, Trkiye,
inakas@metu.edu.tr
** Bakent University Faculty of Dentistry, Department of Oral and Maxillofacial Surgery, 06680, Ankara, Trkiye,
bertanarpak@gmail.com
***Middle East Technical University, Department of Metallurgical and Materials Engineering, 06800, Ankara,
Trkiye, bor@metu.edu.tr
ABSTRACT
Porous TiNi alloys are very promising materials for the biomedical applications due to their superelastic properties
and shape memory behavior in combination with the elastic module that are similar to that of bone. Surface roughness, which is a critical parameter to employ the material as a graft, can be achieved by the powder metallurgical
processes. However, the close control of the pore size, geometry and orientation is still difficult to maintain. In this
study, magnesium space holder technique is employed for manufacturing TiNi foams that consist of interconnected
pores with homogeneous shape, size and distribution in addition to the surface quality necessary for bone growth.
Porous TiNi alloys, which were processed from prealloyed nickel-rich (50.8 at.%Ni) TiNi powder via sintering at
1100 C for 1 hours under protective gas atmosphere, were placed into the created defects on the femur of rats
for a period of 90 days to evaluate the bone healing process. Afterwards, processing technique was improved via
increasing sintering temperature and time to 1200 C and 2 hours, respectively. The processed TiNi foams that have
uniformly distributed and interconnected spherical pores within a size range of 250-600 m, were in fully austenitic
state and the formation of secondary intermetallics as well as the oxidation, which is a major problem in dealing
with titanium alloys, was prevented according to the X-ray Diffraction (XRD) and scanning electron microscope
(SEM) analysis. Bone ingrowth was achieved in TiNi foams that have pore ratio in the range of 59-73 vol.%, and
no infection was observed for these osseointegrated grafts according to the histopathological evaluation. Although
no failure or bone resorption was observed for the grafted TiNi foams, the newly processed porous TiNi alloys were
subjected to compression tests in order to evaluate the mechanical compatibility for biomedical applications. It was
found that the mechanical properties could be adjusted by the alteration of the pore ratio and stress shielding
problem could be eliminated.
Keywords: TiNi, porous, graft, compression, biocompatibility, bone growth
1. INTRODUCTION
Titanium and its alloys have been extensively studied and applied in the field of biomedical applications [1-3].
Among Ti alloys, TiNi has outstanding properties such as shape memory and superelasticity in addition to its elastic
modulus that is similar to that of cortical bone [2, 4]. Processing the TiNi alloys in porous form further enhances the
applicability of this alloy since the control of the mechanical response become possible via the adjustment of the
pore characteristics. On the other hand, there has been a debate about the biocompatibility, especially in terms of
possible toxic effects of Ni [5-8]. However, there are several inquiries indicating that Ni release will not occur since
the implant will not be subjected to such a corrosive environment that is strong enough to reduce the passive TiO2
layer formed on TiNi [6-8].
14

In addition to the mechanical and chemical, surface properties are also of vital importance in graft applications. The
surface roughness required for the bone to have a good contact with the implant material, which can be artificially
introduced to graft materials, is naturally present when the graft was processed via powder metallurgical methods.
Among the several powder metallurgical techniques, sintering with space holder method has the advantage of the
close control of pore shape, size and orientation. Therefore, Ni-rich TiNi foams, which were aimed to be used as
graft materials, were processed by Mg space holder technique. The evaluation of the processed foams as graft
materials were accomplished by the histopathological examination of the porous TiNi alloys after 90 days of implantation to the femur of rats.
In this research, prealloyed Ni-rich TiNi powder (Ti-50.8at%Ni, 99.9% purity, supplied by Nanoval GmbH & Co. KG)
were used as the raw material to overcome the formation of the secondary intermetallics such as Ti3Ni4, Ti2Ni3,
which degrades the mechanical properties. Magnesium (99.82% purity, supplied by TangshanWeihao Magnesium
Powder Co. Ltd.) was selected as the space holder since it prevents the oxidation of TiNi due to its higher oxygen
affinity. Both powders, which were produced by gas atomization, were in spherical shape with average particle sizes
of ~20 m and 356 m, respectively. The porosity ratio was adjusted with the amount of magnesium added. The
powder mixture having predetermined ratios was blended with the addition of polyvinyl alcohol (PVA) solution (2.5
wt.% PVA + distilled water) that was used as binder. After compaction of the powder under 400 MPa pressure that
is applied via hydraulic press, sintering were done at the atmosphere controlled furnaces. High purity (99.995%)
Argon gas was used for the atmosphere control. The compacted powder mixtures with a diameter of 3 mm and
height of 2 mm, which were processed for in-vivo evaluation, were sintered at 1100 C for 1 hour. Another set of TiNi
foams having 10 mm diameter and aspect ratio of 1, were processed via sintering at 1200 C for 2 hours to evaluate
the mechanical response of TiNi foams following the improvement obtained in processing technique. The heating
rate was kept constant at 6.5 C/min for both of the processing techniques to assure sufficient sintering that would
prevent the collapse of the compact upon melting and evaporation of magnesium.
The porosity measurements were done according to the Archimedes principle by a precision balance equipped with
a density measurement kit. Scanning electron microscope (SEM) (JSM 6400, Jeol LTD, Tokyo, Japan) and X-ray
Diffraction (XRD) (Cu-Ka, Rigaku D/Max 2200/PC, Rigaku Corporation, Tokyo, Japan) analyses were employed to
examine the pore structure and the phases present in the sintered porous alloys.
Before the implantation of porous TiNi alloys, the residual MgO particles were eliminated with the nitric and hydrofluoric acid solutions treatment and NaOH solution was used for the neutralization procedure. In addition, TiNi
graft materials were cleaned in ultrasonic bath with deionized water followed by the ethanol application for removing
the possible oil residuals. Moreover, the grafts were autoclaved at 121oC for 30 minutes just before the implantation
to the Sprague Dawley kind rats.
TiNi foams with three different pore ratios in the range of 59 - 73 vol.% were selected as graft materials for the evaluation of bone growth. Accordingly, the rats were separated into 3 groups, each having 10 rats. The graft material
was placed in the bone defect, which was created on the femur of the rat, with 3 mm diameter and 2 mm depth. Only
one graft was implanted for each rat. The rats were continuously monitored for the infection or oedema formation as
well as the change in general behavior. However, no detrimental effects of the placed grafts were observed in any
of the rats during 90 days period of investigation. The grafts implanted were removed together with the femur for
histopathologic examination after the sacrification of the rats. The histopathologic samples were prepared with the
cutting-grinding method by the Sclerogenous Grinding Laboratory in the Dentistry Faculty of Hamburg University.
On the other hand, TiNi foams processed by sintering at 1200 C for 2 hours were subjected to monotonic compression tests to evaluate the mechanical response since the implant materials are generally subjected to compressive
loading. Compression tests were conducted with a constant crosshead speed of 0.1 mm/min by a 100 kN capacity
screw driven mechanical tester (Instron 3367, Instron Co. LTD., Norwood, USA).
Porous TiNi alloys processed with three different amounts of Mg addition, namely 50, 60, and 70 vol.%, for both the
evaluation of bone growth and mechanical characterization. However, the differences in the sintering regime have
resulted in different porosity ratios measured at the end of processing as given in Table 1.
15

Mg added
(vol.%)
Porosity
(vol.%)
50
60
70
50
60
70
59
66
73
49
58
64
Porosity
(vol.%)
1h at 1100C
2h at 1200C
Table 1.The change of porosity with sintering regime and the amount of Mg addition.
The amount of porosity measured for the samples sintered at 1100 C for 1 hour was found to be higher
than the amount of Mg added while the pore ratio is lower than the added Mg for the TiNi foams sintered
at 1200 C for 2 hours. The change in porosity with the sintering regime is believed to be due the change
in the amount of microporosity. As the sintering temperature and time had increased, the diffusion rate
of the atoms and so the extent of sintering was increased. Accordingly, the amount of microporosity that
remained
in between the powders after sintering was decreased. The change of the amount of microporosity with
sintering regime was also revealed by SEM examination (Figure 1).
(a)
(b)
Figure 1. SEM micrographs indicating the microporosity for porous TiNi alloys sintered at (a) 1100 C
for 1 hour and (b) 1200 C for 2 hours.
On the other hand, all of the processed TiNi foams were found to be in austenitic (B2) state at room temperature according to the XRD analysis results. As it was given in Figure 2, extra peaks with low intesity
were observed due to the presence of MgO residuals on the TiNi foams after processing. As mentioned
above, these residuals were removed by acid treatment before implantation.
Figure 2. Representative XRD analysis result for the processed TiNi foams.
16

Histopathologic examination showed that none of the grafts caused foreign body reaction or any inflammatory changes. Independent form the porosity, the bone growth was observed into all samples without
forming a zone. The direct contact between the bone and the TiNi graft was observed indicating the low
level of oxidation that was achieved via sintering with Mg space holder technique (Figure 3a). Moreover,
the extent of osseointegration, which was achieved in 90 days of evaluation, was the evidence of the
biocompatibility of TiNi foams processed (Figure 3b). Although not quantized, the extent of bone growth
was observed to be increased with increasing porosity due to the increase in the interconnection between the macropores.
10 m
Figure 3. The results of hystopathologic evaluation indicating: (a) the direct contact of the bone with
the graft, (b) the extent of bone growth thorugh TiNi graft material.
Although the mechanical properties of porous TiNi foams sintered at 1100 C for 1 hour were verified
to be sufficient for implant applications, the mechanical reponse of the TiNi foams processed with the
improved technique was also analyzed with uniaxial compression tests. The most important parameter
among the mechanical properties is the elastic modulus due to the stress-shielding problem that is
commonly encountered during use of implant materials. Stress-shielding is the resorption of the bone
when all applied load is carried by the implant, which has higher elastic modulus than that of the bone.
Therefore, the implant materials have to optimize high strength with low stiffness. As given in Table 2,
porous TiNi graft materials display a range of elastic moduli varying with porosity, enabling the use of
them as bone graft materials either for cancellous (< 3 GPa) or cortical bone (10-20 GPa) [4].
Porosity (vol.%)
49
58
64
E (GPa)
8.710.24
5.87 0.31
2.93 0.03
y (MPa)
147.93 12.10
91.50 8.50
44.12 7.65
max (MPa)
273.45 9.25
174.75 10.75
93.27 5.30
Table 2. The mechanical properties of TiNi foams sintered at 1200 C for 1 hour, where E is Youngs
modulus, y is yield strength and max is ultimate compressive strength (The given data is the
average of five tests for each level of porosity).
When it was considered that the mechanical properties enhance with the extent of sintering, which can
be achieved by raising the sintering temperature, even lower elastic moduli could have been achieved
for the grafted TiNi foams. Therefore, TiNi foams processed at 1200 C are believed to be more prefereable for implant applications due to the high strength achieved in combination with low elastic modulus.
CONCLUSIONS
In this research, porous TiNi alloys with homogeneously distributed, interconnected, spherical pores
were processed with Mg space holder technique. Two different sintering regimes were applied, one for
processing the graft materials and the other at a higher temperature for the mechanical characterisation.
The graft materials processed via sintering at 1100 C for 1 hour with three different porosity ratio in the
range of 59-73 vol.% were implanted to the femur of the Sprague Dawley kind rats. The histopathological examination revealed that bone growth had occurred into all of the implanted TiNi foams at a rate
17

proportional with the amount of porosity. Although none of the grafts sintered at 1100C was failed or
no bone resorption was observed during 90 days of implantation, TiNi foams that were sintered at 1200
C for 2 hours were mechanically characterized to investigate the possible improvement in mechanical
biocompatibility. It was observed that the elastic moduli varying in a broad range enable the use of the
high temperature processed TiNi foams for a wide range of applications having different requirements.
REFERENCES
1. Niinomi, M., Mechanical Properties of Biomedical Titanium Alloys, Materials Science and Engineering A, Vol. 243, pp. 231236, 1998.
2. Geetha, M., Singh, A.K., Asokamani, R., Gogia, A.K., Ti Based Biomaterials, The Ultimate Choice
For Orthopaedic Implants A Review, Progress in Materials Science, Vol. 54, pp. 397425,
2009. 3. Tarnta,D.,
Tarnta,
,
, D. N., Bzdoaca, N., Mndrla, I., Vaslescu, M., Properties and Medical
Applications of Shape Memory Alloys, Romanian Journal of Morphology and Embryology, Vol.
50, pp.1521, 2009.
4. Bansiddhi, A., Sargeant, T.D., Stupp, S.I., Dunand, D.C., Porous NiTi for Bone Implants: A Review,
Acta Biomaterialia, Vol. 4, pp. 773782, 2008.
5. Eliades, T., Athanasiou, A.E., In Vivo Aging of Orthodontic Alloys: Implications for Corrosion Potential, Nickel Release, and Biocompatibility, Angle Orthodontist, Vol. 72, pp. 222-237, 2002.
6. Wever, D.J., Veldhuizen, A.G., Sanders, M.M., Schakenraad, J.M., Horn, J.R., Cytotoxic, allergic
and genotoxic activity of a nickel-titanium alloy, Biomaterials, Vol. 18, pp. 1115-1120, 1997.
7. Assad,M., Chernyshov, A.V., Jarzem, P., Leroux, M.A., Coillard, C., Charette, S., Rivard, C.H., Porous Titanium-Nickel for Intervertebral Fusion in a Sheep Model: Part 2. Surface Analysis and
Nickel Release Assessment, Journal of Biomedical Materials Research Part B: Applied Biomaterials, Vol. 64B, pp. 121129, 2003.
8. Shabalovskaya, S.A., Surface, Corrosion and Biocompatibility Aspects of Nitinol as an Implant
Material, Bio-Medical Materials and Engineering, Vol. 12, pp. 69109, 2002.
18

TOZ METALURJS YNTEMYLE RETLEN KPREBLR

PREFORM MALZEMELERN TIG KAYNAI LE BRLETRLMES VE
KPREBLRLNN ARATIRILMASI
Arif UZUN*, Hanifi NC**, Halil KARAKO** ve Mehmet TRKER**
Kastamonu niversitesi, Cide Rfat Ilgaz MYO, Kaynak Teknolojisi Blm, Kastamonu,
auzun@kastamonu.edu.tr
**
Gazi niversitesi Teknik Eitim Fakltesi, Metal Eitimi Blm, Teknikokullar, 06500, Ankara, hcinici@gazi.edu.
tr, mturker@gazi.edu.tr
*
zet
Toz metalurjisi yntemi ile karmak ekilli ve yksek mekanik zelliklerde sahip metalik kpk retmek mmkndr. Ancak bu yntem ile ticari boyutlarda kullanlabilecek byk boyutlu metalik kpkleri retmek gtr. nk
retim srecinde kullanlan cihaz ve donanmlar nihai rn ktsnn boyutlarn snrlandrmaktadr. Bundan dolay
kprtme ncesi alminyum preform malzemeler TIG kayna ile farkl akmlarda (130 - 230 A) birletirilmi ve 710
o
C scaklkta kprtme ilemine tabi tutulmutur. Elde edilen kpk numunelerde kaynak blgesi kaynak yaplmam ile gzenek morfolojisi ve lineer genleme asndan karlatrlmtr.
Anahtar Kelimeler: Toz Metalurjisi, TIG Kayna, Alminyum Kpk.
jonng of foamable precursor materals, produced by

powder metallurgy, BY TIG WELDING AND nvestgaton of
ther foamablty
ABSTRACT
It is possible to produce metallic foam, by powder metallurgy, with high mechanical properties and complex-shaped.
However, it is difficult to produce metallic foams with a large commercial scale with this method. Because the device
and equipment used in the production process limited to the size of the final product. Therefore, foamable aluminum
precursor materials was joined by TIG welding with different currents (130 - 230 A) and then foamed at 710oC. The
weld zone was compared in terms of pore morphology and linear expansion with the un-welded foamed samples.
Keywords: Powder Metallurgy, TIG Welding, Aluminum Foam.
1. GR
Teknolojinin geliimine paralel olarak hafif ve dayanm yksek malzemelere ihtiya gn getike artmaktadr. Aratrmaclar, yapsal ve fonksiyonel uygulamalarda bu zellikleri bir arada bulunduran malzemeleri elde etmek iin
eitli araylar ierisine girmitir. Metalik kpkler bu olgu ierisinde nemli bir yere sahiptir. Bu malzemelerin
retiminde dkm ve toz metalurjisi (TM) endstriyel boyutta en fazla kullanlan yntemleridir.
Toz metalurjisi (TM) yntemi ile metalik kpk retimi ilk olarak Fraunhofer Malzeme Aratrma Enstits (IFAM)
tarafndan gelitirilmitir [1]. Bu yntem de sandvi levha eklinde veya karmak ekilli homojen gzenek yaplara
19

sahip kpk paralar kprebilir preform malzemelere uygulanan sl ilem ile retilmektedir [2]. Son zamanlarda
TM ynteminin gelitirilmesine ve maliyetinin azaltlmasna ynelik aratrmalar yaplmaktadr. rnek olarak ok
pahal olan atomize alminyum tozlar yerine, daha ucuz olan alminyum talalarnn kullanlmas, kprebilir preform malzemelerin stlmas ileminde geleneksel n stmal elektrikli frnlarn yerine ok gl gne enerjisi
kaynaklarnn kullanlmas verilebilir [3,4]. Benzer amala toz metalurjisi yntemi ile retilmi kprebilir preform
malzemelerin birletirilmesine ynelik almalarda yaplmtr [5-7]. Bu almada da kprebilir preform malzemeler TIG kayna ile birletirilmi ve kprtme ilemine tabi tutulmutur.
2.MALZEME RETM VE DENEYSEL YNTEM
2.1. Kprebilir Alminyum Preform Malzemelerin retimi
Bu almada Al tozuna % 0,8 orannda TiH2 ve % 7 orannda Si tozlar eklenerek, boyutlu turbula da kartrlmtr. Karm tozlar kalp ierisinde 600 MPa basn altnda tek ynl sktrlarak ham younlukta silindirik blok
numuneler retilmitir. Daha sonra blok numuneler 500 oC scaklkta ekstrzyon ve haddeleme ilemlerine tabi
tutularak kprtme ncesi preform numuneler haline getirilmitir.
2.2. TIG Kayna ve Kprtme lemi
Kaynak ilemi iin hazrlanan 5 mm kalnlndaki preform malzemeler yzeydeki oksit tabakasnn uzaklatrlmas
amacyla tel fra ile mekanik olarak temizlenmi ve saf alkole batrlmtr. Hazrlanan paralar kt aln pozisyonda,
ift tarafl tek pasoda ilave metal kullanlmadan birletirilmi ve atmosfer ortamnda soumaya braklmtr. Birletirme ilemi invertr tipi kaynak makinesi ile argon koruyucu atmosfer gaz altnda yaplmtr. Deney esnasnda
kullanlan kaynak parametreleri izelge 1de verilmitir. Bu parametreler eliinde birletirilen numunelere ait makro
yap fotoraflar ekil 1de verilmitir.
izelge 1. Birletirme ileminde kullanlan parametreler
Kaynak Parametreleri
Kullanlan akm
Alternatif
Gaz ak debisi
12 lt/dk
Elektrod ap, Tipi
2,4 mm, Tungusten
Kaynak akm (A)
130-170-190-230 Amper
Dolgu teli
Kullanlmad
Birletirme sonras, preform numuneler 710 oC scaklkta kprtme ilemine tabi tutulmutur. Kprtme ilemi
dorusal genlemeyi belirlemek iin st yzeyi ak bir kalp ierisinde yaplmtr. Daha sonra maksimum lineer
genleme oranlar belirlendikten sonra btn yzeyleri kapal 25x25x16 mm boyutlarnda kprtme kalplar kullanlmtr.
ekil 1. Farkl akmlarda birletirilmi preform malzemeler
20

3. DENEYSEL SONULAR VE TARTIMA

Eitlik 1de TIG kayna ile birletirilmi numunelerin, birletirilmemi preform (referans) malzemelere kyasla gzeneklilik oranlarn hesaplamada kullanlan forml verilmitir. Burada kaynak ile birletirilmi malzemenin younluunu, s ise referans numunenin younluunu ifade etmektedir. Buna gre kaynak sonras TiH2 ieren numunelerin
kaynak blgelerinde artan akm iddeti ile gzeneklilik orannn artt belirlenmitir. Bu oran 230 A akm iddetinde
birletirilen numunelerde maksimum %10 oranndadr. Kaynak ilemi srasnda, yksek miktarda s girdisinden dolay kaynak blgesinde ksmi kprmeler meydana gelmitir. Bunun neticesinde numunelerin kaynak blgelerinde
ve diki yzeylerinde gzenekler olumutur (ekil 1). Yap ierisindeki TiH2n 400-450oC gibi dk scaklklarda
znerek gaz aa karmas kprme ncesi gzenek oluumunun nedeni olarak grlmektedir [8]. Bu durum
kaynakl blgenin ana malzemeye nazaran daha farkl kprme davran sergilemesine neden olmutur.
Gzeneklilik oran = (1/s) 100% (1)
ekil 2de kalp ierisinde ve serbest olarak tek bir ynde kprtlen preform malzemelerin kpk yap resimleri
gsterilmektedir. Serbest kprtme neticesinde kaynakl blgelerin ana malzemeye nazaran ok daha az kprd aka grlmektedir. Bu problemin nedeni kaynak ilemi esnasnda TiH2 kana engel olunamamasdr.
Kprtc maddenin dk scaklklarda znerek gaz aa karmas ve bu gazn yap ierisinde muhafaza edilememesi serbest kprtme neticesinde kaynakl blge ile ana malzemenin dorusal genleme oranlarnda nemli
lde farklla neden olmutur (ekil 3). rnein 130 A akm iddetinde yaplan birletirmelerde kaynak blgesi
% 289 orannda genleme gsterirken, ana malzeme % 338 orannda genleme sergilemitir. Dolaysyla kaynak
blgesi ile ana malzeme arasndaki dorusal genleme fark % 49dur. Bu oran 170 Ade % 86, 190 Ade % 102 ve
230 Ade % 133tr. Ayn zamanda ekil 2de kaynakla birletirilmi, birletirilmeden aln alna getirilmi ve yekpare
preform malzemelerin kalpta kprtlmeleri neticesinde aldklar son ekil gsterilmektedir. Dikkat edildiinde yekpare numune hari dier numunelerin st ve yan yzeylerinde birletirme blgelerinin izleri grlmektedir. Ancak bu
izlerin ara kesit boyunca srekli olmad, yalnzca yzeysel bir iz niteliinde olduu ekil 4te verilen arakesit fotoraflarndan anlalmaktadr. Kprme ilemi esnasnda numunelerin yzeylerinde oluan oksitlenmenin bu izlerin
olumasna etki ettii dnlmektedir. Yzeyde oluan oksit katman kpn maruz kalaca scakl etkiledii
gibi, geometrik eklini de deitirebilmektedir [9].
ekil 2. Kalp ierisinde ve serbest olarak kprtlen preform malzemelerin kpk yaplar
21

ekil 3. Serbest olarak kprtlen numunelerin genleme oranlar

ekil 4teki ara kesit resimlerine bakldnda serbest halde kprtme ilemi neticesinde kaynak ile birletirilmi
numunelerin ara yzeylerinde ksmi birlemelerin olduu grlmektedir. Kalpta kprtme ileminde ise ara yzeydeki birlemelerin, yeterli lde olduu grlmektedir. Bunun nedeni kprtme ilemi esnasnda kalp ierisinde
bulunan numuneler, nce serbest halde kprme davran sergilemekte ve sonrasnda st yzey kalp duvarlar
genleme dorultusunu yanlara doru deitirmektedir. Dolaysyla serbest kprtme neticesinde birlemeyen d
yzeyler, genleme dorultusu boyunca hareket ederek kalp boluunu doldurmaktadr. Ancak bu ilemler gerekletirilirken kalp ykseklii optimum deerde tutulmaldr. nk gereinden fazla ykseklie sahip olan kalplarda
yaplan kprtme ilemlerinde dzgn geometrik ekilli kpk yaplar elde edilememektedir. Kalpta kprtlen numunelerin ara kesit yzeylerine bakldnda, birleme blgeleri ile ana malzemenin gzenek morfolojisinde nemli
lde farkllk grlmemektedir. Ayrca bu durum, herhangi bir kaynak ilemine tabi tutulmadan aln alna getirilerek kprtlen alminyum kpklerde de gzlemlenmitir.
ekil 4. Kprtme ilemine tabi tutulmu numunelerin gzenek yaplar

4. SONULAR ve NERLER
Yaplan deneysel almalar sonucu kprebilir alminyum malzemeler TIG kayna ile baarl bir ekilde birletirilmitir. Ancak kprtme ncesi kaynak blgesinde oluan gzenekler serbest kprtmede kprebilirlie olumsuz
ynde etki ederken, kalp ierisinde kprtmede ise herhangi bir etki oluturmamtr. Ayrca kaynak ile birletiril-
22

meden aln alna getirilerek kalpta kprtme ilemine tabi tutulan numuneler ile kaynakl numunelerin gzenek
morfolojisinde nemli lde farkllk grlmemektedir.
Toz metalurjisi yntemiyle retilecek byk boyutlu alminyum kpkler iin preform malzemelerin aln alna iyi
sabitlenmesi gerekmektedir. Aksi halde kprtme ilemi olumsuz sonulanabilir. Bunun iin kaynakl birletirme alternatif bir yntem olarak dnlebilir. Ayrca tasarm aamasnda preform malzemelerin kprtme ncesi ekillendirilebilirlikleri nemlidir. Bunun iin kaynakla birletirilmi preform malzemelerin mekanik zellikleri belirlenebilir.
KAYNAKLAR
1. Baumaster, J., US patent, 1992
2. Yu, C.J.,Eifert, H.H., Banhart, J., Baumeister, J., Metal foamingby a powdermetallurgymethod: Production,
propertiesandapplications, Mat Res Innova, 2:181188, 1998
3. Hohlfeld, J., Hannemann, C., Vogel, R., Hipke, T., Neugebauer, R., Alternative starting materials for the production of aluminum foam by the powder metallurgical process, Prod. Eng. Res. Devel. 5:2530, 2011
4. Cambronero, L.E.G., Canadas, I., Martnez, D., Ruiz-Roman, J.M., Foaming of aluminiumsilicon alloy using
concentrated solar energy, Solar Energy 84:879887, 2010
5. Kramer, I., Simancik, F., Florek, R., Nosko, M., Mllerov, K., Tobolka, P., Mishina, O., FrictionStirWelding of
Foamable Materials and Foam Core Sandwiches, 11. Conference on Materials, Processes, Friction and
Wear, Vela Luka, 347-352, 2006
6. Drfler, S., Otto, A., Merklein, M., Geiger, M., Processing of Aluminium Foam Sandwich Tailored Blanks,
International Conference Advanced Metallc Materals, Smolenice, Slovakia,59-64, 2003
7. Horn H., FrictionStirWelding of AluminiumFoamMaterials In: Proceedings of the International Conference on Joining Technology of Dissimilar Materials and Structural Integrity Problems of so Jointed
Structures. Ljubljana, 107-112, 2001
8. Lehmhus, D., Approaches to tailoring titanium hydride decomposition kinetics by annealing in various atmospheres, Adv. Eng. Mat, 2004
9. Solrzano, E., Garcia-Moreno, F., Babcsn, N., Banhart, J., Thermographic Monitoring of Aluminium Foaming Process, Nondestruct Eval, 28:141148, 2009
23

WC-Co KESC U HURDALARINDAN PROMETALURJK

YNTEMLE WC ve Co TOZLARININ GER KAZANIMI
Engin AHN, Kenan YILDIZ, Fatih STEL
Sakarya niversitesi, Mhendislik Fakltesi, Metalurji ve Malzeme Mhendislii, 54187 Sakarya,
enginsahin48@gmail.com, kenyil@sakarya.edu.tr, ustel@sakarya.edu.tr
ZET
Gnmzde WC ve kobalt malzemesinin geri kazanmna ynelik yaklamlar sadece ekonomik faktrler ynnden
deil evresel ve ekolojik faktrler nedeniyle de nem kazanmtr. Dnyada kesici ularn imalatnda kullanlan
volfram karbrn (WC) te biri hurdalardan salanmaktadr. Son yllarda WC ve Co geri kazanmna ynelik gelitirilen bir teknikle, sert metal ularn hurdalar bir erimi metal (Zn) banyosunda zndrlerek geri kazanlmaya
allmaktadr. Bu iki metalin ok farkl zellikleri olmasna karn, Zn-Co ikili denge diyagramna gre birbirleri
iinde snrl znrlkleri vardr. Bu durum, sert metal ularnn asit ve uurma proseslerine alternatif bir ekilde
daha ekonomik ve evreye duyarl olarak geri kazanmn mmkn klmaktadr. Bu almada WC-Co kesici u
hurdas farkl scaklk ve srelerde erimi inko banyosunda tutulmu, inko buharlatrldktan sonra WC ve Co
tozlar geri kazanlmtr.
Anahtar Kelimeler: WC-Co hurdas, Geri kazanm, Pirometalurji
RECOVERY OF WC AND Co POWDERS FROM WC-Co CUTTING

SCRAPS BY PYROMETALLURGICAL METHOD
ABSTRACT
Nowadays, the approaches for recovering of WC and Co materials are not only becoming economically important
but also, due to the environmental factors, it is ecologically significant. In the world, the one third of the consumption
of WC in cutting tools is being produced from their scrap. In recent years, a new technique for recovering of WC and
Co using molten zinc (Zn) bath has been developed from hard cutting tool scraps. Although very different properties
of these two metals, there is a limited solubility one over another according to Zn and Co binary phase diagram.
With this, hard cutting tool materials will be enabled to be recovered alternatively in contrast to acid leaching and
evaporation methods. In this study, WC-Co cutting scrap was treated with molten zinc at different temperatures and
durations, WC and Co powders were recovered after the evaporation of zinc.
Keywords: WC-Co scrap, Recovery, Pyrometallurgy
1. GR
Kesici ular, ncelikle talal imalat operasyonlarnda youn olarak kullanlmaktadr. Ayrca ucun karbrn oluturan volfram metali madencilik, elik sanayi, refrakter malzeme, uak uzay sanayi gibi kullanm alanlarna sahip
olmakla birlikte volframn byk ounluu kesici takm ucu retiminde (WC olarak) kullanlmaktadr. Kesici u
24

retiminde kullanlan semente karbrlerin kullanm sonras nispeten kolay toplanabiliyor olmalar ve hurda olarak
yksek ekonomik deere sahip olmalar nedeniyle geri kazanmlar gerek ekonomik gerekse evresel nedenlerle
nemlidir. Volframn pahal bir metal olduu dnldnde, geri dnm hayati bir nem arz etmektedir. Bu
nedenle kesici ularn geri kazanmna ynelik bilimsel aratrmalar ve endstriyel lekteki almalar uzun yllardan beri devam etmektedir.
Volfram karbr kesici ularn geri kazanmna ynelik almalar 3 ana grupta toplanmaktadr. Bunlar; (i) kesici ularn hidrometalurjik asit lii prosesleri (asetik, slfrik, nitrik ve hidroklorik asit), (ii) hidrotermal oksidasyon prosesi
ve (iii) yksek scaklk oksidasyonu-redksiyon prosesi ile geri kazanmlar eklindedir. Ayrca daha snrl olarak
elektrokimyasal zndrme ve hurda ularn toz haline getirildii mekanik tme proseslerine de bavurulduu
grlmektedir. 1970li yllarda ortaya kan inko kazanm prosesi de geri dnm uygulamalarnda kullanlan
farkl bir yntemdir [1,2].
Genel olarak kimyasal proseslerin btn hurda trlerini ileyebilme ve empriteleri uzaklatrabilme gibi avantajlar
vardr. Fakat bu yntemler yksek maliyet, yksek zc ve enerji tketimi gereksinimi, daha dk verimlilik ve
direkt metotlara gre daha fazla atk kmas gibi dezavantajlara sahiptir. Kimyasal geri dnm ile direkt geri
dnm prosesleri arasndaki denge, volfram endstrisini geri dntrlen malzemelerdeki emprite seviyesini
ve geri dnm maliyetlerini azaltmaya yneltmitir. Bu nedenle volfram bazl hurdalar ilemek iin birok metot
ortaya kmtr [3].
Asidik li ilemleriyle geri dnm prosesleri, sert metal u ierisindeki balaycnn zeltiye alnmas ve metal
karbr partikllerinin serbest hale gemesi dncesine gre yaplmaktadr. Balayc kobalt metalin zndrlmesine ynelik olarak birok asit bileenleri denenmitir. Her ne kadar kobalt birok asit iinde znse de, emisyon
problemleri oluturmadan endstriyel bir proses ina etmek zordur. Slfrik, nitrik veya hidroklorik asit kullanan operasyonlarn evreye olumsuz etkileri bulunmaktadr ve kullanlan dk pH, asidin selektif li zelliine etki etmekte,
oluan tungstik asit, li edilen blgelerdeki gzeneklere kerek li ilemini snrlayc etkiler meydana getirmektedir
[4]. Bu durumu nlemek iin hurda birka yz mikron boyutuna paralanmakta, ancak bu boyut kltme ilemi
maliyeti artrmakta ve demir kirlenmesi meydana geldiinden tercih edilmemektedir. Orijinal boyut ve ekildeki sert
metal hurdalarn ekolojik adan li etmek iin asetik asit kullanlmaktadr. Bu yntemin avantajnn hurda boyut
kltme ilemine gerek duyulmamas olduu ifade edilmektedir.
Asetik asit, balayc kobalt selektif olarak zeltiye almaktadr [5]. Semente volfram karbr hurdalarnn deerlendirilmesinde kullanlan bir dier asidik li ilemi nitrik asitle yaplmtr. Hurda vibrasyonel bir deirmende tlm, akabinde nitrik asitle li edilmi ve balayc olan kobaltn znme verimleri incelenmitir [6]. Nitrik asidin
yan sra hidroflorik (HF) asidin de kullanld bir baka almada WC-Co hurdalarnda hidrotermal oksidasyon
ilemiyle WO3 tozlar elde edilmi, kobalt ise zeltiye gemitir. Sonu olarak WC-Co hurdalarndan W ve Co
kazanmada bu yntemin tercih edilebilir yntemlerden biri olduu belirtilmitir [7]. Bir baka hidrometalurjik deerlendirme ynteminde ise WC-Co hurdalar HCl zeltisinde 110Cnin zerinde hidrotermal ileme tabi tutulmu
ve Co balayc faz zndrlmeye allmtr. Kobaltn zndrlerek uzaklatrlmasndan sonra elde edilen
WC tozlarnn olduka gevrek olduu ve kolaylkla pulverize edilebilecei de ifade edilmitir [8]. Asit liine benzer
bir yntem olarak, kesici u hurdalarndan volfram karbrn ve kobaltn elektrolitik olarak kazanlmas hedeflenmi
ve elektrolit olarak kullanlacak farkl asitlerin (HCl, H3PO4) kobalt zmlendirilmesine etkileri tespit edilmitir. Asit
liinin uzun sreli olmas ve yksek enerji sarfiyat (1000 Amper) nedeniyle bu yntem kullanmnn ekonomik olmad ifade edilmitir [9].
Oksitleyici ekstraksiyon prosesinde geri dntrme ileminin ilk kademesi hurda, NaNO3 ve NaNO2 gibi oksitleyici bileenlerle kavrulmakta, elde edilen malzeme suyla muamele edilerek sodyum tungstat zndrlmekte,
filtrasyon ve ktrme ilemleriyle empriteler uzaklatrlmaktadr. Sodyum iyonlarn ayrmak iin kerosen ve alkil
benzen gibi organik zcde amin gibi znen bir maddeyle sodyum tungstat zeltisinde volfram paracklar
ekstrakte edilmektedir. Amonyum polytungstat zeltisi elde etmek iin sulu amonyak zeltisi ile yeniden ekstrakte
edilip, buharlatrma yntemiyle zeltiden amonyum paratungstat kristalize edilmektedir. Elde edilen amonyum
paratungstat kalsine edilip akabinde hidrojenle redklenerek volfram metali elde edilmektedir [2].
Oksidasyon-Redksiyon prosesi de WC-Co sert metallerinin geri dnmnde kullanlan yntemlerden biridir. Bu
yntemde WC-Co sert metali dner frnda CoWO4 ve WO3 oksit formlarna dnmekte, daha sonra bu oksit tozlar
azot gaz ortamnda kat karbonla W ve Coa karbotermal olarak redklenmektedir [10].
25

1970lerin sonunda ticarileen inko geri dntrme prosesinde, temizlenmi hurda asal bir gaz atmosferi altnda 650-800C scaklk aralndaki bir elektrikli frnda bulunan ergimi inko iine daldrlr. inko, balayc olan
kobaltla reaksiyona girer ve karbr paracklar orijinal hacminin iki katndan daha fazla bir hacime ier. Optimum
koullar Co ieriine ve inko/kobalt oranna baldr. inko vakum altnda 700-950C de destile edilir ve geri kazanlr. Karbr paracklar ince toz haline getirilmek zere pulverize edilir ve elenir. Partikllerin iinde halihazrda
kobalt bulunur ve tane boyutu olarak orijinal sinterlenmi hurdadan bir farkllk gstermez [2,3]. inko banyosunda
WC-Co sert metal bileiinin geri kazanm veriminin dier proseslere gre %95 daha verimli olduu ifade edilmektedir [11].
Geri dnm erevesinde semente karbrlerin tlerek yeniden retim srecine katlmas ekonomik zorunluluun bir gereidir. ABDde semente karbr hurdalarnn %35inin kimyasal proseslerin kullanmyla, %25inin
inko banyosu prosesi ile geri kazanld ve %5 orannda hurdann ise deerlendirilmedii rapor edilmitir. inko
prosesinin semente karbrlerin dnmnde kullanm son yllarda artmaktadr[12,13].
Bu alma 110M201 nolu TBTAK projesinin balang almalarn iermekte olup WC-Co kesici u hurdalar
erimi inko banyosu iinde farkl scaklk ve srelerde tutularak WC ve Co partikllerinin geri kazanlmas amalanm ve elde edilen veriler sunulmutur.
2. DENEYSEL ALIMALAR
2.1. WC-Co Hurdasnn Karakterizasyonu
Deneysel almalarda kullanlan WC-Co kesici u hurdasnn X-n difraksiyon analizi Rigaku Ultima X-In Difraktometresi ile Cu K-alfa kullanlarak yaplmtr. JEOL 6060 LV marka tarama elektron mikroskobu ile hurda
malzemenin ve proses sonras elde edilen rnlerin SEM/EDS analizleri yaplmtr.
2.2. Pirometalurjik Geri Dnm Prosesi
WC-Co kesici u hurdalarn erimi inko banyosunda zndrlmesi ve WC ile Co tozlarnn geri kazanmnn
yapld ve deneysel almalarda kullanlan frn inko oksit retim tesislerinde kullanlan frnn bir kopyasdr.
Frn, ayarlanabilir s rejimi ile maksimum 1100C ye kadar kabilmektedir. Frn ierisine, arzu edildii taktirde azot
veya argon gaz, istenilen debi deerlerinde beslenebilmektedir. Yaplan deneysel almalar srecinde, inkonun
eritilmesi ve buharlatrlmas srecinde ortama srekli olarak koruyucu gaz olarak argon gaz beslenmitir. Bu
ekilde inkonun eritilmesinde, erime scakl yksek olan ZnO oluumu nlenmi olup banyo ortamnda metalik
karakterde inko bulunmas salanmtr. Erimi inkonun iinde kobalt znmesinin salanmasnn akabinde
inkonun buharlatrlmas amacyla frn 1000C ye karlm, bu esnada kullanlan koruyucu gaz, ortamdaki inko
buharnn uzaklamasn da salamtr. ekil 1de kullanlan frn(a) ve frn iindeki grafit potann (b) grnts
verilmitir. ekil 2de ise erimi inko banyosunda WC ve Co tozlarnn geri kazanm ematik olarak gsterilmitir.
Frn alma scaklklar 700, 750 ve 800C olarak seilmi, bu scaklklarda bekletme sreleri ise 1, 2 ve 3 saat
olarak kabul edilmitir.
(a)
(b)
ekil 1. Deneysel almalarda kullanlan frn (b) ve frn iindeki grafit pota (b)
26

ekil 2. ematik erimi inko

banyosunda geri kazanm prosesi
Deneysel almalarda yaklak 28 g hurdaya karlk 300 g inko kullanlmtr. Erimi inko banyosunda hurdalar
bekletilmi, hurdalardaki kobaltn znmesi salanmtr. inko buharlatrma kademesinde ise ortamda metalik
olarak bulunan inko, frnn 1000C ye karlmasyla buharlatrlm, frn dnda bulunan toplama blgesinde
kat inko oksit tozlar olarak elde edilmitir.
3. DENEYSEL SONULAR
3.1. Hurdann Karakterizasyonu
ekil 3de kesici u hurdasnn X-n difraksiyon analizi, ekil 4de ise hurdann SEM analizleri ile EDS analizleri
verilmitir. X-n difraksiyon analizinden grld gibi numunede ana madde volfram karbr (WC) olup kobalt
(Co) ve az miktarda vanadyum oksitte (VO) bulunmaktadr.
ekil 3. WC-Co kesici u hurdasnn X-n analizi

ekil 4de verilen SEM resimlerinde WC partiklleri belirgin ekilde grlmektedir (1 nolu blge). Partikller arasnda ise (2 nolu blge) kobalta zengin blgeler bulunmaktadr. ki farkl blgeden alnan EDS analizleri, kobalt
orannn partikller arasnda daha fazla olduunu gstermektedir.
(1 nolu blge)
ekil 4. WC-Co kesici u hurdasnn
SEM grnts ve iki farkl blgedeki
EDS analizi
(2 nolu blge)
27

3.2. Pirometalurjik Yolla WC ve Co Geri Kazanm

WC-Co kesici u hurdalar 700, 750 ve 800C de bulunan erimi inko banyosunda 1, 2 ve 3 saat bekletilmi,
akabinde frn scakl 1000C ye karlarak inkonun ortamdan uzaklatrlmas salanmtr. Bu ilemler argon
atmosferi altnda gerekletirilmitir. Elde edilen rnler tme ilemine tabi tutularak WC ve Co tozlar elde edilmitir.
700C scaklkta yaplan almalarda elde edilen rnlerin ince partikller haline getirilmesi iin yaplan tme
ilemleri sonras homojen boyut dalml tozlar elde edilememitir. Bu scakln tam olarak yeterli gelmedii tespit
edilmitir. Tm alma scaklklarnda 1 saatlik ilemler, uygun WC ve Co tozlarnn geri kazanmnda yeterli gelmedii de gzlenmitir. 750 ve 800C de inko banyosunda 3 saat sre beklenmesi sonrasnda elde edilen partikller
ekil 3(a ve b)de grlmektedir. inkonun ortamdan uzaklatrlmasnda sonra elde edilen partikller sngerimsi
yapda olup tme sonras kolaylkla toz haline gelmektedir. Scaklk arttka daha kolay tme ve levhasal ekilde daha kk boyutta tozlar elde edilmitir.
ekil 5. inko banyosunda (a) 750C de ve (b) 800C de

3 saat ilem sonras elde edilen tozlar
ekil 5de grlen levhasal bir partikln 10000 bytme ile elde edilen SEM grnts ve burann alan analizi
ekil 6da verilmitir. ekil 4den de grlecei zere, balayc olan kobaltn ayrlmas sonucu partikl yzeyinin
sngerimsi bir grnmde olduu anlalmaktadr. 1 mden kk WC paracklarnn bulunduu bu tozlar, erimi
inkoda geri dnm prosesi sayesinde elde edilmitir ve yaplan EDS analizlerinde kalnt inkoya rastlanmamtr. Geri kazanlan bu tozlar, daha ileriki aamalarda birok ama iin tekrar kullanlabilecek durumdadr. Mevcut
alma devam etmekte olup elde edilen tozlarn daha detayl karakterizasyonu ve kaplama sektr gibi uygulamalarda kullanm da test edilecektir.
ekil 6. inko banyosunda 800C de 3 saat ilem sonras elde edilen

WC partikl yzeyinin SEM ve EDS genel analizi
4. SONULAR
WC-Co kesici u hurdalar erimi inko banyosunda farkl scaklk (700,750 ve 800C) ve farkl srelerde (1, 2 ve 3
saat) bekletilerek kobaltn znmesi salanm, ortamdaki inko uzaklatrldktan sonra WC ve Co tozlar geri kazanlmtr. Yaplan deneyler sonucunda 1 saat gibi ksa sreli ilemlerde yeterli kobalt znmesi salanamam,
sre 3 saate ktka daha kk boyutta ve levhasal WC partiklleri elde edilmitir.
Teekkr: 110M201 nolu proje kapsamnda yaplan bu almaya verdikleri maddi destekten dolay TBTAK kurumuna teekkr ederiz.
28

KAYNAKLAR
1. Gotou, H., History of Igetalloy, SEI Technical Review, No.68, p.1-10, April 2009.
2. Sudarshan, T.S., Nano-sized WC-Co holds promise for the future, MPR, p.26-33, March 1998.
3. Shed, K.B., Tungsten recycling in the United States in 2000, USGS, Open-File Report 2005-1028, 2005.
4. Schiesser, R., Werstoff-Recycling wolframhaltiger sekundarrohstoffe, PhD Thesis, TU-Vienna, 2003.
5. Edtmaier, C., Schiesser, R., Meissl, C., Schubert, W.D., Bockb, A., Schoen, A., Zeiler, B., Selective removal of
the cobalt binder in WC/Co based hardmetal scraps by acetic acid leaching, Hydrometallurgy, 76, p.6371,
2005.
6. Grmen, S., Recovery of nano-sized cobalt powder from cemented carbide scrap, Turkish J. Eng. Env. Sci.,
29, p.343-350, 2005.
7. Sasai, R., Inagak, F., Itoh, H., Resource recovery from cemented carbide by subcritical hydrothermal treament,
Journal of the Soc. of. Materials Science, Japan, Vol 55. No.3, pp. 254-257, 2006.
8. Kojima, T., Shimizu, T., Sasai, R., Itoh, H., Recycling process of WC-Co cermets by hydrothermal treatment,
Journal of Material Science, 40, p.5167-5172, 2005.
9. Karayazgan, N., WC-Co esasl kesici ularn elektrolitik geri kazanm, Yksek Lisans Tezi, T Fen Bil. Ens.,
2005.
10. Joost, R., Pirso, J., Viljus, M., Recycling of hardmetal scrap to WC-Co powder by oxidation-reduction process, 6th International DAAAM Baltic Conference, 24-26, Tallinn-Estonia, April 2008.
11. http://www.hmtg.de/
12. Stjernberg, K., Johnson, J.JR., Recycling of cemented carbides, in 1998 Int. Con. on Powder Metallurgy
& Particulate Materials, Las Vegas, Nev., May 31-June 4, 1998, Proceedings: Princeton, N.J., Metal Powder
Industries Federation and APMI International, 1, 1998, p. 173-179.
13. Payne, M., U.S. Tungsten market update: International Tungsten Symposium-Outlook for Tungsten Production and Applications in the 21st Century, 9th, Pittsburgh, Pa., , Presentation, 19 p., September 30-October
4, 2002.
29

SNTEST Toz metal paralarda atlak ve gzeneklilik

tespiti iin gelitirilmi tahribatsz enstrman
A.ATAS1, A. Bulkai2, P. Tomek2, G. Tth2
1TOZMETAL Tic. Ve SAN. A.S. stanbul Cad.No:61 Grpnar, Bykekmece, stanbul, TRKYE
www.tozmetal.com
2MFKK Invention and Research Centre Services Co. Ltd, 1119, Ttnyi t 93,
Budapest, HUNGARY www.mfkk.hu
ZET
Geleneksel otomobil pazar ierisinde Toz Metal paralara olan talebin artaca ngrlmektedir, fakat sektrn
gelecekteki gelimesi direkt olarak uzay ve ila endstrilerine sfr hatal para retebilme kabiliyetine baldr.
Kalite gvence penceresinden bakldnda, yeterli kontrol sisteminin olmamas kontrol maliyetlerini, test iin harcanan zamanlar ve sarf edilen malzeme miktarn arttracandan olduka nemlidir. Son yllarda Eddy Current,
bilgisayarl tomografi, X-Ray grntleme gibi birok tekniin Toz Metal paralarn kontrol iin uygulanabilirlii
aratrlmtr. Fakat yaplan almalar gstermitir ki bu yntemlerin hepsin eksik olduu noktalar vardr ve bu
durum onlar tam ve gvenilir bir atlak tespiti ya da younluk problemi tespiti iin geersiz klmaktadr. Avrupa
Birlii Komisyonu fonlar kullanlarak, pulse echo ultrasonik teknolojinin robot teknolojisiyle birletirilmesiyle sinter
paralarn global bir younluk haritasnn karlabildii yeni bir kontrol ekipman gelitirilmitir.
Anahtar Kelimeler tahribatsz muayene, kalite kontrol, sinterlenmi paralar, kusur tespiti, younluk haritas,
ultrasonik gzeneklilik tespiti, ultrason sinyal ileme
SINTEST - Non-InvasIve Instrument for determInIng the

porosIty of powder metallurgy parts
Abstract
The demand for P/M parts in its traditional automotive market is predicted to grow, but future sector expansion depends directly upon its capability to manufacture zerodefect parts for industries such as aerospace and medicine.
The lack of adequate inspection systems has important implications from the view of quality assurance, since it
increases the costs, time and wasted material. In recent years the applicability of several techniques for the inspection of P/M parts have been investigated, such as Eddy current testing, computer tomography or X-Ray imaging,
but studies have revealed that all of them have deficiencies that make them unavailable for a complete and reliable
flaw detection and density defect recognition. Using funding from the European Commission, a new inspection tool
has been developed based on pulse echo ultrasonic technology combined with robotics, which makes it possible to
provide a global density map of sintered parts.
Keywords - non-destructive test, quality control, sintered parts, flaw detection, density mapping, porosity ultrasonic
inspection, ultrasound signal processing
1. GR
Toz metalurjisi (T/M) mekanik paralarn metal tozlar ve dier bileenlerden retilmesidir ve ok geni bir alanda
endstriel sinter para retiminin temel retim rotasdr. Bugn otomotiv endstrisi T/M paralar iin en byk pa-
30

zardr ve toplam pazarn %70ini oluturmaktadr. Bununla birlikte T/M paralar endstriyel eitlilik ierisinde dk
maliyetleri ve fonksiyonel esneklilikleri sebebiyle dnya apnda olduka talep grmektedir. T/M firmalar, elektrikelektronik sektrne, ev gereleri sektrne, el aletleri retimine, hidrolik sektrne, motor ve manyetik malzeme
retimine, savunma sanayine ve birok dier sektre mekanik paralar retmektedir. Dnya T/M pazarnn senelik
sat 30 milyar Euroyu amaktadr.
Sektrn gelecekteki genilemesi direk olarak uzay teknolojileri, tp sektr ve sfr hatal retim talep eden sektrler gibi alanlara ok daha karmak mekanik zelliklere sahip yksek kaliteli T/M para retebilmesine baldr.
Bununla birlikte bu yksek standartlarda para retebilmek iin mevcut retim srelerinin optimize edilmesi uzun
zaman alacaktr, nk paralarn iyaplarn test edebilmek iin gerekli, hzl ve sistematik ekipmanlar ya da test
prosedrleri yoktur. Son yllarda Eddy Current, bilgisayarl tomografi, X-Ray grntleme gibi birok tekniin Toz
Metal paralarn kontrol iin uygulanabilirlii aratrlmtr. Fakat yaplan almalar gstermitir ki bu yntemlerin
hepsin eksik olduu noktalar vardr ve bu durum onlar tam ve gvenilir bir atlak tespiti ya da younluk problemi
tespiti iin geersiz klmaktadr. Diren testi, gaz geirgenlik testi, manyetik partikl testi gibi geleneksel test yntemlerine ait yaynlarda da umut verici sonular elde edilememitir. Bir T/M parann blgesel gzenekliliinin tespitinde en gvenilir yntem parann sinterleme sonrasnda kesilip, parlatlp bu parlatlm yzey zerinde mikroskop
altnda iyapsndaki hatalarn incelenebildii optik mikroskop yntemidir. Ne yazk ki bu yntemle ie yarayacak
sonular elde edebilmek iin numunelerin ok zenle hazrlanmas gerekmektedir ve bu durum da yntemi hem
yava hem de pahal yapmaktadr.
Kalite gvence penceresinden bakldnda yeterli muayene ynteminin olmamasnn nemli etkileri vardr. Ne
yazk ki bugn sinterlenmi paralarn iyapsn uygun bir ekilde ortaya karmaya ynelik bir test yntemi yoktur.
T/M paralarn iyaplarndaki hatalar ya da younluk sapmalar gibi durumlara ait kolay eriilebilir ve gvenilir
bilgiler elde edilememesi Toz Teknolojisinin yaygnlamasn engellemekte ve kullanmn standart para retimiyle
snrlamaktadr.
Bu gelimeler T/M paralarn hat zerinde daha etkin bir ekilde kontrol edilmesini salayan yeniliki, etkili ve dk
maliyetli, ultrasonik teknoloji tabanl bir sistemi iaret etmektedir. Yeni kontrol ekipman pulse echo ultrasonik teknoloji tabanl gelitirilmitir ve bu da sinter paralarn global bir younluk haritas karlabilmesini mmkn klmaktadr.
Bu sayede pazardaki rnn daha iyi bir ekilde kontrol salanabilecek, reticinin T/M para tedarii asndan
gvenilirlii ve rekabet gc artacaktr. Ultrason teknolojisi hali hazrda kompak formlarda retim hattnn zerinde,
ksmen ezamanl, volumetrik muayene sistemidir.
2. HEDEFLER
Bu alma toz metalurjisi ile retilmi paralarn muayenesi alannda aratrma ve gelitirme yapmak amacyla
mevcut teknolojinin zerine kurulmutur. Bununla birlikte sinter paralarn (bitmi rn) younluk haritasn elde
etmek amacyla ultrason teknolojisine dayanan yeni bir yaklam kullanlacaktr. Ultrason tahribatszdr, X-ray gibi
iyonize radyasyon eklinde deildir ve bu sebeple znde olduka gvenlidir. Ultrasonik sistemler uzun periyodlarda ksmen dk altrma maliyetleriyle kendi hallerinde alr halde braklabilirler. Bu alma T/M endstrisinin
iki temel ihtiyacn yerine getirecektir:
1. Bitmi rnn performansn ciddi risk altna sokacak i yzeydeki atlaklarn hzl ve gvenilir ekilde tespit
edilmesi ve bylece btn hatal paralarn retim hattnn sonunda ayrlabilmesi. Ultrason teknolojisi birok
endstride hasar ve korozyon tespiti, kalnlk lm ve kaynak ve malzeme analizlerinde kullanlyor olduundan tahribatsz muayene iin uygun bir enstruman olduunu kantlamtr. Mevcut birok ticari hasar tespit
enstruman metaller, plastikler ve kompositler gibi mhendislik malzemelerinde gizli iyap hatalarn tespit
edebilirler.
2. Sinter paralarn iyap younluk haritalarnn karlarak muhtemel blgesel younluk hatalarn tespit edilmesi ve bu sayede parann alma esnasnda orta vadede yaratabilecei sorunlar ortadan kaldrlmas. Bu bilgi
parann final kalite kontrol srasnda ok kullanl olabilecei gibi yeni paralara yeni kalplar tasarlamak iin
gerekli zaman ve maliyetleri de azaltacaktr.
3. METODOLOJ
SINTEST iki ana alana blnebilir. Sistemin kalbi, kendine zg bir bilgisayar yazlm ile kontrol edilen 6 eksenli bir
robotik kol ile retim prosesine entegre edilebilen, pulse echo ultrason teknolojisidir.
31

3.1 Ultrasonun Kullanm

Sistem pulse-echo yaklamyla tek transduser kullanr. Ayn transduser ultrasonik dalgalar retir ve test edilen paradan geri dnen yanklar alglar. Hem transduser hem de test paras evrelerinde dolaan ultrasonik dalgalarn
transmisyonunu kolaylatrmak amacyla bir svya daldrlrlar. Sistemin emasn ekil 1.de grebilirsiniz
ekil 1. Ultrason alt sisteminin emas

Sistem bloktan olumaktadr. Ultrasonik transduser, ultrasonik verici ve ultrasonik alc. Ultrasonik verici ultrasonik transdusere elektrik voltaj demetleri gnderir. Ultrasonik transduser de bu demetlerden ultrasonik sinyaller
retir. Sinyal tekrarlama frekans ise harici bir bilgisayar tarafndan kontrol edilir. Ultrasonik transduser tarafndan
retilen elektrik sinyalleri alcya geldiklerinde genellikle ok zayflardr ve bilgisayara iletilip ilenmeden nce alc
tarafndan ykseltilmesi gerekir. Birok alternatif denendikten sonra ticari olarak bulunabilen odakl daldrmal prob
seilmitir. Transduserin ana parametreleri aadaki gibi zetlenebilir.

retici: Panametrics-NDT
Model: V324-SU
Frekans: 25 MHz
Nominal eleman bykl: 6 mm diameter
Odak: 50,8 mm
Ultrasonik verici ultrasonik transdusere elektrik voltaj demetleri gnderir. Ultrasonik transduser de bu demetlerden
ultrasonik sinyaller retir. Sinyal tekrarlama frekans ise harici bir bilgisayar tarafndan kontrol edilir. Verici aadaki
spesifikasyonlar gerekletirir:
Maksimum negatif voltaj demeti k: 300 Va kadar
Sinyal tekrarlama frekans: 5 kHz (dardan kontroll)
Ultrasonik transduser tarafndan retilen elektrik sinyalleri alcya geldiklerinde genellikle ok zayflardr ve bilgisayara iletilip ilenmeden nce alc tarafndan ykseltilmesi gerekir. Alc bir zaman ilerleme kontroll ykselticiden
(Time Gain Controlled Amplifier, TGCA), bir voltaj rampa reticiden ve bir logaritmik ykselticiden olumaktadr.
TGCA, ultra dk ses ykselticisi ve deiken alg ykseltici ieren Analog Devices marka AD8331 entegre devre
temeline dayanmaktadr. TGCAnn alglad sinyaller bir voltaj rampa retici tarafndan control edilir ve dolam
mesafesi ierisinde ultrasonik dalgalarn zayflamasn geen zaman ierisinde telafi ederek sinyalleri ykseltir.
Logaritmik ykseltici Analog Devices marka AD8310 entegre devresi tabanldr. Alcnn spesifikasyonlar aadaki
gibi zetlenebilir:

Bant Genilii: 50 MHz

Alg aral: 14 - 110 dB
Giri empedans: 300
k empedans: 50
Elde edilen sinyaller sonularn yorumlanmasn kolaylatrmak amacyla grntlere dntrlerek ilenirler. Sonular B-scan ve C-scan grntleri eklinde sunulur. B-scan grntleri ardk noktalardan geri dnen sinyallerin
yakalanp birletirilerek bir doru haline getirilmesiyle oluturulur. C-scande ise sinyalin yansyan enerjisi muayene
edilen alann her bir noktasnda bir renkle temsil edilir. B-scan grntleri bir doru oluturacak ekilde ardk olarak test edilmi noktalardan elde edilen sinyal genliini (nceden artlandrlm) temsil edecek ekilde oluturulur.
B-scan grntleri parann dikey bir kesiti eklindedir ve grntdeki renk deiiklikleri ya gzeneklilikle ya da
atlaklardan kaynakl kesintilerle alakaldr. Dier taraftan C-scan grntleri bir alan oluturacak ekilde test edilen
32

ardk noktalardan yansyan sinyalin enerjisini temsil edecek ekilde oluturulur. C-scan grntler test edilen
parann yatay bir kesitini temsil eder ve sadece belirli bir derinlik aralndan elde edilen enerjinin birletirilmesiyle
oluturulur. Bu sebeple bu tr bir grntde atlak olan bir yerden ok daha fazla enerji yansyacandan kolaylkla
renk farkllklar grebiliriz.
3.2 Online Direkt Robot Kontrol
Prototip srasnda probun manipulasyonu iin NX100 endstriyel robot kontrol tarafndan ynlendirilen bir Motoman HP6 ok kullanml robotu kullanlmtr. NX100 kontrolrnn RS232 ve Eternet gibi harici iletiim kanallar
olduundan cihazla kiisel bilgisayarlarda Motoman tarafndan gelitirilmi iletiim protokol kullanlarak kolaylkla
iletiim kurulabilmektedir. SINTEST projesinde pahal orijinal ktpane yerine robotun uzaktan kumandasn ve
sistemin kontroln gvence altna alcak ekilde bilgi alveriini salayan kendi ktphanesi oluturulmutur.
ekil 2. NX100n iletiim protokol

ekil 2.de grld gibi iletiim iki ana faza ayrlmtr; balatma ve iletiim. Balatma sadece bir kez program
balangcnda yaplr. letiim basit bir UDP datagram zerinden komut ve mesajlar yaln tekst formatnda gndererek ve alarak yaplr. Komutlar basit bir yolla gnderilirken ve alnrken mesajlar zel balklar eklinde ksaltlrlar.
Ayrca Microsoft Game Studio 3.1 ve NET Framework 3.5 ieren en yeni ve en stn 3D ( boyutlu) grntleme
teknolojisi kullanlarak zel bir ok evreli GUI (Graphical User Interface, Grafiksel Kullanc Arayz) gelitirilmitir.
Bu kendine zg aralar ilemci zamannn ounu veri analizine ayracak ekilde hesaplama gerekliliklerinin greceli olarak dk seviyelerde tutulmasna olanak vermitir. GUIde gerek ortamn bir dijital modeli oluturulmu
ve robotu ve lmn yaplaca tezgah da ierecek ekilde kalibre edilmitir. Model ayrca bir alma alanna da
aktarlabilir ve zel bir algoritma, ultrasonik sensrn hareket edecei yolu istenilen znrlkte otomatik olarak
hesaplar. Hesaplama test edilecek parann ekline dayanr ve sonu olarak her nokta ilgili yzey noktasndan tam
olarak eit mesafede olacak ekilde tespit edilir. ekil 3.te model ve prob hareketi hesaplamas grlebilir.
Sanal bir ortama sahip olmas sebebiyle sistem lmn tamamn kendi kendine simle edebilir ve bu sayede
sensrn sistemin dier bileenlerine arpp arpmayaca tespit edilebilir. Bu da sensr kafasnn korunmasn
kolaylatrr. Bu zellik ayrca btn bir set parann taranmas iin gerekli zamann evirimd bir simulasyonda
hesaplanmasna olanak verdiinden sre planlamasnn erken fazlarnda da kullanl olabilir. Aktr ki eer bilgisayara balanm bir robotunuz varsa onu direkt olarak istediiniz yrngede kontrol edebilirsiniz. ok zel durumlar iin bir hareket izleme sistemi de mevcuttur ve bu sistem birleme yerlerinin pozisyonlarn tanmlayarak ya da
ekipmann pozisyon ve oryantasyonunu ileterek robot kolun direkt kontroln garanti altna alr.
ekil 3. SINTESTin grafiksel kullanc arayz
33

4. SONULAR
Ultrasonik sistemin tasarmnn uygunluunu onaylamak iin birok deneme gerekletirilmitir. Denemeler daha
nce karakterize edilmi T/M paralardan seilmi rnekler zerinde gerekletirilmitir. Gzenekliliin deerlendirilmesi asndan sistemin performans ekil 4.te grlen ayn geometrili parann deiik basn altnda sktrlm ve bu sayede deiik younlukta elde edilmi rnekleri zerinde kantlanmtr.
ekil 4. Gzeneklilik/Younluk lmnde

kullanlan rnek paralar
Sonular B-scan grntleri olarak sunulmutur. ekil 5, 6 ve 7 incelenen numunenin ayn kesitindeki B-scan
sonularn gstermektedir. ekiller kesitin sadece kk bir alann gstermektedir. Bu ekillerden de grlmektedir ki younluk ne kadar dkse o kadar deiken bir grnt elde edilmektedir. Bunun sebebi younluk dtke
gzenekliliin artmas ve bu sebeple ultrasonik dalgalarn ok daha fazla yansmaya uramasdr. Bu grntler bir
iso-genlikli hat tespit algoritmas vastasyla numuneler arasndaki farkllklar arttrmak iin ilenmitir.
ekil 5. rnek # 1in B-Scani (younluk 6.85 g/cm3)
ekil 6. rnek # 2nin B-Scani (younluk 6.07 g/cm3)
34

ekil 7. rnek # 3n B-Scani (younluk 5.51 g/cm3)

Ultrasonik sistem sinterlenmi numunelerde atlak tespiti iin de deerlendirilmitir. ekil 8.de lmlerde kullanlm T/M paray grebilirsiniz. Bu paralarda i kademe kenarnda ekil 8.de belirtilen blgede atlak olduu
rapor edilmitir.
ekil 8. Numunelerdeki hasarl blgeler

Numunedeki atlaklar ok ak ekilde B-scan grntlerde fark edilebilmektedir. atlak blgeden gelen yanklar
yzeyin yaklak 2 mm. altnda, sv ve numune ara yzeyinden hemen sonradr. atlak tespiti ekil 9 ve 10daki
hasarl ve hasarsz paralarn kyaslama grntlerinde ok daha ak yaplabilir.
ekil 9. Hasarsz rnein (stte) ve hasarl rnein (altta) radyal ynde B-Scan grntleri
35

Ayrca hasarl paradaki atlaklar ok ak ekilde C-scan grntsnde de (krmz blgeler) fark edilebilmektedir.
atlak tespiti ekil 11de de gsterildii ekilde hasarl ve hasarsz parann kyasland grntler zerinde ok
daha kolaylkla yaplabilir.
ekil 10. Hasarsz rnein (solda) ve hasarl rnein (sada) D apa dik ynde B-scan grntleri
ekil 11. Hasarsz rnein (solda) ve hasarl rnein (sada) tm yzey C-scan grnts
5. DEERLENDRME
Yaplan deneyler gstemitir ki ultrasonik dalgalar hatalarn ve hasarlarn ounlukla mevcut olduu derin blgelere
ulaabilmektedirler. Ayrca deneyler gstermitir ki ultrason teknolojisi sinter paralarda younluk ve gzeneklilik
farkllklarn, hasar ve atlak tespitini olanakl klmaktadr. Bu laboratuar testleri pulse echo ultrason teknolojisinin
toz metalurjisi endstrisinde tahribatsz muayene iin ok uygun bir yntem olduunu kantlamtr. Sonular bu
teknoloji kullanlarak hasarn ak grsel bir sunumunun elde edilebileceini gstermitir. Bu da hatalarn bykl
ve yerinin tespitinde kullanlabilir. Bu sebeple teknoloji sadece grntleme/tespit amal olarak deil kalp tasarm
ve retim srelerindeki parametrelerin iyiletirilmesine yardmc olacandan bir kalite gvence ekipman olarak ta
deerlendirilmelidir. Sistemin bir dier ana avantaj ise maliyetidir. lmler iin tek bir prop kulland iin gerekli
ekipman snrldr. Sistemin veri analizi dahil ultrasonik ksm ve robot kontrol bileenlerinin toplam maliyeti birka
36

bin Eurolar civarndadr. Ve bu miktar dier T/M muayene ekipmanlarna kyasla olduka nemsizdir. Sistemin en
pahal ksm endstriyel robottur fakat yazlm herhangi bir robota kolayca adapte edilebilecek ekilde gelitirilmitir. Bu esneklik kullancnn sistemi kendinde mevcut bir robota ya da ikinci el bir robota adapte etmesine olanak
verir. Muayene iin gerekli hassasiyet greceli olarak dktr ve bu sebeple bu uygulama iin bir orta zellikli
robot yeterli olacaktr. Bu durumlar gze alndnda SINTEST muayene ekipman nihai sat fiyat 25.000 Euroyu
gemeyecektir ve bu da rekabet gcnn olduka yksek olacan gstermektedir. Teknoloji uygunluu laboratuar
koullarnda yaplmtr ve endstriyel uygunluk iin ekipmann eksiksiz ve evrensel bir ekipman olduunu kantlamak amacyla denemeler ferritler dahil deiik T/M paralar zerinde devam edecektir.
6. TEEKKR
SINTEST projesi Avrupa birlii Komisyonunun 7. ereve Program tarafndan deneklendirilmi ve MFKK firmas
tarafndan koordine edilmitir. Proje bir konsorsiyum tarafndan yrtlmtr bu sebeple Tozmetal A.S, Sinterpress
S.L, Danalco Wear & Welding Tech, TKI-Ferrit, M-iNG I&I, Ingenieurbro Gammatec, & Multitest Ltd. dahil btn
partnerlere teekkrlerimizi sunarz.
37

BORON
www.turkishpm.org
38

HOLDING CONDITIONS ON MECHANICAL PROPERTIES OF CAST

AL-B ALLOYS
Necip Fazl YILMAZ*, Mehmet ZTRK**
*Gaziantep University, Faculty of Engineering, Department of Mechanical Engineering, 27310, Gaziantep, Turkey,
nfyilmaz@gantep.edu.tr
**Gaziantep University, Faculty of Engineering, Department of Mechanical Engineering, 27310, Gaziantep, Turkey, mehmetozturk@gantep.edu.tr
ABSTRACT
In this study, mechanical properties of Al-B alloys, prepared by the addition of borax to 99.70% pure commercial
aluminum, were investigated. In this process, amount of borax, holding temperature and holding time were realized
as affecting parameters. By considering these parameters three specimens were prepared for each condition and
they were subjected to mechanical tests such as tensile and impact tests. As a result of tests, tensile strength of the
alloy with the incorporation of borax was found 33% increase in comparison to pure aluminum while 21% increase
in impact energy value. A substantial quantity of aluminum-boride flakes were observed in the microstructural investigation of the samples.
Keywords: Al-B alloy, Mechanical Properties, Metal Alloys, Casting
1 INTRODUCTION
In recent years, investigations in finding new materials superior than the conventional ones and improving the
already existent materials properties have an increasing demand to respond the need in the use of light-weight
functional material in emerging industrial applications. In this regard, stimulated intensive research activities have
been observed on aluminum alloys [1-3]. The most important characteristics of Al alloys are low density, high
strength-weight ratio and resistance to corrosion that have enabled them to be one of the dominant structural material families of the 21th century.
Mechanical properties of Al can be greatly improved by incorporating with some chemical elements. Pure aluminum
has a tensile strength of about 49 MPa and if it is formed into an alloy this value can be increased up to around 700
MPa [4]. Most of the chemical elements possessing metallic characteristics readily alloy with aluminum, but only a
few are important major alloying ingredients in commercial aluminum-base alloys. The typical alloying elements are
copper, magnesium, manganese, silicon, and zinc [5].
Al-B alloys are widely used commercially in the production of electrical conductive grade aluminum to scavenge
transition metal impurities, such as titanium, vanadium, chromium and zirconium elements and have also great importance for its usage as grain refining agent for aluminum castings [7-10]. In this work, boron element was used as
an alloying element to investigate a new generation aluminum alloy. This paper presents the experimental studies
to determine the mechanical properties such as tensile and impact properties of the cast Al-B alloy.
2 EXPERIMENTAL PROCEDURE
2.1 Materials
Materials used in this study were 99.70% pure commercial aluminum (AA1070) and borax powder (Na2B4O7.10H2O).
Primary unalloyed aluminum ingots were obtained from Seydisehir Aluminum (Turkey) and borax was provided from
Eti Mine Works (Turkey). The chemical composition of AA 1070 aluminum used in the present work is given in Table
1. Main impurities of AA 1070 aluminum are iron and silicon. In this study borax was used as a boron source to
produce Aluminum-Boron alloy.
39

Al
99.7
Cu
0.04
Table 1. Chemical Composition of AA 1070 (%)

Fe
Mg
Mn
Si
Ti
V
Zn
0.25
0.03
0.03 0.2 0.03
0.05
0.04
Others
0.03
2.2 Manufacturing Conditions and Specimens

During the experimentation, conventional casting method was used to produce aluminum-boron alloys. Some fabrication parameters were established to compare the effects of parameters on the mechanical properties of alloys
[11]. All these parameters and mutual dependence are demonstrated in Figure 1.
Figure 1. Parameters Used in the Experiments

Borax addition was performed within 5, 10, 15 and 20 weight percentage of pure aluminum and three temperatures,
namely: 800, 1000 and 12000C were carried out during casting process. All samples were also hold 30, 45 and 60
minutes in the oven at elevated temperatures before casting into dies.
The preparation steps of Al-B alloys were considered to consist of three distinct and consecutive steps (Figure 2).
Figure 2. Production Steps of Al-B alloys

Fabrications of alloys were carried out on an about 400 gram batch scale. AA 1070 aluminum alloy ingots were
placed into a graphite crucible with borax powder together and were brought to predetermined temperature using
an electrical resistance furnace.
The molten alloy thus obtained was held to establish a reaction between the aluminum and borax. During holding
dross was generated on the surface and this dross provided an effective mechanism for protecting the molten alloy
from the environmental effects. There was no stirring during holding to avoid excessive oxidation. Before casting
into a permanent mold, dross was skimmed off from the surface and the melt was stirred thoroughly with graphite
rods for 30 seconds to ensure homogeneity. As a last step, the melt was poured into a metal mold, made by cast
iron, with a diameter of 20 mm and a height of 200 mm.
Mechanical tests play a significant role in evaluating fundamental properties of materials. All samples were subjected to tensile and impact tests to observe the variations of mechanical properties. The tensile test was carried out
on a cylindrical specimen with a gauge length of 75 mm and a diameter of 15 mm by using Shimadzu AGX universal
testing device at RT. Impact test was performed on specimens with square cross section 10x10 mm and length of 55
mm by using Tinius Olsen charpy-type impact test equipment at RT. All impact test specimens have v type notch
with the degree of 45 and 2 mm depth. Tensile and impact specimens are shown in Figure 3.
a) Tensle
B) Impact
Figure 3. Specimens for Tensile and Impact Testing
40


Many experiments were carried out during this work but only 45 test results were emphasized in this paper. All test
results were evaluated by averaging the results of 3 successive measurements in every sample.
3.1 Tensile Properties
Tensile test results of samples as UTS values with and without incorporating borax are presented in Table 2. The
data reveal that certain amount of borax addition increases ultimate tensile strength of pure aluminum.
Table 2. Tensile Test Results (MPa)
Pure
%5 Borax
800 1000 1200 800 1000 1200
(0C) (0C) (0C) (0C) (0C) (0C)
30 min 52,2 54,7 49,1 62,0 64,6 59,7
45 min 58,7 59,7 51,1 63,6 79,5 72,6
60 min 55,9 53,1 50,9 67,0 73,5 70,5
%10 borax
800 1000 1200
(0C) (0C) (0C)
62,7 72,8 61,1
71,8 78,1 73,7
67,7 75,3 63,7
%15 Borax
800 1000 1200
(0C) (0C) (0C)
66,8 73,8 50,5
73,0 76,0 53,2
75,1 75,2 58,8
%20 borax
800 1000 1200
(0C) (0C) (0C)
71,2 66 52,3
70,6 68,5 56,4
67,7 63,5 54,7
The variations in the measured UTS value according to borax addition and holding times for varying holding temperature are respectively plotted in Figure 4. Highest UTS values were recorded at 5 and 10% borax addition as 79.5
and 78.1 MPa respectively. As shown in Figure 4, it is very clear that increasing holding temperature from 8000C to
10000C resulted in greater UTS values. Increasing holding temperature to 12000C has almost completely negated
the UTS value of the samples almost in all conditions. When the effect of holding time on tensile test results are
taken into consideration, holding time increasing up to 45 minutes improved UTS value almost in all cases. Holding
for more than 45 minutes does not seem to offer any improvement in UTS values.
Figure 4. UTS variations of the samples
41

3.2 Impact Properties

Impact test results are depicted in Table 3. Data indicate that certain amount of borax addition to the pure aluminum
yielded an improvement in impact resistance.
Table 3. Impact Test Results (J)
30 min
45 min
60 min
Pure
%5 Borax
%10 borax
%15 Borax
800 1000 1200 800 1000 1200 800 1000 1200 800 1000 1200
(0C) (0C) (0C) (0C) (0C) (0C) (0C) (0C) (0C) (0C) (0C) (0C)
4,7
4,9
1,1 6,0
6,2
1,8 5,9
6,6
1,1 6,2
6,1
1,3
5,0
5,7
1,2 6,6
6,9
2,1 6,2
6,8
1,2 6,7
6,7
1,0
4,5
4,1
0,9 6,2
6,5
3,3 5,5
6,7
1,1 6,6
6
0,9
%20 borax
800 1000 1200
(0C) (0C) (0C)
6,4 6,1
1,2
6,4 5,7
1,4
6,5 5,4
1,4
Variations of the impact energy value of the samples as a function of holding temperature for varying holding times
and borax addition are displayed in Figure 5. The greatest impact energy values were obtained at 5 and 10% borax addition as 6.9 and 6.8 joule respectively. There is strong relationship between the holding temperature and
impact energy as seen in Figure 5. Increasing holding temperature up to 10000C improved impact energy values.
A significant point was observed that increasing holding temperature from 10000C to 12000C resulted in a dramatic
reduction in impact resistance for both pure aluminum and alloyed samples in all conditions.
Figure 5. Impact Energy Variations of the sample

Higher impact energy values were observed when the holding time increased from 30 to 45 minutes. However,
further increasing holding time caused a reduction in impact energy values.
Maximum results obtained from the tensile and impact tests and their fabrication conditions are summarized in
Table 4.
42

Table 4. Maximum Test Results

Borax
(%)
Holding
Temperature (0C)
Holding Time
(min)
Pure
Max.
Value
Increment
Tensile strength (MPa)
1000
45
59.7
79.5
33%
Impact Energy (kg.m)
1000
45
5.7
6.9
21%
3.3 Microstructure
Standard metallographic procedures were employed to prepare the produced samples. In this work, specimens
firstly were cut transversally in a band saw with a height of 20 mm then fixed into Weber mounting device. In order
to obtain a highly reflective surface for microscopic examination that is free from scratches and damages, the specimens were carefully grinded and polished. All samples were gently grinded with 240, 400, 600, 800, 1000, and 2000
mesh SiC emery papers. Afterwards samples were roughly polished by 6 and 1 diamond solutions and then final
polishing was performed by colloidal silica to obtain highly reflective surface. All grinding and polishing operations
were made with Metkon Forcipol 2V grinding and polishing device. All samples were chemically etched with 0.5
ml hydrofluoric acid (HF) in 100 ml pure water for 45 seconds [6]. The microstructure examinations of the alloyed
samples have been done by Nikon MA-100 optical microscope.
(a)
(b)
(c)
Figure 6. Microstructure of produced Al-B alloy:

a) 10X b) 50X c) 100X
43

Figure 6 depicts the microstructure of the sample prepared by holding 45 minutes at 10000C with the addition of 5%
borax, which has the highest UTS and impact energy value. The bright region represents the aluminum, the dark
gray particles as aluminum-borides in micrographs. A substantial quantity of thick and long aluminum-boride flakes
are observed in microstructure.
4. CONCLUSIONS
A systematic experimental method has been achieved successfully in this work. The casted products have been
machined according to the tests. It is possible to say that mechanical properties of AA 1070 aluminum can be enhanced by incorporating with borax by considering the experimental results and all about the data.
By imposing various borax additions, holding temperatures and times on the samples, the following conclusions
can be drawn from this study:
The greatest mechanical test results obtained in %5-10 borax addition ranges.
Optimum holding temperature was obtained at 10000C for tensile and impact properties of Al-B alloys.
Optimum holding time for the highest mechanical properties has been described at 45 minutes.
Increase in mechanical properties of the alloyed sample are:

33% for UTS value

21% for impact energy
when comparing the maximum values with pure aluminum produced in the same conditions.
Microscopic observations of alloyed samples reveal homogeneous distribution of aluminum boride
particles and fewer porosity levels.
Acknowledgement
The authors would like to thank Scientific Research Projects Governing Unit of Gaziantep University for the financial
support during the period of this research work.
REFERENCES
[1] Birol, Y., Production of Al-Ti-B grain refining master alloys from B2O3 and K2TiF6, Journal of Alloys and Compounds, Vol. 443, pp. 94-98, 2007.
[2] Kerti, I., Toptan, F., Microstructural variations in cast B4C-reinforced aluminum matrix composites (AMCs),
Materials Letters, Vol. 62, pp. 1215-1218, 2008.
[3] Mohanty, R.M., Balasubramanian, K., Seshadri, S.K., Boron carbide-reinforced aluminum 1100 matrix composites: Fabrication and Properties, Materials Science and Engineering, Vol. A498, pp. 42-52, 2008.
[4] Totten, G.E., MacKenzie, D.S., Handbook of aluminum, M. Dekker, New York, 2003.
[5] American Society for Metals, Aluminum: Properties, physical metallurgy and phase diagrams, Ohio, Chapman & Hall Ltd, 1971.
[6] Birol, Y., Production of Al-Ti-B grain refining master alloys from Na2B4O7 and K2TiF6, Journal of Alloys and
Compounds, Vol. 458, pp. 271-276, 2008.
[7] Wang, X., The formation of AlB2 in an Al-B master alloy, Journal of Alloys and Compounds, Vol. 403, pp.
283-287, 2005.
[8] Hall, A.C., Economy, J., Preparing high and low aspect ratio AlB2 flakes from borax or boron oxide, Journal of
the Minerals, Vol. 52(2), pp. 42-44, 2000.
[9] Setzer, W.C., Boone, G.W., The Use of Aluminum/Boron Master Alloys to Improve Electrical Conductivity,
Light Metals, pp. 837844, 1992.
[10] Fjellstedt, J., Jarfors, A.E.W., Svendsen, L., Experimental analysis of the intermediary phases AlB2, AlB12 and
TiB2 in the Al-B and Al-Ti-B systems, Journal of Alloys and Compounds, Vol. 283, pp. 192-197, 1999.
[11] Ozturk, M., An Experimental Study on Mechanical Properties of Aluminum-Boron Compounds, MSc Thesis,
Gaziantep University, Gaziantep, 2011.
44

VIBRATION DAMPING CHARACTERISTICS OF

BORON COMPOSITES
H. Ibrahim UNAL*, Ozlem EROL*, O. Yunus GUMUS**, Berrak CETIN*, Turgay ERGIN***
*Gazi University, Chemistry Department, Smart Materials Research Lab., Ankara, Turkey,
iunal@gazi.edu.tr
**Nevsehir University, Chemistry Department, Nevsehir, Turkey
***Hacettepe University, Department of Automotive, Ankara, Turkey
ABSTRACT
Electrorheological (ER) fluids can be classified as smart materials due to their controllable and reversible rheological characteristics under external electric fields. Most ER fluids consist of polarizable solid powders dispersed in
insulating non-polar liquids. Recently, conducting polymers have gained interest in boron derivative containing
conducting composites. Conducting polymer/boron derivative composites can be fabricated with controlled levels
of conductivity and enhanced anti-sedimentation stability.
In this study, vibration damping characteristics of borax and polyindene/colemanite composites were investigated.
After characterizing these materials by various techniques, volume fraction series of dispersions were prepared in
silicone oil (SO). Anti-sedimentation stabilities of these suspensions were determined. Flow rate measurements
of these dispersions were measured at various electric field values; flow times and threshold energies were determined. Finally, vibration damping capacities of the materials were tested under external electric field, using an
automobile shock absorber and were calculated as 68% and 27% for borax/SO and polyindene/colemanite/SO
systems, respectively.
Keywords: Conducting Polymer Composite, Electrorheological Fluids, Borax, Colemanite, Vibration Damping,
Shock Absorber.
1. INTRODUCTION
Electrorheological (ER) fluids are colloidal dispersions that commonly compose of polarizable powders dispersed in
non-conducting liquids. ER fluids exhibit reversible changes (liquid-like to solid like and vice-versa) in their rheological properties as a function of the electric field strength (E). In the presence of sufficient electric field strength, the
dispersed particles are polarized and aligned in the field direction to form a solid-like network of fibrillar structures
and these structures cause to observe changes in rheological properties of dispersion.
The solid powder comprises inorganic non-metallic, organic or polymeric semi-conductive materials [1]. Borax
(Na2B4O7.5H2O) and colemanite (2CaO.3B2O3.5H2O) are important boron containing commercial borate minerals
and can be candidates for being ER material. Also, preparing their composites with conducting polymer is another
option since the interactions between organic and inorganic component of composite materials could enhance the
desired properties. Because of the rapid and reversible changes in their rheological properties with the external
applied E, ER fluids have been widely investigated for the purpose of various industrial applications such as shock
absorbers, engine mounts, clutch/brakes and vibration dampers. ER shock absorbers are characterized by a valve
containing a pair of electrodes between which the ER fluid flows [2].
The aim of this study was to investigate the vibration damping capacities of borax/SO and polyindene/colemanite
composite/SO dispersion systems. Thus, borax was kindly ground milled and polyindene was polymerized in the
presence of colemanite. The materials were dispersed in SO. Anti-sedimentation ratios of the dispersions were
determined under constant temperature. Flow rates and threshold energies of the materials were investigated
under various E. The effects of surfactant and polar additives on vibration damping capacities of the polyindene/
colemanite/SO were also examined. Results implied that all the systems perceive the applied electric field and try
to act as a vibration damper.
45

2. EXPERIMENTAL
Borax and colemanite were kindly supplied by ETI Mining Co. (Turkey) and were ground milled. All the other chemicals were Aldrich products and used as received. Indene was used after distillation. Polyindene (PIn) was in-situ
polymerized in the presence of colemanite using FeCl3 as oxidizing agent taking the monomer to initiator ratio as
2:1 in CHCl3. The prepared PIn/colemanite was ground-milled and subjected to particle size measurement using
a Malvern Nano-ZS particle size analyzer. The obtained PIn/colemanite was subjected to various characterization
techniques, namely: FTIR, particle size, density, conductivity, TGA, XRD and SEM.
All the materials were subjected to solid pellet preparation (cylindrical in shape). Further, the apparent densities and
conductivities (by a four probe technique) of the materials were measured.
Dispersions of borax, colemanite and PIn/colemanite composite were prepared in SO at a series of volume fractions
( = 525%) and the anti-sedimentation stability of the dispersion systems were measured (T = 250.1C).
The non-ionic surfactant examined was Triton-X (t-octylphenoxypolyethoxyethanol) and the concentration of TritonX in the colemanite and PIn/colemanite dispersions was 5 wt.%. To prepare the dispersions containing Triton-X,
firstly, SO and surfactant were homogeneously mixed by using an ultrasonicator and then the materials, (colemanite
and PIn/colemanite), were added and mixed again, with the volume fraction of 25%. These surfactant containing
dispersions were coded as T-colemanite and T-PIn/colemanite. To enhance the ER activity of colemanite/SO and
PIn/colemanite/SO dispersions, glycerol was added as 10 L/mL and the resultant dispersions were coded as Gcolemanite and G-PIn/colemanite. All the prepared dispersions were allowed to equilibrate for overnight before ER
and vibration damping measurements.
Flow rate measurements were carried out between two brass electrodes, which were connected to a high-voltage
dc power supply. Oscillatory tests were carried out by a Termo-Haake RS600 parallel plate torque electrorheometer.
Vibration damping experiments were carried out on an automobile shock absorber for Borax/SO ( =15%), under
E = 0-0.3 kV/mm conditions on Therpa Hydraulic vibration damping test device. The hydraulic vibration test equipment contained a wheel (with a spring coefficient of 65400 N/m), an axle, a spring (with a coefficient of 13000 N/m),
a shock absorber, an electrically operated drum to turn the wheel, a vibrating mass (60 kg), a non-vibrating mass
(14 kg), control units and an external electric field generator (Fug Electronics). During the experiments, vibrations
occurring on the body and on the axle were recorded by a recorder, which was operated at 400 V and 16 A.
250 mL of colemanite/SO, G-colemanite/SO, T-PIn/colemanite/SO and PIn/colemanite/SO dispersion systems were
used with = 10% under the external electric field strength sweep of E = 0-170 V/mm and the experiments were
carried out using Roehrig 20VS model shock absorber test equipment. During the experiments, a modified automobile shock absorber was placed to the vibration test device and a dc external electric field generator was connected
to the inner and outer tubes of the shock absorber. The test parameters were set up using the Shock 6.3 shock
absorber test program as following: Amplitude: 25.12 mm, test temperature: 25C, maximum test speed: 0.1 ms-1,
frequency: 0.63 Hz, type of the input wave: sinusoidal.
3. RESULTS AND DISCUSSIONS
The FTIR spectra proofed that the PIn/colemanite composite was successfully synthesized. SEM image of PIn/
colemanite composite reveals that porous structures of colemanite particles were homogeneously surrounded by
close packed PIn chains, which supports the successful PIn/colemanite composite formation. The XRD pattern of
PIn/colemanite composite showed sharp peaks at 2 = 15, 22 and 28 which indicates that colemanite was in the
composite structure. The thermal stability of PIn/colemanite composite was observed to be higher than the thermal
stabilities of colemanite and PIn [3].
The average particle size, apparent density, conductivity and anti-sedimentation ratios of the materials are given in
Table 1. The conductivity values were decided to be in a suitable range for ER measurements.
Table 1. Same physical properties of the samples.
Sample
Borax [4]
Colemanite
PIn/colemanite
Average particle
size (m)
6.35
1.2
2.2
Apparent
Conductivity (Scmdensity (gcm-3) 1)x104
1.51
1.69
1.02
1.3
3.14
2.48
46
Anti-sedimentation ratios
(%, at the end of 25 days, = 25%)
67
73
93

Colloidal stability of the ER fluids against sedimentation is one of the important factors from industrial and application
points of view. The ER fluids are supposed to be homogeneously dispersed before applying external electric field
strength, and so that the stable fibrillar structures are formed under E between the upper and lower electrodes. At
the end of 25 days of observation, 93% of PIn/colemanite composite particles were determined to remain unsettled.
PIn/colemanite/SO dispersion system was significantly stable against gravitational sedimentation than colemanite/
SO and borax/SO systems. It can be concluded that in composite structure PIn chains surrounded the colemanite
particles and formed steric hindrance that holds the particles in suspended positions against agglomeration.
To observe the effect of dc electric field on the ER activity, flow rate measurements were carried out on all the
dispersions. For this purpose, dispersions were prepared at a series of particle volume fractions ( = 525%) in
SO and flow times were measured under E 0 kV/mm and E = 0 kV/mm conditions. During the flow time measurements, it was observed that electric field response time decreases with increasing volume fractions as a result of
formation of fibrillar chain-like structures between the electrodes. On the other hand, a significant fibrillar structures
between the electrodes was not observed for PIn/colemanite/SO system.
The external frequency (f) is an important factor for characterizing the dynamic viscoelastic properties of ER fluids
in vibration damping processes. Stress sweep was first carried out to determine the proper stress value to measure
the storage modulus (G) in the linear viscoelastic regime. Figure 1 shows G as a function of frequency for borax/SO
( = 20%, E = 2 kV/mm), colemanite/SO, T-colemanite/SO, PIn/colemanite/SO and T-PIn/colemanite/SO dispersion
systems ( = 25%, E = 1.5 kV/mm).
Figure 1. Change in storage modulus with frequency for all the dispersions.
It was observed that Borax/SO system showed the highest G values and G values of all dispersions except PIn/
colemanite/SO were showed slight increments in the whole frequency sweep range and owing to not providing fully
elastic solid-like structure in the dispersions, but they showed viscoelastic behavior. However, G values of PIn/colemanite/SO increased notably with increasing frequency. This suggests that fibrillar structure between the electrodes
could not occur for PIn/colemanite [5].
Figure 2. Change in damping forces with piston velocity of shock absorber.

Sample: T-PIn/colemanite/SO, = 10%.
Figure 2 represents the damping forces (Fdamping) as a function of piston velocity of the modified automobile shock
absorber for just T-PIn/colemanite/SO system under the constant conditions of T = 25C, = 10% and E = 0-170
V/mm. As the electric field increased, Fdamping of the ER damper, filled with T-PIn/colemanite/SO, also increased
thereby requiring more force to move the piston. This was mainly attributed to the increment of the shear stress of
47

the ER fluid with increasing applied E. The percentage increment of vibration damping of the samples was determined from the following equation:

(1)
Vibration damping (%) of the materials calculated to change in the following order: T-PIn-colemanite (30%)>G-colemanite (28%)>PIn-colemanite (27%)>Colemanite (14%). The addition of Triton-X or glycerol caused to increase in
the percentage of vibration damping of PIn/colemanite/SO and colemanite/SO. It was concluded that the presence
of surfactant/promoter improved the performance of ER fluid.
For Borax/SO system ( = 15%), positive body vibration amplitudes (recorded in the course of opening of the shock
absorber) were observed to be bigger than the negative body vibration amplitudes (recorded in the course of closing
of the shock absorber). Results showed that the amplitudes of body and axle, which are 10.2 and 12.6 mm, respectively, under non-electric field were reduced to 3.2 and 8.7 mm, respectively, by applying E = 300 V/mm external
electric field. Thus, the vibration damping values were calculated as 68% on the body and 31% on the axle. These
reductions on the amplitudes indicate that borax/SO system is able to perceive applied electric field strength and
significantly increase the vibration damping capacity of the automobile shock absorber [6].
ACKNOWLEDGEMENTS
The authors thank to Turkish Scientific and Technological Research Council for the financial support of this work
(Project no: 107 T 711).
REFERENCES
1. Hao, T., Electrorheological suspensions, Advances in Colloid and Interface Science, Vol. 97, pp. 1-35, 2002.
2. Wereley, N.M., Nondimensional HerschelBulkley Analysis of Magnetorheological and Electrorheological
Dampers, Journal of Intelligent Material Systems and Structures, Vol. 19, pp. 257-268, 2008.
3. Cetin, B., Unal, H.I., Erol, O., Synthesis, Characterization and Electrokinetic Properties of Polyindene/
Colemanite Conducting Composite, Clay and Clay Minerals, submitted, 2011.
4. Gumus, O.Y., Unal, H.I., Erol, O., Sari, B., Synthesis, Characterization, and Colloidal Properties of
Polythiophene/Borax Conducting Composite, Polymer Composites, Vol. 32, pp. 418-426, 2011.
5. Ramos-Tejada, M.M., Espin M.J., Perea, R., Delgado, A.V., Electrorheology of suspensions of elongated
goethite particles, Journal of Non-Newtonian Fluid Mechanics, Vol. 159. pp. 34-40, 2009.
6. Gumus, O.Y., Erol, O., Unal, H.I., Polythiophene/Borax Conducting Composite II: Electrorheology and Industrial
Applications, Polymer Composites, Vol. 32, pp. 756-765, 2011.
48

Production of Al- B4C functionally graded material by

powder metallurgy method
Aykut Canakci1, Temel Varol1, Ihsan Gokhan Zerin, Serdar zkaya
1
Department of Metallurgical and Materials Engineering, Karadeniz Technical University, Trabzon, Turkey aykut@
ktu.edu.tr, tvarol@ktu.edu.tr
Abstract
The aim of this study is to examine the effects of the processing conditions on the final microstructure of Al-B4C
functionally graded materials (FGMs). Al-B4C functionally graded material (FGM) having a compositional gradient
from Al to B4C was obtained by powder metallurgy method with Al and B4C powders as starting materials. For this
purpose laminar type of functionally graded Al-B4C with 1, 2 and 3 layers, which have different compositions, were
produced. The functionally graded materials were analysed using a scanning electron microscopy (SEM). The
microstructure, elemental distribution and microhardness variation of the sintered Al-B4C samples were investigated. The experimental results show that the distributions of structure properties strongly depend on the variation
of microstructure. It is observed that hardness increases and ductility decreases with the increase of B4C, which
is attributed to the variation of the matrix phase from the metal to the ceramic. Morever, The results showed that
laminar type is an effective method for Al-B4C functionally graded materials production.
Keywords: Functionally graded materials, Powder metallurgy, Boron carbide (B4C)
1. Introduction
Functionally graded material (FGM) is a new concept in material design. FGMs with continuous changes of microstructures and properties across the material are expected to have low residual and thermal stresses and improved
bonding strength between dissimilar materials and ceramic coatings. The unique characteristics in structure distribution makes FGM offer great promise in applications in many areas and the researches have been widely performed. It is well known that FGM performance depends mainly on the composition distribution. The composition
distribution in FGMs can be tailored to specific requirements and properties of the constituent materials. For example, the structure of ceramic/metal FGMs is designed by considering the thermomechanical properties of the metal
that has high mechanical strength and thermal conductivity of the ceramics that acts as a heat-resisting thermal
shield. Therefore, ceramic/metal FGMs have received growing attention as prospective thermal barrier materials.
A number of numerical analyses and experimental methods have been developed to evaluate the mechanical and
thermal properties of FGMs [1-5].
Various techniques have been employed to the fabrication of FGM, including physical and chemical vapor deposition, sintering, plasma spraying, electroplating and combustion synthesis. Powder metallurgical processing is one of
the most viable routes for FGM, because the composition and microstructure as well as shape forming of FGM can
be easily controlled in a wide range [2,6,7]. The powder metallurgy (PM) or ceramic technology route for processing
of materials and engineering parts includes powder production, powder processing, forming operations and sintering or pressure assisted hot consolidation. Powders of many metals, alloys, compounds and ceramic materials with
particle sizes ranging from nanometers to several hundred micrometers are available from industrial sources or
may be produced by the methods developed over decades in the field of PM or ceramics. Since the material used
to form the sintered part is dispersed into very small portions of individual powder particles nearly ideal conditions
exist to build-up graded materials with varying chemistry or microstructure by using the particles as building blocks.
Practical considerations towards an efficient process design suggest the use of powder mixtures with changing
average particle size or composition during deposition of the material prior to the forming operation. It depends
on the method applied for powder deposition whether a smooth change or a stepwise variation is obtained in the
49

green body. Since the consolidation of the green parts during sintering or hot pressing requires high temperatures at
which diffusion processes are fast enough to enable densification, chemical reactions between particles of different
compositions and the influence of particle size on the sintering behavior have to be taken into account for the final
microstructure and dimensional control of the part. On the other hand thermodynamic factors acting during sintering
may be used to create a gradient, e.g. during liquid-phase sintering [3,8].
The purpose of this research is to develop fundamental constitutional control technique of FGM by powder metallurgy, expecting to optimize FGM fabrication process and further improve its performance.The microstructure and
the composition of the fabricated FGM by powder metallurgy were studied and the relative density and the Brinell
hardness of each layer in the FGM were measured. The relationship between microstructure, composition,
and some physical and mechanical properties were discussed.
2. Experimental procedures
Aluminium powders and B4C particles were used as raw materials to fabricate the FGMs. An average particle size
of B4C particles used as reinforcement material and Al powders (Etial 7) used as matrix materials were 102m and
113m, respectively. Fig. 1(a) and (b) shows the morphologies of the as received Al matrix powders and B4Cparticles [9].
(a)
(b)
Fig. 1. Morphology of as-received powders: (a) Al alloy and (b) Al2O3 particles.
The Al matrix powders are ligamental in shape and the B4C particles are polygonal in shape. These powders are
mechanically mixed and single-axis press, compressed raw samples produced at different pressures. The stacked
layer were pressed at a pressure of 400 and 500 MPa. In ths work, experiments on single-layer, two-layer and
three-layer of Al-B4C FGM, as shown in Fig. 2 and Table1, are conducted [9].

(a)
(b)
(c)
Fig. 2. The composition distribution model of Al-B4C FGMs. (a) Single-layer samples,
(b) Two-layer samples, (c) Three-layer samples
50

Table 1.Configuration of FGMs.

Coded Samples
Composition
Alsingle(400)
100 wt.% Al
Pressure (MPa)
Layer
400
Single
Alsingle(500)
100 wt. % Al
500
Single
Al-5single (400)
95 wt.% Al + 5wt.% B4C
400
Single
Al-5single (500)
95 wt.% Al + 5wt.% B4C
500
Single
Al-10single(400)
90 wt.% Al + 10wt.% B4C
400
Single
Al-10single (500)
90 wt.% Al + 10wt.% B4C
500
Single
(Al+Al-5)two(400)
100 wt. % Al and 95 wt.% Al + 5wt.% B4C
400
Two
(Al+Al-5)two(500)
500
Two
(Al+Al-10)two(400)
400
Two
(Al+Al-10)two(500)
500
Two
(Al+Al-5+Al-10)three(400)
100 wt. % Al , 95 wt.% Al + 5wt.% B4C and 90 wt.% Al + 10wt.% B4C
400
Three
100 wt. % Al , 95 wt.% Al + 5wt.% B4C and 90 wt.% Al + 10wt.% B4C
500
Three
The as-received Al alloy powder, the conventionally mixed (CM) powders were
uniaxially cold pressed in a rectangular die with dimension of 30x30x20mm at 400
and 500MPa, with graphite as the die lubricant. The green compacts were sintered
600 oC for 3h under argon atmosphere. The sintered compacts were cooled to
room temperature in the sintering furnace. The experimental density of the composite samples was measured using Archimedes method. In this technique, density is determined by measuring the difference between the samples weight in air
and when it was suspended in distilled water at room temperature. The theoretical
density was calculated using the mixture rule according to the volume fraction of
the B4C particles. The porosities of FGMs were then evaluated from the difference between the expected and the observed density of each sample. To evaluate
microstructure of produced composites the surface of samples were polished to
achieve a rough surface of about 0.05m. The morphologies and distribution of
the B4C particles and the microstructures of the conventionally both mixed and the
milled Al-B4C FGMs were analyzed on a Zeiss Evo LS10 scanning electron microscope (SEM) and a stereo microscopy.
The particle size distributions were determined using laser diffraction (Malvern,
Model mastersizer Hydro 2000e), connected to a compute that models the volume
size distribution, D10, D50, D90 calculation automatically; three measurements were
carried out for each sample. The hardness of the samples was measured using
Brinell hardness method under a load of 31.25 kg held for 20s. Reported hardness
values were the average of five measurements. With the variation of composition,
the Al-B4C uniform compacts undergo very different shrinkage during densifications as shown in Fig. 3.

3. Results and discussions
Fig. 3. Developing
procedure of FGMs [9].
3.1. Microstructure distribution

The optical and SEM images of the cross-section of the prepared FGM component are shown in Fig. 4 and Fig. 5,
respectively.
(a)
51

(b)
Fig. 4. Optical micrographs of different Al-B4C FGM fabricated by
powder metallurgy (pressed at 500MPa). (a) Single-layer samples,
(b) Two-layer samples, and (c) Three-layer sample.
(c)
(a)
(b)
(c)
Fig. 5. Scanning electron microscopy micrographs at different positions in FGMs. (a) Single-layer samples (pressed
at 500MPa), (b) Two-layer samples (pressed at 400MPa), and (c) Three-layer sample (pressed at 400MPa)
52

It can be seen that the microstructure of the sample takes on a compositional gradient change along the thickness
direction. The layer boundaries were observed clearly, which indicates that the structures of the FGMs were macroscopically heterogeneous due to the graded distribution of the composition. There arent delaminations or defects
at the interlayer boundaries. In the images, it is noted that the light phase in the FGMs is Al and the dark phase is
B4C, which is seen particularly clearly in the SEM image (Fig. 4). The microstructure of the sintered Al-B4C FGMs
is presented in Fig. 5, where the gray and dark phases are Al and B4C, respectively. These images show a good
gradual compositional variation in the FGMs.
The obvious macroscopic interfaces are not observed even on the interfaces between different layers where the
material composition jumps. Fig. 5 shows a typical variation of the microstructure in the FGMs. The varying microstructure is characterized by the gradual variation of the matrix phase from the metal to the ceramic with the increase of B4C. In the metal-rich side, the ceramic particles are dispersed in the metal matrix. With the increase of
B4C, the clusters of the ceramic are formed and their further growths result in the formation of a network structure.
Then, the network of the metal is gradually diminished and turns into the isolated metal particle dispersed in the
ceramic matrix in the ceramic-rich side.
3.2. Some physical properties of FGMs
The graded change of the chemical compositions and microstructure in FGM leads to a continuous distribution of
the properties. As shown in Fig. 6, 7 and Table 2, the density of theoretical, green and sintered and porosities of the
FGMs according to the weight fractions of B4C particles. Al-B4C system show various graded distributions corresponding to constitutional change. Fig. 6, 7 and Table 2 show that density of green and sintered samples decreases
with increasing B4C content. The graphs of green and sintered densities of the FGMs according to the weight fractions of B4C particles are shown in Figs. 6 and 7, respectively.
Table 2. Physical properties of FGMs [9].
Theoretical density
(g cm-3)
Coded samples
Green density
(g cm-3)
Sintered density
(g cm-3)
Green
porosity (%)
Sintered
porosity (%)
Alsingle(400)
2.70
2.52
2.60
6.54
5.19
Alsingle(500)
2.70
2.60
2.61
3.70
3.34
Al-5single (400)
2.69
2.51
2.51
6.74
6.58
Al-5single (500)
2.69
2.59
2.60
3.82
3.50
Al-10single(400)
2.68
2.49
2.50
7.12
6.86
Al-10single (500)
2.68
2.57
2.58
4.27
3.69
(Al+Al-5)two(400)
2.70
2.52
2.52
6.63
6.38
(Al+Al-5)two(500)
2.70
2.59
2.60
3.75
3.42
(Al+Al-10)two(400)
2.69
2.51
2.51
6.88
6.58
(Al+Al-10)two(500)
2.69
2.59
2.60
3.84
3.49
2.69
2.50
2.51
7.09
6.72
2.69
2.59
2.59
4.20
3.75
(a)
(b)
Fig. 6. The green densities of FGMs for different pressing pressure.(a) at 400MPa, (b) at 500MPa.
53

(a)
(b)
Fig. 7. The sintered densities of FGMs for different pressing pressure. (a) at 400MPa, (b) at 500MPa.
Table 3 shows that some theoretical density values of the FGMs decrease (as expected from the rule of mixtures).
Although a decrease was also seen in the experimental densities (green and sintered density values), the value are
lower than those theoretical ones. The density measurements showed that FGMs contain some porosity, and the
amount of porosity in the green and sintered of FGMs increased with the increasing weight fraction of the particles
(Fig. 8 and 9), as observed in the previous investigations [10-17].
(a)
(b)
Fig. 8. The green porosities of FGMs for different pressing pressure.(a) at 400MPa, (b) at 500MPa.
(a)
(b)
Fig. 9. The sintered porosities of FGMs for different pressing pressure.(a) at 400MPa, (b) at 500MPa.
3.3. Hardness of FGMs
The influence of the varying microstructure on the hardness of the FGM sample is obvious, as shown in Fig. 10. As
the content of B4C increases from 0% to 10%, the slope of the hardness curve changes and the hardness increases
substantially. This is mainly caused by the gradual variation of the microstructure inthe FGMs. In these layers, the
matrix phase varies from the softmetal to the hard ceramic, as shown in Fig. 4 and 5. The Brinell hardness of the
FGMs and single-layers were given in Table 3. The relation between the B4C particle content and the hardness of
the FGMs were plotted in Fig. 10. It was seen from Fig. 10 that the hardness of the FGMs increased with increasing
particle weight fraction. As compared to the Alsingle matrix alloy, the hardness of the FGMs was found to be greater,
and addition of B4C particles increase the hardness of the Al alloy [11,18].
54

Table 3. The hardness properties of FGMs.

Coded samples
Brinell Hardness (BHN)
Alsingle(400)
170
Alsingle(500)
189
Al-5single (400)
201
Al-5single (500)
213
Al-10single(400)
226
Al-10single (500)
250
(Al+Al-5)two(400)
170-201
(Al+Al-5)two(500)
195-226
(Al+Al-10)two(400)
175-213
(Al+Al-10)two(500)
195-241
166-195-220
185-220-250
An increase in the hardness of the Al-B4C FGM with increasing weight fractions of B4C from the matrix to B4C
graded regions, for both the FGM fabricated at 400 and 500MPa, respectively (Table 3, Fig. 10), as observed in
the previous investigations [19,20].
(a)
(b)
(c)
Fig. 10. The Brinell hardness of FGMs.(a) Single-layer samples, (b) Two-layer samples, (c) Three-layer sample.
55

4. Conclusions
Single, two and three staged Al-B4C FGMs had been successfully fabricated by powder metallurgy technique. The
relative density of the FGM was more than 93%. The relative density of the three stage FGM (500Mpa) was more
than 95%. Microstructure analysis showed that a good graded composition of FGM had been obtained. The B4C
particles were well embedded into the matrix by solid state sintering. The present work provides a effective approach to fabricating ceramicmetal FGM by powder metallurgy technical for different applications.
1. Al-B4C functionally graded material (FGM) has been successfully developed by the powder metallurgical process
2. Green and sintered density values increases with increasing pressure.
3. Green and sintered density values decreases with increasing B4C content.
4. Hardness of FGMs increases with the increasing B4C content.
Acknowledgement
The authors are grateful to Karadeniz Technical University Research Fund for the financial supporting of this research work (No: 2007.112.10.2).
References
1. Gang Jin, Makoto Takeuchi, Sawao Honda, Tadahiro Nishikawa, Hideo Awaji, Materials Chemistry and Physics
89 (2005) 238243
2. Jingchuan Zhua, Zhonghong Lai , Zhongda Yin, Jaeho Jeon, Sooyoung Lee, Materials Chemistry and Physics
68 (2001) 130135
3. B. Kieback, A. Neubrand , H. Riedel, Materials Science and Engineering A362 (2003) 81105
4. Xin Jin, LinzhiWu, Yuguo Sun, Licheng Guo, Materials Science and Engineering A 509 (2009) 6368
5. S. Lopez-Esteban, J.F. Bartolome , C. Pecharroman, J.S. Moya, Journal of the European Ceramic Society 22
(2002) 27992804
6. Zhang-Jian Zhou, Juan Du, Shu-Xiang Song, Zhi-Hong Zhong, Chang-Chun Ge, Journal of Alloys and Compounds 428 (2007) 146150
7. Zeming He, J. Ma, G.E.B. Tan, Journal of Alloys and Compounds 486 (2009) 815818
8. Li Sun, Basak Oguz, Patrick Kwon, Powder Technology 195 (2009) 227234.
9. I.G. Zerin, S. Ozkaya, Karadeniz Technical University, Department of Metallurgical and Materials Engineering,
Trabzon, Turkey, Graduation Thesis, 38 pages, 2011.
10. Manumanth GS, Iron GA (1993) J Mater Sci 28:2459. doi: 10.1007/BFO1151680
11. Kk M (2005) J Mater Process Technol 161:381
12. Kk M (2006) Composites A 37:457
13. Ghost PK, Ray S (1988) AFS Trans 775782:88
14. Akhlaghi F, Lajervardi A, Maghanaki HM (2004) J Mater Process Technol 155156:1874
15. McCoy OW and Franklin EW (1988) In: Fishman SG, Dhingra AK (eds) Cast reinforced metal composites.
Chicago, USA, p 77
16. Ray S (1988) In: Fishman SG, Dhingra AK (eds) Proceedings of the survey on fabrication methods of cast
reinforced metal composites. ASM/TMS, p 77
17. Ccen U, nel K (1996) Mater Sci Eng A 221:187
18. Purazrang K, Abachi P, Kainer KU (1994) Composites A 25(4):296
19. Rao AG, Mohape M, Kathar VA, Gowtam DS, Deshmukh VP and Shah AK (2010) Materials and Manufacturing
Processes, 25: 572576.
20. Lin CY, Bathias C, McShane HB and Rawlings RD (1999) Powder Metallurgy 42(1): 29-33.
56

YKSEK ENERJL BLYEL TME YNTEM LE

BOR NTRR NANO TP RETM
S. Hale GLER, Ertan EVN, mer GLER, Mustafa AKSOY
Frat niversitesi, Metalurji ve Malzeme Mhendislii Blm, Elaz,Trkiye
ZET
Bu almada tme ve tavlama metodu kullanlarak Bor Nitrr Nano Tpler (BNNT) sentezlenmitir. Balang
tozu olarak amorf bor tozu kullanlm ve bu toz bir planeter bilyal deirmende (Fritsch Pulverisette 7) 20 ve 40
saat boyunca azot atmosferi altnda tlmtr. Yeterli tme salandktan sonra elde edilen tozlar bir tp frn
ierisinde amonyak gaz altnda 1300 oC de 2 saat boyunca tavlanmtr.
Sonu olarak bu teknik kullanlarak BNNTler retilmitir. retilen tpler X-n difraksyon analizi (XRD),yksek
ayrma gl geirimli elektron mikrobu (HR-TEM) kullanlarak incelenmitir.
Anahtar Kelimeler: Bor Nitrr, Nano tp, tme
PRODUCTION OF BORON NITRIDE NANOTUBES USING

HIGH ENERGY BALL MILLING METHOD
S. Hale GLER, Ertan EVN, mer GLER, Mustafa AKSOY
Firat University, Department of Metallurgical and Materials Engineering, Elazg,Turkey
ABSTRACT
In this study , Boron Nitride Nanotubes (BNNTs) were synthesized using a ball-milling and annealing method. Starting powder was used as the amorphous boron powder and in a plenetary ball mill (FritschPulverisette 7) was ball
milled for 20 and 40 hours under nitrogen atmosphere. After sufficent milling, to obtined powders were annealed
under ammonia gas flow at 1300C for 2 hours in tube furnace.
Consequently, the nanotube was produced by using this tecnique. Synthezed tubes were determined by using Xray diffraction analysis (XRD),high-resolution trasmission electron microscopy (HR-TEM)
Keywords: Boron Nitride, Nanotubes, Ball milling
1. GR
Bor nitrr nano tpler (BNNT) teorik olarak 1994 ylnda Rubio tarafndan kefedilmi [1] ve 1995 ylnda Chopra
tarafndan Berkeley niversitesinde baaryla sentezlenmitir [2]. Karbon nano tplerde (KNT) olduu gibi BNNT
lerinde tabakalar arasnda sp2 balar mevcuttur ve BNNT ler de tp eklindeki yaplarndan dolay iyi mekanik
zelliklere sahiptirler. BNNT ler hegzegonal bor nitrr (hBN) tabakalarn, sarlarak silindir eklini almas ile olumulardr. hBN n tabakal yaps BNNT lerin anlalmas iin bir gayet nemlidir [3].
57

KNT lerin elektronik cihazlarn yapsnda kullanlmas ile birlikte aratrmaclar nano lekte elektronik devreler iin
yeni malzemeler aramaya balamlardr. BNNT lerin 5,5eV bant aralna sahip olduu saptanm ve yaltkan
malzeme olarak kullanm ngrlmtr. Bu bant aral tp apna, tpn yapsna, duvar saysna bal olarak
deimektedir [1]. BNNT ler KNT lerin uygun olmad, nano lekte elektronik ve foto elektronik yeni devrelerin
retiminde kullanlabilirlii aratrlmaktadr. Yksek termal stabilitesi, iyi sl direnci, yaltkan zellii eitli korozif
ortamlarda kimyasal direnci, bor nitrr nanotplerin iyi bilinen zelliklerindendir [3].
BNNT lerin retiminde KNT lerde olduu gibi farkl yntemler mevcuttur. Bu yntemler farkl apta, farkl saflkta
ve farkl yapda tp sentezi salamaktadr. Bu amala kullanlan yntemler; ark boaltma, lazer biriktirme, kimyasal
buhar biriktirme (CVD) ve mekanik alamlamadr. Mekanik alamlama iin konvansiyonel deirmenler ve yksek
enerjili bilyeli deirmenler (YEBD) kullanlmaktadr. YEBD ler ilk olarak 1960 l yllarda Benjamin ve grubu tarafndan kullanlm ve konvansiyonel deirmenler yeterince enerji salamadndan dolay ODS alamlarn sentezlemek iin gelitirilmitir. YEBD lerde partikl krma ve boyut azaltma ilk aamada grlmekte ve bu nedenle YEBD
lerde uzun tme zamanlarna gerek duyulmamaktadr. YEBD ler iin tme atmosferi ve tme iddetinin kontrol nem arz etmektedir. nk bu parametrelerin kontrol ile tme sresi boyunca kimyasal ve yap deiimleri gereklemektedir. YEBD lerin farkl tipleri mevcuttur. Bu deirmen tipleri; spex, planeter, atritr, vibrasyonludur.
Nanotp sentezleme aratrmalar iin vibrasyonlu ve planeter bilyeli deirmenler kullanlmaktadr [4].
Bu almada nano tp retmek amac ile, tme ilemi sresince mekanik enerji yardmyla kimyasal dnm
reaksiyonu (in-situ dnm) oda scaklnda gerekletirilmi ve sonraki tavlama ileminde dk scaklklarda
tp oluumu salanmtr.
2. DENEYSEL ALIMA
tme deneyleri bir planeter bilyeli deirmende (Fritsch Pulverisette 7) gerekletirilmitir. Balang malzemesi
olarak Merck kGAA firmasndan temin edilen % 98 saflkta amorf bor tozu kullanlmtr. Deneylerde bilye/toz oran
32/1 olarak seilmi ve B tozu deirmende 20 ve 40 saat boyunca azot atmosferi altnda 400 devir/dak lk bir hzda
tlmtr. tme ilemi oksidasyonu nlemek amac ile koruyucu atmosfer (N2) altnda gerekletirilmitir.
tme ileminden nce, kaplar ierisindeki kalnt oksijeni uzaklatrlmas amacyla tme kaplar azot gaz ile
birka kez temizlenmitir. Daha sonra tlen tozlar 1300C de 2 saat NH3 atmosferi altnda bir tp frn ierisinde
tavlanmtr. NH3 gaznn debisi 500 ml/min olarak seilmitir. tlm ve tavlanm numuneler Frat niversitesi
(F.) Metalurji ve Malzeme Mhendislii Blmnde Bruker D9 marka X-n difraksyon cihaznda (CuK radyasyonu vastasyla) veF. Fizik Blmmde yksek ayrma gl geirimli elektron mikrobu (JEOL JEM 2100F
HR-TEM) kullanlarak incelenmitir.
3. SONU VE TARTIMA
Bor tozunun tavlama esnasnda BNNT lere dnmesi iin ncelikle nano boyuta indirilmesi gereklidir. Bu amala
amorf bor tozu bilyeli deirmende 20 ve 40 saat sreyle tlmtr. Ayrca tme esnasnda tme kaplar
ierisinde bulunan tozlarn bir ksmnn N2 atmosferi ile reaksiyona girerek amorf yapl nano tozlara dnt XRD
incelemeleri ile tespit edilmitir
ekil 1.a-bde 20 ve 40 saat tlm numunelerden elde edilen XRD sonular verilmitir. ekilden de grld
gibi 20 saat tmenin ardndan yaklak 44o de bir pik ortaya kmtr. Bu pik, BN ve FexBy pikleridir. 44o deki bu
pikin 40 saat tme sonunda geniliinde artma meydana gelirken, iddeti nispeten azalmtr. Amorf bor tozunun
azot atmosferinde tlmesinden dolay 20 saat tme sonunda yapda nano boyutlu BN partiklleri olumutur.
Ayrca, tme ilemi srasnda tme kabnn ve bilyelerin anmas ile yapya karan Fe partiklleri tme
sresinin artmas ile birlikte bor ile reaksiyona girerek FexBy ye dnmtr. ekil 1.cde grlen 40 saat tme
ve 1300Cde 2 saat tavlama sonucunda elde edilen XRD analizinde yaklak 26o de ortaya kan (002) pikinin
h-BN ilikili olduu tespit edilmitir ve baz almalarda bu pikin BNNT olduu belirtilmektedir [5]. tme ilemi
srasnda 44o de ortaya kan pikin iddeti, sl ilemden sonra daha da azalmtr. Muhtemelen sl ilem ile beraber FexBy faznda ayrma meydana gelmitir. Pikteki azalmann sebebinin ise bu durum olduu dnlmektedir.
Isl ilem ile beraber yapdaki demir partiklleri de amonyak ile reaksiyona girerek FexN eklinde demir nitrrlere
dnmlerdir. Yapdaki demirin bir ksm ise sl ilem scaklnn etkisiyle bor ile reaksiyona girerek farkl formda
FexBy e dnmtr. Yapda BN piklerinin tamam BN nanotpe ait pikler olmayp, farkl formlarda olumu BN
de yapda bulunmaktadr.
58

ekil 1. XRD sonular; (a) 20 saat tme

sonunda,(b) 40 saat tme sonunda ve (c)
40 saat tme ve 1300Cde 2 saat tavlama
sonucunda
Bu sonular dahilinde tme sonucunda elde edilen metastabil amorf yapnn tpe dnt grlm ve baz
aratrmaclar tarafndan da belirtilmitir [6]. Bu yksek miktarda hata ieren yap difzyon prosesini harekete geirmektedir. Partikl boyutunun nano boyuta dnmesi difzyon mesafesini azaltmaktadr. BN tpn oluabilmesi
iin iki nemli gereksinim vardr. Bunlar; ekirdek alanlar ve serbest atom kaynaklardr. Nano katalizr partiklleri
ve yzey difzyonunun etkisi ile bu zel yaplarn olutuu bilinmektedir [8]. Atomlarn, yzey ksmlarnda ok zayf
balar kurmas ve yzey difzyonunun ortam gazlarnn adsorbsiyonundan byk lde etkilenmesinden dolay
malzeme tanmnda yzey difzyonunun baskn mekanizma olduu dnlmektedir [7,8].
ekil 2de 20 saat (a-b) ve 40 saat (c-d-e) tme ileminden sonra tavlanan numunelerin TEM grntleri verilmitir. ekilde aka grld gibi matris iinde dalm nano Fe partikllerine rastlanmtr. Bu partikllerin
yapya tme kabnn ve bilyelerin anmasndan tr getii sanlmaktadr. tme zamann artmas ile birlikte
Fe partikl miktarnn dereceli olarak artt dnlmektedir [5]. Bu metal partikllerinin nanotp oluumu iin
pozitif bir rol oynadklar ve ekirdekleme iin katalizr grevi yaptklar ekil 2.bde grlmektedir ve ekil 2.bde
ekil 2. 1300Cde 2 saat NH3

atmosferi altnda tavlanan numunelerin TEM resimleri
tpn u ksmndaki Fe partikl zerinden nanotp gelimektedir. Ayrca ayn ekilde nanotpn evresinde farkl
boyutlarda Fe partiklleri mevcuttur. Bu partikllerin etrafnn dnmemi amorf yap ile kapl olduu grlmektedir. Elde edilen TEM grntlerine gre rnlerin bambu tipli nanotpler olduu aka grlmektedir. Bambu tipli
nanotplerin oluum modeli ekil 3 de verilmitir.
59

ekil 3. Bambu tipli BNNTlerin

byme modeli [5].
Bu mekanizmaya gre tme kab ve bilyelerden tozlara geen metal partiklleri tme prosesi boyunca amorf
yap ierisinde homojen olarak dalmtr. 1300Cde nano boyutlu Fe partikllerin hacim ve yzey difzyonu bor
nitrr ve karbondan daha byk olduu varsaylmaktadr [8]. Ergime noktas 1535C olmasna ramen nano boyutlu
olmas nedeniyle demir keltiler yava bir ak davran iine girerek yar kresel duruma gemektedir [8]. Bor
atomlar nano Fe partikl iine difze olurken, azot atomlar nce Fe yzeyler zerinde amonyaktan ayrlmakta ve
daha sonra nano Fe partikl iine difz etmektedir (ekil 3.a). Zaten, tavlama sonunda verilen XRD analizlerinde
Fe4N in bulunmas bu mekanizmay destekler niteliktedir. B ve N yeterli miktara ulatnda ar doymu kat zelti oluturmakta ve bu zeltiden BN tabakalarn oluumu devam etmektedir (ekil 3.b). BNNTler BN kabuklar ve
katalizr arasndaki ara yzeylerden olumaya balamaktadr. Bu byme aamasnda d kabuk partikln her iki
tarafndan gerilip, ayrlrken i kabuk ise kavislenmektedir. Nano tpn klcal etkisinden dolay katalizr partikl
tp iine emilmeye balamaktadr (ekil 3.c). Katalizr partiklnn yzey gerilimini artmasna neden olan bu reaksyonda bor ve azot arasndaki temas alannn azalmasndan dolay emilen katalizr partikl (ekil 3.d) bor ve
azot kayna olarak grev yapmaktadr. Katalizr partikl geri itilip yar kresel ekle geri dndnde bir bambu
yumru olumaktadr (ekil 3.e). Sonuta bu ilemin tekrarlanmas ile bambu tip nano tp byyebilir (ekil 3.f-g).
Bu byme modeli KSK (Kat-Svi-Kat) mekanizmas olarak isimlendirilmektedir [5].
Deneyler sonunda elde edilen nanotplerin boylarnn 200 nm den birka mikrona kadar deitii ve aplarnn
20-100 nm arasnda deitii tespit edilmitir. 40 saat tlm numuneler 20 saat tlm numunelerle karlatrldnda, 40 saat tlen numunelerde tp miktarnn arttrd ve tplerin aplarnn azald tespit edilmitir.
Bunun nedeni; tme sresinin artmas ile beraber azot gaznn absorbsyonun artmasna ve tozlarn partikl
boyutunun daha da azalmasna balanmaktadr [5].
4. GENEL SONULAR
Bu yntem kullanlarak bambu tipli BNNTler baar ile retilmitir. Verilen byme modeline gre nanotplerin
olutuu tespit edilmitir. 20 saat ve 40 saat tlen numuneler karlatrldnda, sl ilemden sonra 40 saatlik
numunelerdeki rn miktarnn artt ve tp apnn azald tespit edilmitir. Bunun nedeni tme ile oluturulan
ekirdek yap saysnn 40 saatte daha ideal olmasna ve tme sresinin artmasyla tlm tozun demir konsantrasyonunun artmasna balanmaktadr.
5. KAYNAKLAR
1. Rubio, A., J. L. Corkill and M. L. Cohen, Theory of Graphitic Boron NitrideNanotubes, Physical Review B, Vol. 49, pp. 5081-5084, 1994.
2. Chopra, N. G.; Luyken, R. J.; Cherrey, K.; Crespi, V. H.; Cohen,M. L.; Louie, S. G.; Zettl, Boron-Nitride
Nanotubes A. Science , Vol. 36 269-966,1995
3. H. Zhang and Y. Chen Boron Nitride Nanotubes:Synthesis and Structure,Nanotubes and nanofibers,
pp 157-174, Australia,2006
4. Y. Chen and J. S. Williams Synthesis of Boron Nitride Nanotubes Using a Ball-Milling and Annealing
Method, Nanoengineering of Structural,Functional, and Smart Materials,pp 182-208, Australia,2006
5. Y. Chen, M. Conway, and J.S. Williams,Large-quantity production of high-yield boron nitride nanotubes,
J. Mater. Res., Vol. 17, No:8, Australia,2002
6. E.J.M. Hamilton, S.E. Dolan, C.M. Mann, H.O. Colijn, C.A.McDonald, S.G. Shore, Preparation of
Amorphous Boron Nitride from the Reaction of Haloborazines with Alkali Metals and Formation of a Novel
Tubular Morphology by Thermal Annealing Chem. Mat.Science,Vol7, pp 11-117,1993.
7. German R.M.,Sintering Theory and Practce, Joyn Wiley & Sons. Inc., USA,1996
8. L. T. Chaddertona, Y. Chen A model for the growth of bamboo and skeletal nanotubes: catalytic capillarity, Physics Letter A, Vol. 263, pp 401-405,Australia,2001
60

BOR KARBRL ELMASLI KESC SOKETLERN MKROYAPI VE

MEKANK ZELLKLER
Serkan ISLAK*, Durmu KIR**, Halis ELK***, Erturul ELK****
Kastamonu niversitesi, Cide Rfat Ilgaz Meslek Yksekokulu, 37600 Kastamonu, sislak@kastamonu.edu.tr
**
Kocaeli niversitesi, Gebze Meslek Yksekokulu, 41400 Kocaeli, durmuskir@gmail.com
***
Frat niversitesi, Teknoloji Fakltesi, Metalurji ve Malzeme Mh. Blm, 23100 Elaz,
durmuskir@gmail.com, hcelik@firat.edu.tr
****
Tunceli niversitesi, Mhendislik Fakltesi, Makine Mh. Blm, 62000 Tunceli
ecelik@tunceli.edu.tr
ZET
Bu almada, doal ta kesme ilerinde kullanlan elmasl kesici soketlere bor karbr (B4C) ilavesinin mikroyap ve
mekanik zellikleri zerine etkisi aratrlmtr. Bu amala, deneylerde B4C arlka % 2, 5 ve 10 oranlarnda kullanld. Tm deneylerde scak presleme ilemi 35 MPa basnta, 700 C scaklkta ve 3 dakika sreyle yaplmtr.
Soketlerin mikroyap ve faz bileimi taramal elektron mikroskobu (SEM), X-n difraktogram (XRD), X n enerji
dalm spektrometresi (EDS) ile belirlenmitir. Mikrosertlik ve eme dayanm deerleri ise srasyla sertlik ve
noktal eme test cihazyla llmtr. Soketlerin sertlik ve eme dayanmlar bor karbrn oranna bal olarak
deimitir.
Anahtar Kelimeler: Elmasl soketler, bor karbr, scak presleme
MICROSTRUCTURE AND MECHANICAL PROPERTIES OF DIAMOND

CUTTING SEGMENTS WITH BORON CARBIDE
ABSTRACT
In this study, effect of boron carbide (B4C) addition on microstructure and mechanical properties of diamond cutting
segments that are used in cutting works of natural stones were investigated. For this purpose, the boron carbide
was changed as 2, 5 and 10 wt. % percents. In all of the experiments, hot pressing process was carried out at 35
MPa pressure, at 700 C temperature and 3 minutes sintering time. Microstructure and phase composition of segments were determined by scanning electron microscopy (SEM), energy dispersive spectroscopy (EDS) and X-ray
diffraction (XRD) analysis. Microhardness and bending strength values were measured by hardness and threepoint bending test devices, respectively. Hardness and bending strength values of segments changed depending
on boron carbide rate.
Keywords: Diamond segments, boron carbide, hot pressing
1. GR
Sentetik elmasn kullanm alanlar arasnda, sert malzemelerin kesilmesi, talanmas, delinmesi ve parlatlmas
ilerinde kullanlan elmasl takmlar en byk paya sahiptir. Elmasl takmlarn piyasada, dairesel testereler, karotlar,
elmasl teller ve matkaplar gibi birok eidi mevcuttur [1]. Bu takmlar genellikle toz metalurjisi yntemleri ile retilmektedir. Toz metalurjisi yntemi ile retilecek paralarn preslenmesi genellikle oda scaklnda yaplmaktadr.
Son yllarda oda scakl zerindeki ortamlarda da scak presleme ile para retimi salanmaktadr. Bu yntem
61

kullanlarak daha az kalp-metal tozu ara yzey srtnmesi ile, daha dk presleme basnlarnda daha yksek
younluun elde edildii grlmtr [2-5]. Scak presleme esnasnda, elmas tanecikleri fiziksel ve kimyasal etkileimler ile metal matrise balanr. Elmasl kesici takmn kesme performansn olumsuz ynde etkileyen, elmasn
grafitlemesi, znmesi ve zarar grmesi gibi faktrlerden kanmak iin sinterleme parametrelerinin ok dikkatli
seilmesi gerekir [6].
Elmasl kesici takmlarn kesme performans ve kullanm sresi birok faktr tarafndan etkilenmektedir. Bu temel
faktrler; elmas ve matris zellikleri, soket retim metodu, kesme artlar (kesme hz, evresel hz ve kesme derinlii), kesme modu (ayn ve zt ynl kesim), doal tan minerolojik ve mekanik zellikleri, soutma etkisi, kesme
makinesinin zellikleri ve operatrn becerisidir [7]. Elmasl kesici takmlardaki soketlerin retiminde kullanlan
metalik matrislerin iki temel fonksiyonu vardr. Birincisi elmas skca tutmak, ikincisi ise elmas kayb ile uyumlu
bir oranda optimum olarak anmaktr [8,9]. Bu ilikiyi en st dzeye getiren teknikler metal-elmas ara yzeyinde
atomik balanma, mekanik dayankllk ve anma hznn kontroln kapsar. Elmas tanelerinin matrisin ar bir
ekilde anmas sonucunda desteksiz bir ekilde matris yzeyinden ne fazla miktarda kmal ne de zamanndan
nce matristen kopmaldr. Bunun iin matrisin anma direnci kesilecek malzemenin anabilirlik zellii ile uyumlu
olmaldr [10,11].
Literatrde bir ok almada Fe, Co, Ni, Ti, W, Cu ve CuSn matris malzemesi olarak kullanlmtr. Nitkiewicz ve
Swierzy [12], elmasl soketlerde kalayn kesme performans zerine etkisini incelemiler ve belirli miktarda ilavesinin kesme performansna olumlu etki yapt gzlenmi ve demirli matrislerle farkl takmlarda da kullanlabilecei
ett edilmitir. Barbosa ve arkadalar [13], Fe-Cu-Co matrisli elmasl takmlar retmilerdir. En uygun matris bileiminin Fe-% 60 Cu-%20 Co olduunu yaplan noktal eme ve anma testleriyle gstermilerdir. Artan Cu miktar
ile soketlerin younluu artm ve sertliklerinde de iyileme gzlenmitir.
Metalik matrisin anma direncini arttrmak ve elmas ile matris ara yzeyinde ba glendirmek amacyla matrise
karbrler ilave edilmektedir. Literatrde bu konuda kstl alma mevcuttur. Meszaros ve Vadasdi [14] Co-% 2 WC
matrisli elmasl kesici takmlar retmilerdir. Yaplan almada WCn abrasyon ile matrisin ktle kaybn kontrol
ettii ve bu ekilde anma direncini arttrd rapor edilmitir. Oliveira ve arkadalar [4], elmasl kesici takm iin
matris olarak Fe-Cu-SiC tozlarn kullanmlardr. SiC ilavesi ile anma orann kontrol edici etkiye sahip olan sertlikte % 14 orannda bir art gzlenmitir. Ayrca ilave edilen SiCn tane boyutu arttka matrisin anma direncinde
art meydana gelmitir.
Son zamanlarda, yksek ergime noktas, yksek sertlii, dk younluu, yksek kimyasal kararllk ve mkemmel mekanik zelliklere sahip olan bor karbr (B4C) ileri teknoloji iin nemli bir malzemedir. Bor karbr elmas ve
kbik bor nitrrden (cBN) sonra bilinen en sert malzemedir. Yksek sertliinden dolay anma direncinin iyiletirilmesi amacyla kullanlmaktadr. Yksek dayanm/younluk oran onu endstri iin ideal bir malzeme yapmaktadr
[15-18].
Bu almada, doal ta kesme ilerinde kullanlan elmasl soketlere bor karbr (B4C) ilavesinin mikroyap ve mekanik zellikleri zerine etkisi aratrlmtr. Bu amala, deneylerde B4C arlka % 2, 5 ve 10 oranlarnda ilave
edilmitir. Tm deneylerde scak presleme ilemi kullanld. Soketlerin mikroyap ve faz bileimi taramal elektron
mikroskobu (SEM), X-n difraktogram (XRD), X n enerji dalm spektrometresi (EDS) ile belirlenmi; mikrosertlik ve eme dayanm deerleri ise srasyla sertlik ve noktal eme test cihazyla llmtr.
Deneysel almalarda matris olarak CuSn ve B4C tozlar kullanlmtr. Bor karbr tozu farkl yzde arlk oranlarnda matrise ilave edilmitir. Soket retiminde kullanlan matris gruplar Tablo 1de, kullanlan tozlarn zellikleri
ise Tablo 2de verilmitir. ekil 1de soket retiminde kullanlan CuSn ve B4Cn SEM fotoraflar ve XRD grafikleri
grlmektedir. Bronz tozu kresel ekilli ve bor karbr tozu ise keskin keli bir ekle sahiptir.
No
Tablo 1. Soket retiminde kullanlan matris gruplar ve retim parametreleri

Sinterleme
Sinterleme
Basn
Matris (% a.)
CuSn
B 4C
S1
100
S2
98
S3
95
S4
90
10
scakl (C)
sresi (dak.)
(MPa)
700
35
62

Tablo 2. Kullanlan Tozlarn zellikleri

Tozlar
zellik
Tane boyutu (m)
CuSn
% 85 Cu, % 15 Sn, % 99.9 saflk
45-50
B4 C
% 79 B, % 20.5 C, % 99.9 saflk
~20
ekil 1. Soket retiminde kullanlan tozlarn SEM fotoraflar ve XRD grafikleri: (a) CuSn tozu, (b) B4C
Tablo 1de ki gibi hazrlanan matris gruplar mikserde 30 dakika sre ile 20 d/d hzda % 1 orannda parafin ya
karma eklenerek krom kaplanm elik bilyeler ile birlikte kartrlmtr. elik bilye kullanmndaki ama karma
katlan parafin yann topak oluturmasn engellemektir. Toz halindeki soketler 15 MPa basnla souk olarak
preslendi. Biskvi eklindeki soketler grafit kalplarda scak presleme teknii kullanlarak nihai soket haline dntrld. Her bir soket 35 MPada 700 C scaklkta 3 dakika sinterleme sresinde elde edildi. ekil 2de soketlerin
grafit kalba yerletirme dzeni ve sinterleme grafii grlmektedir.
ekil 2. (a) Soketlerin grafit kalba yerletirme dzeni ve (b) sinterleme grafii
63

Scak presleme yntemi ile retilen soketlerin bal younluu, sertlii ve eme dayanm tespit edilmitir. Numunelerin bal younluk lm Archimedes prensibine gre yaplmtr. Sertlik lm iin Karl Frank marka
sertlik lme cihaznda 62,5 kg yk ve 2.5 mm apnda bilye ile numunelerin sertlii Brinell cinsinden llmtr.
Soketlerin eilme dayanmlar, 40 mm x 7 mm x 3.2 mm lsndeki numuneler kullanlarak noktal eme testi
ile tespit edilmitir.
Metalografik incelemeler iin numuneler, 3.2 mm x 7 mm x 10 mm llerinde kesilmitir. Elde edilen metalografi
numuneleri 80-1200 meshlik zmpara kadna tutularak yzeyleri temizlenmitir. Daha sonra 1 ve 6 mlik elmas
pasta ve inceltici yardmyla yan kesit yzeyleri parlatlmtr. Mikroyap incelemeleri iin numuneler 20 saniye sreyle 5 gr. FeCl3, 50 ml HCl ve 100 ml H2O zeltisinde dalanmtr. Soketlerin mikroyapsnn retim koullarna
bal olarak nasl deitiini ve faz yaplarn tayin etmek iin ve krk yzeylerini incelemek iin taramal elektron
mikroskobu (SEM), enerji dispersive spektograph (EDS), X- n difraksiyonu (XRD) ve spektral analizlerden yararlanlmtr. XRD analizleri 30 kV ve 15 mAde CuK radyasyonu kullanlarak Rigaku Geigerflex X-n difraktometresi ile elde edilmitir.
3. SONULAR VE TARTIMA
CuSn ve CuSn-B4C matrisli soketler scak presleme yntemi ile 700 C scaklkta, 35 MPa basnta ve 3 dakika sinterleme sresinde baaryla retildi. CuSn matrisinin mikroyapsnda -Cu ve -bronzu (Cu3Sn) fazlar olumutur.
Bu durum Cu-Sn ikili faz diyagram (ekil 3) ve ekil XRD grafii (ekil 4) ile de desteklenmektedir. Cu3Sn faz ekil
5deki SEM fotoraflarndan da grld gibi Cu partikllerinin tane snrlarnda kelmitir.
ekil 3. Cu-Sn ikili faz diyagram [19]
ekil 4. Soketlerin XRD grafii
64

CuSn tozuna arlka % 2, 5 ve 10 oranlarnda B4C ilave edilerek CuSn-B4C kompoziti retilmitir. retilen CuSnB4C matrisinde B4C paracklar mikroyapda nispeten homojen olarak dalmtr ve CuSn tarafndan kuatlmtr
(ekil 5). takviye partikllerin matris ierisinde homojen olarak dalmad durumlarda kompozitin mekanik ve
fiziksel zellikleri olumsuz ynde etkilenmektedir [20]. Bu takviyeli matrislerin SEM fotoraflarnda koyu renkli ve
keli partikller B4Clerdir. Bor karbr oran arttka, B4C partiklleri CuSnnin tane snrlarna doru yaylarak bir
a oluturmutur (ekil 5b-c-d). Ayrca bor karbr ilave miktar arttka soketlerin XRD grafiklerindeki B4C piklerinin iddetleri artmaktadr. XRD grafikleri CuSn ve B4C arasnda herhangi bir kimyasal reaksiyonun olmadn da
gstermektedir. CuSn-B4C soket matrislerinin mikroyapsnda gzenekler tane snrlarnda olumutur. Bor karbr
oran arttka gzeneklilik miktar artmtr. Bu durum B4Cn sinterlenebilme zelliin dk olmasndan kaynaklanmaktadr.
CuSn-B4C matrisli soketlerde B4C ilavesinin sktrlabilirlik zellikleri zerine belirlemek iin soketlerin deneysel
younluklar lld. Matrislerin deneysel ve teorik younluklar kullanlarak bal younluklar belirlendi. ekil 6da
bor karbr ilavesinin soketlerin deneysel ve bal younluklar zerine etkisi verilmitir.
ekil 5. Soket matrislerinin SEM fotoraflar: (a) CuSn, (b) CuSn-% 2 B4C, (c) CuSn-% 5 B4C ve
(d) CuSn-% 10 B4C
Tablo 3te ekil 5deki SEM fotoraflarnda belirlenen blgelerin EDS analizi verilmitir. 1 blgesinin EDS analizi
tane kesinde oluan Cu3Sn ve B4C fazlarn iaret etmektedir. 2 nolu blge matris faz yani CuSnyi gstermektedir. 3 nolu blgenin analizi % 99.142 C ve % 0.858 Sndir. Bu bor karbr tanesi zerinden alnan analizdir. Fakat
EDS analizinde B elementinin okunmamasnn sebebi karbon ve borun atom aplarnn ok kk ve birbirine yakn
olmasdr. 4 nolu blge tane snrlarnda oluan Cu3Sn fazdr.
Tablo 3. Soketlerde verilen blgelerin EDS analizi
Blge
Kimyasal bileim (% a.)

B
Cu
Sn
1 blgesi
0.000
13.425
53.142
33.433
2 blgesi
0.000
0.000
85.461
14.539
3 blgesi
4 blgesi
0.000
0.000
99.142
0.000
0.000
62.281
0.858
37.719
65

ekil 6. Bor karbr ilavesinin soket matrisinin deneysel ve bal younlua etkisi
Artan bor karbr orannda younluklarda d meydana gelmitir. Bu durum bor karbrn younluunun (2,52 gr/
cm3) bronzun younluundan (8,68 gr/cm3) dk olmasyla ilgilidir. Yine artan bor karbr ilavesiyle bal younluklarda d meydana gelmitir. Bu durum artan bor karbr orannn sinterlenebilirlii olumsuz etkilemesiyle aklanabilir [21]. Dier bir sebep ise, matris ile takviye eleman yani bronz ile bor karbrn ergime noktalar arasndaki
byk farkllk, sinterleme annda partikllerin tekrar dzenlenmesinde nleyici bir faktr olmasdr. Bor karbr ilaveli
soketlerde en iyi younlama CuSn-% 2 B4C matrisinde yaklak % 93,01lik bal younluk ile olmutur (ekil 6).
ekil 7de CuSn ierisine farkl oranlarda ilave edilen bor karbrn sertlik zerine etkisi grlmektedir. Her bir numune iin toplam alt adet lm yaplmtr. Deerlendirmede lmlerin ortalamas kullanlmtr. Bor karbr ilavesiyle elde edilen CuSn-B4C soket matrislerin sertliklerinde belirgin bir art olmutur. CuSn, CuSn-% 2 B4C, CuSn-%
5 B4C ve CuSn-% 10 B4C soketlerinin sertlikleri srasyla 78 HB, 87 HB, 109 HB ve 118 HB olarak llmtr. Bu
sertlik artna bor karbrn dalm mukavemetlendirme etkisi sebep olmutur. Sertlik art ile soket matrisinin
anma direnci arttrlmaya allmtr.
ekil 7. B4C ilavesinin soketlerin eme mukavemeti ve sertliine etkisi

Krlma tokluunu belirlemek iin CuSn ve CuSn-B4C matris numunelerine 3-noktal eme testi uygulanmtr. Her
bir matris iin noktal eme testi beer defa tekrarlanmtr. Elde edilen deerlerin ortalamas alnarak retim
66

parametrelerinin etkisi tartlmaya allmtr. Eme mukavemeti zerine bor karbr ilavesinin etkisi yine ekil
7de grlmektedir.
Bor karbr ilave miktar arttka soket matrislerin eme mukavemeti deerlerinde d gzlenmitir. CuSn, CuSn% 2 B4C, CuSn-% 5 B4C ve CuSn-% 10 B4C soket matrislerinin eme dayanmlar srasyla 477.40 MPa, 412.00
MPa, 372.42 MPa ve 244.48 MPa olarak llmtr. Eme mukavemeti deerlerinde bu dn sebebi yksek
sertlie sahip bor karbrn artan miktarlarda soket matrisini gevrekletirmesidir. Ayrca takviye eleman ile snek
matris arayzeyinde genleme katsays farkllndan dolay gerilim younlamas meydana gelir. Bu gerilim younlamas eme mukavemetinin dmesine yol amtr [22]. Ksaca bor karbr bronz matrisinin krlmasnda hata
unsuru olmutur.
Kompozit malzemelerde genel olarak krlma olay partikl krlmas, arayzeyde zayf balanma ve matris malzemesinin deformasyonu olmak zere hata mekanizmas ile oluur [23]. Bor karbr takviyesiz olan soket numunesinde matrisin plastik deformasyonu krlma olaynda hkim mekanizmadr (ekil 8a). Yine bu numunede boyun
verme olay dier numunelere gre daha youn miktardadr. Bor karbr takviyeli soketlerin krlma yzeyinde ise
bor karbr taneleri ile CuSn matrisi arasnda zayf balanmas sz konusudur. Bor karbr miktar arttka matris
ile bor karbr taneleri arasndaki balanma daha da zayflamaktadr. Bu durum ekil 8b-c-dde ak bir ekilde
grlmektedir. Bu zayf balanma olay sinterleme koullarnn yetersizliinden kaynaklanmaktadr. Daha yksek
presleme basnc ve sinterleme scakl kullanlarak matris (CuSn) ile takviye eleman (B4C) ara yzeyindeki zayf
balanmann stesinden gelinip eme dayanmnn arttrlaca dnlmektedir.
ekil 8. Soket matrislerinin krma yzeylerinin SEM fotoraflar:

(a) CuSn, (b) CuSn-% 2 B4C, (c) CuSn-% 5 B4C ve (d) CuSn-% 10 B4C
3. GENEL SONULAR
Scak presleme ile 700 C sinterleme scakl, 35 MPa presleme basnc ve 3 dakika sinterleme sresinde retilen
CuSn-B4C matrisli soketlerde bor karbrn matris iinde nispeten homojen olarak dald SEM almalaryla
gzlenmitir. Bor karbr taneleri bronzun tane snrlarnda olumu, bronz tarafndan kuatlmtr. Ayrca artan bor
karbr ilavesinde gzenek miktarnda art gzlenmitir. Bor karbr ilavesiyle elde edilen CuSn-B4C soket matrislerin sertliklerinde belirgin bir art olmutur. En yksek sertlik deeri % 10 B4C ilavesinde 118 HB olarak llmtr.
Bor karbr ilaveli soketlerde en iyi younlama CuSn-% 2 B4C matrisinde yaklak % 93,01lik bal younluk ile
olmutur. Bor karbr ilave miktar arttka soket matrislerin eme mukavemeti deerlerinde d gzlenmitir. En
dk toklua 244.48 MPa eme dayanm ile arlka % 10 B4C ieren numune sahiptir. Bor karbr ilavesiyle
takviye ve matris ara yzeyinde zayf ara yzey balanmalar tespit edilmitir. Bu durum sinterleme koullarnn
yetersizlii ile ilikilendirilmitir.
67

4. TEEKKR
Bu almann yrtlmesi ve sonulandrlmas ile ilgili konularda TEF.10.01 nolu proje ile maddi destek salayan
Frat niversitesi Bilimsel Aratrmalar Projeleri Birimine (FBAP), teekkr ederiz.
5. KAYNAKLAR
1. Xu, X.P., Friction studies on the process in circular sawing of granite, Tribology Letters, Vol. 7, pp. 221-227,
1999.
2. Sun, J., Liu, C., Wang, R., Low pressure hot pressing of B4C matrix ceramic composites improved by Al2O3 and
TiC additives, Materials Science and Engineering: A, Vol. 519, pp. 27-31, 2009
3. Kim, T.W., Determination of densification behavior of Al-SiC metal matrix composites during consolidation
processes, Materials Science and Engineering: A, Vol. 483-484, pp. 648-651, 2008
4. Oliveira, L.J., Bobrovnitchii, G.S., Filgueira, M., Processing and characterization of impregnated diamond cutting tools using a ferrous metal matrix, International Journal of Refractory Metals and Hard Materials, Vol.
25, pp. 328-335, 2007.
5. zel, S., elik, E., Turhan, H., The investigation of microstructure and mechanical properties of Cu-Al/B4C
composites produced by using hot press, e-Journal of New World Sciences Academy, Vol. 4 (1), pp. 106112, 2009.
6. Zeren, M., Karagz, ., Defect characterization in the diamond cutting tools, Materials Characterization, Vol.
57, pp. 111-114, 2006
7. Byksa, I.S., Effect of cutting mode on the sawability of granites using segmented circular diamond sawblade, Journal of Materials Processing Technology, Vol. 183, pp. 399-406, 2007
8. Konstanty, J., Production of Diamond Sawblades for Stone Sawing Applications, Key Engineering Materials,
Vol. 250, pp. 1-12, 2003
9. Konstanty, J., Factors affecting diamond retention in stone sawblade segments, Key Engineering Materials,
Vol. 250, pp. 13-20, 2003
10. Karagz, ., Zeren, M., The microstructural design of diamond cutting tools, Materials Characterization, Vol.
47, pp. 89-91, 2001
11. Konstanty, J., Powder Metallurgy Diamond Tools, Elsevier Ltd, The Metal Powders Technology Series,
pp. 106-107, 2005
12. Nitkiewicz, Z., Swierzy, M., Tin influence on cutting behaviour of diamond sawblades for Stone cutting, 13th
International Scientific Conference on Achievements in mechanical and materials Engineering, 16-18
May 2005, Gliwice-Wista, Poland, pp. 467-470, 2005
13. Barbosa, A.P., Bobrovnitchii, G.S., Skury, A.L.D., Guimares, R.S., Filgueira, M., Structure, microstructure and
mechanical properties of PM FeCuCo alloys, Materials and Design, Vol. 31, pp. 522526, 2010
14. Meszaros, M., Vadasdi, K., Process and equipment for electrochemical etching of diamond-containing Co-Wc
tools and recovery of diamond from used steel tools, International Journal of Refractory Metals and Hard
Materials, Vol. 14, pp. 229-234, 1996
15. Pierson, H.O., Handbook of Refractory Carbides and Nitrides, William Andrew Pub., Noyes, 1996
16. Spohn, M.T., Boron Carbide, Minerals Review, Vol. 6, pp. 113-115, 1994
17. Jiang, T., Jin, Z., Yang, J., Qiao, G., Investigation on the preparation and machinability of the B4C/BN nanocomposites by hot-pressing process, Journal of Materials Processing Technology, Vol. 209, pp. 561-571,
2009
18. Ma, Q.C., Zhang, G.J., Kan, Y.M., Xia, Y.B., Wang, P.L., Effect of additives introduced by ball milling on sintering behavior and mechanical properties of hot-pressed B4C ceramics, Ceramics International, Vol. 36, pp.
167-171, 2010
19. Saunders, N., Miodownik, A.P., Cu-Sn (Copper-Tin), Binary Alloy Phase Diagrams, vol. 11, pp. 278-87,
1990.
20. Lee, D.W., Ha, G.H., Kim, B.K., Synthesis of Cu-Al2O3 nano composite powder, Scripta Materialia, Vol. 44,
pp. 2137-2140, 2001
21. Rahimian, M., Ehsani, N., Parvin, N., Baharvandi, H.R., The effect of particle size, sintering temperature and
sintering time on the properties of Al-Al2O3 composites, made by powder metallurgy, Journal of Materials
Processing Technology, Vol. 209, pp. 5387-5393, 2009
22. Samuel, A.M., Gotmare, A., Samuel, F.H., Effect of solidification rate and metal feedability on porosity and
SiC/Al2O3 particle distribution in an AlSiMg (359) alloy, Composites Science and Technology, Vol. 53, pp.
301315, 1995
23. Park, K.T., Mohamed, F.A., Creep strengthening in a discontinuous SiCAl composite, Metall. Mater. Trans.
A, Vol. 26, pp. 31193129, 1995
68

B4C TAKVYEL ALMNYUM KPKLERN KPRME

ZELLKLERNN ARATIRILMASI
Uur GKMEN*, Halil KARAKO**, Arif UZUN***, Mehmet TRKER**
Gazi niversitesi, Atatrk MYO, Makine ve Metal Teknolojileri Blm, Teknikokullar, 06500, Ankara,
ugokmen@gazi.edu.tr
**
Gazi niversitesi Teknik Eitim Fakltesi, Metal Eitimi Blm, Teknikokullar, 06500, Ankara,
halil.karakoc@hotmail.com,
mturker@gazi.edu.tr
***
Kastamonu niversitesi, Cide Rfat Ilgaz MYO, Kaynak Teknolojisi Blm, Kastamonu, a
uzun@kastamonu.edu.tr
ZET
Bu almada n alaml Alumix 231 tozu ierisine, % 1 orannda TiH2 ve farkl oranlarda (arlka % 3, 6, 9 ve 12)
B4C tozu ilave edilerek kartrlmtr. Karm tozlar 600 MPa basn altnda tek ynl preste sktrlm ve 550
o
Cde n stmaya tabi tutulmutur. Daha sonra numuneler sktrma ynnde deforme edilerek kprebilir kompozit preform malzemeler haline getirilmitir. Elde edilen preform numuneler 710C scaklkta kprtme ilemine tabi
tutularak metal matrisli kompozit kpkler retilmitir. retilen metalik kpklerde B4C ilavesinin kprme davran
zerine etkileri aratrlmtr.
Anahtar Kelimeler : Alminyum Kpk, Alumix 231,B4C, Kprme Davran
INVESTIGATION OF THE FOAMING BEHAVIOUR OF B4C

REINFORCED ALUMNUM FOAMS
ABSTRACT
In this study, Alumix 231, 1% titanium hydrate (TiH2) and various amount of B4C (3%, 6%, 9% and 12 % by weight)
powders were mixed, and then compacted at 600 MPa pressure by using a uniaxial action press and pre-heated to
550 oC in a furnace. Then the samples were deformed in the direction of compression to produce foamable composite precursor materials. Produced precursor samples were foamed at 710C in order to produced metal matrix
composite foams. Effects of B4C addition on foamability behavior of metallic foams were invested.
Keywords: Aluminum Foam, Alumix 231, B4C, Foaming Behaviour
1. GR
Kapal gzenekli alminyum kpkler mekanik ve fiziksel zelliklerinden dolay yapsal ve fonksiyonel uygulamalar
iin cazip hale gelmi malzemelerdir. Bu malzemelerin endustriel boyutta retiminde dkm ve toz metalurjisi (TM)
en fazla kullanlan yntemlerdir. Ancak TM yntemi net ekilli paralarn dorudan retimine olanak salamas
aratrmaclar bu yntem zerine daha da ok yneltmitir. TM yntemi ilk olarak Fraunhofer Malzeme Aratrma
Enstits (IFAM) tarafndan gelitirilmitir [1]. Bu yntem de sandvi levha eklinde veya karmak ekilli homojen
gzenek yaplara sahip kpk paralar kprebilir preform malzemelere uygulanan sl ilem ile retilmektedir [2].
lem sreci yksek younlukta preform malzeme retimi iin Al tozlar ile kprtc madde tozlarnn kombinasyonu ile balamaktadr. Daha sonra preform malzemelerin alminyumun ergime derecesinin biraz zerindeki bir
69

scaklkta kprtlmesi ile ilem sreci tamamlanmaktadr. Bu srete ergiyik hale gelen alminyum ierisinde, kprtc madde znerek hidrojen gaz aa karmaktadr. Yap ierisinde giderek artan hidrojen gaz, gzenekli
alminyum kpk oluumunu salamaktadr. Ancak ergiyik halde bulunan Al kpk, plato snrlar ve hcre duvarlar
boyunca ergiyik drenaj ve artan yzey alan nedeniyle termodinamik ve kinetik adan kararl deildir [3,4]. Bu etkiler mekanik zellikleri dk, homojen olmayan kpk yaplarn oluumuna neden olmaktadr. Daha nce yaplan
almalarda kpn kararlln ayarlayabilmek iin yap ierisine SiC, Al2O3, TiB ve TiC gibi seramik paracklar
ilave edilmektedir [5-8]. lave edilen seramik paracklar ergiyik halde bulunan alminyumun viskozitesini artrarak,
hcre duvar boyunca ergiyik akn drmekte, drenaj orann ve hcre duvar kntlerini azaltmaktadr. Fakat
slatlabilirlii iyi olan paracklarla bu durum daha etkin hale gelebilmektedir. Bu almada ise B4C paracklarnn
kprebilirlie etkisi aratrlmtr.
Deneysel almalar uygun miktarlarda hazrlanan n alaml Alumix 231 (2,5 Cu, 0,5 Mg, 14 Si - < 160 m), TiH2
(arlka % 1 - < 45 m) ve B4CP ( arlka % 3, 6, 9 ve 12 - < 10 m) tozlarnn karm ile balamtr. Karm
boyutlu kartrcda (turbula) 30 dakika sreyle plastik bir kap ierisinde gerekletirilmitir. Daha sonra karm
tozlar, kprebilir metal matrisli kompozit (MMK) preform malzemeler retmek amac ile elik kalp ierisinde tek
ynl olarak 600 MPa basn altnda Preslenmitir ( ekil 1-a). Presleme sonras 550 Cde 4 saat bekletilen numuneler % 50 orannda deforme edilmitir (ekil 1-b). Daha sonra kprebilir kompozit preform malzemeler 710
C scaklkta, yaklak 10 dakika frn ierisinde bekletilerek kprtme ilemine tabi tutulmutur. Bu ilem sresince
herhangi bir kprtme kalb kullanlmamtr. retilen kpk numunelerin younluklar ve hacimsel olarak genleme oranlar 0,1 mg hassasiyetteki terazi ve younluk kiti ile llmtr. Buna gre younluk hesab E.1de verilen
Arimet prensibi esasna gre yaplmtr. Bu eitlikte, * kpn younluunu, mhava kpn havadaki arln
ve msu kpn su ierisindeki arln ifade etmektedir.
*=mhava/(mhavamsu) (1)
Genleme oran ise E. 2de verilen formle gre hesaplanmtr. Bu formlde V* kpn hacmini, V ise kprtme
ncesi numunenin ilk hacmini ifade etmektedir.
Hacimsel Genleme ( HG ) = (V*/V-1) x 100
(2)
ekil 1. Souk preslenmi (a) ve % 50 deforme edilmi preform malzemeler (b)

3. DENEYSEL SONULAR ve TARTIMA
ekil 1de % 1 orannda TiH2 ieren ve 710C scaklkta kprtme ilemine tabi tutulan numunelerde takviye elaman
(B4C) miktarna bal olarak hacimsel genileme ve younlukta meydana gelen deiimler gsterilmitir. Grafie bakldnda parack ilavesinin hacimsel genlemeye azaltc, younlua ise artrc ynde etki ettii grlmektedir.
ekil 1. B4C miktarna bal hacimsel genileme ve younluk deiimi
70

ekil 2de takviyeli ve takviyesiz alminyum kpklerin ara kesit fotoraflar verilmitir. Serbest kprtme neticesinde elde edilen numunelerde B4C ilavesinin kprme davranna ve gzenek morfolojisine olumsuz ynde etki ettii
aka grlmektedir. Parack miktar % 6y getiinde numunelerde yeterli kprme meydana gelmemektedir.
% 3 ve % 6 orannda parack ieren numunelerde ise gzenek boyut dalmnn, takviyesiz numuneye kyasla
homojen olmad grlmektedir.
ekil 2. B4C miktarndaki arta bal olarak gzenek yaps ve younlukta meydana gelen deiim
ekil 3te % 6 B4C ieren Almix 231 matrisli kompozit kpklerin SEM grnts verilmektedir. Bu grntlerde
B4C paracklar net olarak tespitedilememitir. Ancak yaplan EDX analizlerinde 1 nolu blgede C elementine
rastlanmtr. Paracn bu blgede matris ierisine gmlm olduu dnlmektedir. Bu durum parack-matris
uyumunun iyi olduunu gsterebilir. Fakat baz aratrmalarda dkm yntemi ile retilen Al-B4C kompozitlerde
1100oCnin altnda alminyum ile bor karbr arasndaki slanmann dk olduu bilinmektdir. Bundan dolay ilave edilen parack ya kaplanmakta yada sl ileme tabi tutulmaktadr [9]. SEM grnts haritalandrldnda
(FastMap) B ve C elementinin yap ierisinde homojen bir ekilde dald grlmektedir (ekil 4). Bundan dolay
ilave edilen paracklarn hcre duvarlarnda homojen dalm sergiledii sylenebilir. Matris malzemesi olarak n
alaml Alumix 231 kullanldndan alminyumdan sonra yapda en fazla Si elementine rastlanmaktadr. Silisyum,
TM yntemi ile kpk retiminde matris ierisine ilave edilen en yaygn alam elementlerindendir [10]. Si, tektik
noktay drdnden dk scaklklarda ergiyik hale gelen Al ile parack ara yzey uyumu artabilir.
ekil 3. % 6 B4C ieren Almix 231 matrisli kompozit kpklerin SEM grntleri
71

ekil 4. % 6 B4C ieren Almix 231 matrisli kompozit kpklerin FastMap analiz yzeyi
4. SONULAR ve NERLER
Bu almada toz metalurjisi yntemi ile retilmi metal matrisli kompozit kpklerde B4C ilavesinin kprme davran zerine etkisi incelenmi. Elde edilen verilere gre B4C oranndaki art younlukta ata, hacimsel genlemede
ise azalmaya neden olmutur. Parack ilavesinde kritik deer % 6 olarak belirlenmitir. nk % 6dan sonra gzenek morfolojisinde ve kprme davrannda olumsuz ynde etkiler sz konusudur. Ayrca parack boyutunun (<10
m) kklnden dolay matris/parack ara yzey uyumu tam olarak gzlenememitir. Ancak hcre duvarlarnda
homojen dalm sergiledii FasMap analizi ile belirlenmitir. Daha sonra yaplacak almalarda parack boyutunun etkisi ve mekanik zellikler belirlenebilir. Bu sayede daha ak sonulara ulalabilir.
KAYNAKLAR
1. Baumaster, J., US patent, 1992
2. Yu, C.J.,Eifert, H.H., Banhart, J., Baumeister, J., Metal foamingby a powdermetallurgymethod: Production,
propertiesandapplications, Mat Res Innova, 2:181188, 1998
3. Gergely V., Jones R.L. and Clyne T.W., The Effect of Capillarity-driven Melt Flow and Size of Particles in Cell
Faces on Metal Foam Structure Evolution, Trans. JWRI, 30:371-376, 2001
4. Gergely V. and Clyne, T.W., Drainage in standing liquid metal foams: modelling and experimental observations. Acta Mater., 52(10): 3047-3058, 2004
5. Kennedy A.R. and Asavavisithchai S., Effect of ceramic particle additions on foam expansion and stability in
compacted Al-TiH2 powder precursors, Adv. Eng. Mater., 6(6): 400-402, 2004
6. Guden M. and Yuksel S., SiC-particulate aluminum composite foams produced from powder compacts: foaming and compression behavior, J. Mater. Sci., 41(13): 4075-4084, 2006
7. Kennedy A.R. and Asavavisithchai S., Effects of TiB2 particle addition on the expansion, structure and mechanical properties of PM Al foams, Scr. Mater., 50(1): 115-119, 2004
8. Asavavisithchai, S., and Opa, A., Effect of TiC Particles on Foamability and Compressive Properties of Aluminium Foams, Chiang Mai J. Sci., 37(2) : 213-221, 2010
9. Kennedy, A.R., Bramton, B., The Reactive Wetting and Incorporation of B4C Prticles into Molten Aluminium,
Scripta Materiala, 44:1077-1082, 2001
10. Esmaeelzadeh, S., Simchi, A., Foamability and compressive properties of AlSi73 vol.% SiC0.5 wt.% TiH2
powder compact, Materials Letters 62:15611564, 2008

72

CHARACTERIZATION
OF POWDER AND
PARTS
www.turkishpm.org
73

Transverse Rupture Strength Properties of

Diamond Impregnated Metal Matrix
James D. Dwan
Mechanical Engineering Dept. ITT Dublin, Tallaght, Dublin 24, Ireland
Abstract
The determination of mechanical properties of diamond impregnated metal matrices (DIMMs) is very important if
proper understanding of the relationship between workpiece and the diamond tool is to be achieved. Transverse
Rupture Strength (TRS) is a common mechanical test carried out on metal matrices as used in diamond tools. This
is mainly because standard tensile testing is more problematic to carry out successfully due to the more brittle
nature of the metal matrices used in diamond tools, especially cobalt matrix. Mechanical testing of DIMMs is rarely
carried out mainly due to cost. This paper reports on TRS properties of diamond impregnated cobalt metal matrix
(DICoMM). The effects of diamond size and concentration on the TRS of PM cobalt have been investigated. A measure of ductility called Displacement-at-Break derived from bend testing is also reported. The results presented
and effect of the addition of diamond to the failure of DICoMM materials proposed.
1.0 Introduction
Most research work carried out to-date into the mechanical properties of diamond impregnated metal matrix materials has concentrated solely on the metal matrix. However, some work has been conducted on mechanical property
determination of DIMMs [1, 2, 3, 4, 5, 6, & 7]. However, their work was very limited in a number of areas [8, 9 &
10]. The optimum wear of the diamond impregnated metal matrix is paramount to the efficient operation and life of
the diamond tool. However, the matching of the mechanical properties of the diamond tool to its workpiece in order
to achieve this optimum is not very well understood. The purpose of this present paper into Transverse Rupture
Strength (TRS) is only part of an overall investigative work into the wear-matching of the diamond tool and the
workpiece.
2.0 Transverse Rupture Strength (TRS) Testing & PM/PMMC Type Materials
As mentioned in previous papers by the author [1, 2, 3 & 5]. PM and particulate metal matrix composites (PMMCs) materials are related to DIMMs in their macro and microstructure. They are used by the author as reference
materials in developing and understanding the mechanical properties of DIMMs. Particulates used in PMMCs can
be regular or irregular in shape and can arranged in a random or with a preferred orientation. The PM process is a
common method used for the fabrication of PMMCs and these will only be considered here [11, 12, 13, 14 & 15].
Transverse rupture testing of PM as well as PMMCs is a very common test. Regarding hardmetals, it is used as a
characteristic of resistance to fracture [16]. Various versions of it are used, e.g. 3-point and 4-point, and standards
e.g. ASTM B528-76, different sample preparations are carried out including the grinding & polishing of the surfaces,
different specimen dimensions, crosshead speeds and spans e.g. 16-40mm, are used, and so one must take care
in using such values unless all test parameters are mentioned [17, 16, 18]. TRS of PM-type PMMCs depends on
structure and composition but is also especially sensitive to the degree of porosity both micro and macro-pores
which act as internal flaws.
In TRS testing, maximum tensile stress is experienced on the outer fibres of the loaded beam and so any flaws
present on this outer surface will be potential crack initiators. Having measured the load to break the specimen, the
Modulus-of-Rupture (MOR) or simply TRS which is valid if no plasticity is detected in the bend test is calculated.
Also, depending whether it is three-point or four-point type test will influence the failure stress and the statistical probability of finding a critical flaw on the outer surface. So this high sensitivity to external flaws (stress concentrations)
results in relatively high scatter of values. So for minimisation of scatter in results, sample preparation is paramount
e.g. polished samples are often used.
74

In PMMCs it is found that TRS is affected both by the size and type of the ceramic particles [17], some researchers
found that the addition lowered TRS values [19], also that TRS increased with decreasing particle size and which
also caused an increase in variability in TRS data. There was also an increased scatter in the bending strength
data [20].
3.0 Experimental Procedure
Eurotungstene COUF ultrafine cobalt powder was used as the metal matrix in its granulated form (63-350m) with
approx.1.3 % binder. Element 6 synthetic diamond SDA 85+ grade was used in the following US Mesh sizes: (25/30,
35/40, 45/50, 60/70 & 80/100). The diamond concentrations (DCs) used were 1, 10, 20, 30 & 40 for all the above
sizes. The nominal specimen dimensions were 55mm x 5mm x 10mm. Specimens were hot pressed at 800oC with
the preparation procedure and hot pressing profile as already described in [5]. 100% cobalt specimens were also
hot pressed using the same temperature of 800oC. Replication was achieved by using four (4) specimens for each
treatment of diamond size and concentration. Randomisation of the experimental testing was also practised to ensure good experimental protocol. In total, 121 samples were tested. Density was determined for all the specimens
using the standard Archimedes Principle method.
An Instron 8516 servohydraulic universal testing machine with Instron proprietary interface software SERIES-IX
[21] was used. A 10kN load cell with a strain rate of 0.5mm/min was used. A three-point bend fixture with a span
of 40mm was used with an external linear variable differential transducer (LVDT) to accurately measure the beam
deflection, allowing the Displacement-at-Break to be determined (Figure 1).
Figure 1. Three-Point Bend Fixture Mark I showing TRS specimen & LVDT extensometer.
A safety cage also allowed the recovery of broken specimens.
Having measured the load to break the specimen, the TRS was calculated using the conventional formula, Equation
3.1, as found in the ASTM Standard B528-76:

(3.1.)
where P = break load (N),
L = (span) distance between the supporting rollers (mm), (40mm),
t = thickness of the test specimen (Specimen Depth or Height) (mm),
w = width of the test specimen (mm).
4.0 Results & Discussion
4.1. TRS Specimens Results - % Theoretical Density (%TD)
Figure 2 shows for the TRS type specimens the average %TD value for each DC. Included is the %TD for CoMM in
red in the graph. As can be seen in Figure 2, the addition of diamond does cause a reduction in %TD when added
to the cobalt matrix. The average %TD for CoMM is 95.6% whereas the average for all TRS DICoMM specimens
is 93.9%.
75

Figure 2.TRS Specimen Results: Figure shows the Average %TD achieved for CoMM and DICoMMs
for each DC. The average values recorded on the graph are the overall average obtained for each DC. CoMM
is included for comparison purposes.
Figure 3 represents the %TD results for each individual specimen for each US Mesh size plotted against DC.
Figure 3. TRS Specimen Results: Figure shows %TD for each specimen achieved for CoMM and
DICoMMs for each US Mesh size used plotted against DC.
The graph shows the large spread found for each of the DCs. Another observation is that the increasing addition
of diamond to the Co matrix seems to increase the amount of scatter in %TD as can be seen as DC increases.
Standard Deviation of %TD for each US Mesh size plotted against DC does show increasing scatter for increasing
DC can be seen in Figure 4.
Figure 4. TRS Specimen Results: Figure shows the Standard Deviation for %TD achieved for CoMM and
DICoMMs for each US Mesh size within each DC. The results indicate that increasing diamond causes
an increase in scatter in %TD.
76

4.2. TRS Specimens Results - TRS Test Results

Figure 5 shows the individual TRS failure stress achieved for CoMM and DICoMMs specimens for each DC, showing
a large amount of scatter. Included in the graphs are the TRS results for the 100%Co matrix for comparison.
Figure 5. TRS Specimen Results: Figure shows the individual specimen TRS results for CoMMs
(40mm Span) & DICoMMs (40mm spans) plotted against DC. The results are for each specimen for each
US Mesh size and DC. CoMM specimen results shown in red.
Averaging all the TRS results for 100% cobalt and the DICoMM specimens for each diamond concentration the
graph in Figure 6 clearly shows that with increasing diamond concentration, failure stress decreases.
Figure 6. TRS Specimen Results: Average failure stress for each DC for specimens which were tested using
40mm span. CoMM average TRS result (40mm span) shown in red.
What is not evident in Figures 5 & 6 is how failure stress behaves with increasing diamond concentration for each
US Mesh size. As an example, Figure 7 shows the average failure stress for 60/70 US Mesh diamond DICoMM
specimens showing that as diamond concentration increases the failure stress decreases. This effect is found for
all the other US Mesh sizes with some showing it clearly while others not as strongly.
Figure 7. TRS Specimen Results: Figure shows the average failure stress for 60/70 US Mesh diamond
DICoMM specimens showing that failure stress decreases as diamond concentration increases. CoMM average
TRS result (40mm span) shown in red.
77

Figure 8 shows clearly when diamond size decreases there is an increase in TRS failure stress. This effect is found
for all DCs even though the effect is more pronounced in some in comparison to others the effect is still present. The
effect is in keeping with that found in the literature. Another observation is that as diamond concentration increases
there is a drop in TRS failure stress which was already pointed out previously.
Figure 8. TRS Specimen Results: All DC10 and DC30 TRS specimens tested using 40mm span, showing the
effect of increasing failure stress with decreasing diamond size is still showing significance at different diamond
concentrations.
Figure 9. TRS Specimen Results: Figure shows the Standard Deviation for Failure Stress achieved for CoMM
and DICoMMs for each DC used.
As can be seen in Figure 9, the standard deviation for each US Mesh size is plotted against DC. From the graph
it can be seen that there is a decrease in the level of scatter with increasing DC. Within each DC, there is a slight
increase in the range of scatter for DC1 and DC10 in comparison with the other DCs.
Regarding the level of scatter with diamond size (US Mesh), in all DCs there is no significant increase or decrease
in scatter as measured by standard deviation with diamond size discernable. Interestingly, the level of scatter for
100% cobalt is greater than any DC as seen in the figure.
The ductility of bend specimens can be measured as the Displacement-at-Break. Hosking et al. [22] have found
that for PMMCs the ductility is a function of volume-fraction but is independent of particle size. Regarding DICoMM
materials, it is found that diamond concentration and particle size strongly influence ductility as measured by Displacement-at-Break, as can be seen in Figures 10 and 11 below.
The results are just for the TRS tests carried out on DICoMM specimens using 40mm span. For diamond size,
results for different DCs are plotted against diamond size and show a reasonable correlation, with correlation coefficients for DC1 of R = 0.41, DC20 of R = 0.40 & DC30 of R = 0.48.
78

Figure 10. TRS Specimen Results: Graph of Displacement @ Break plotted against diamond size.
The trendline showing a decreasing displacement with increasing diamond size, DC1, DC20 and DC30.
R values for DC1 = 0.41, DC20 = 0.40 & DC30 = 0.48.
Figure 11. TRS Specimen Results: Graph of Displacement @ Break plotted against DC. The trendline showing a
decreasing displacement with increasing DC, R = 0.40.
In Figure 11 where Displacement-at-Break is plotted against diamond concentration shows with increasing diamond concentration Displacement-at-Break decreases with a correlation coefficient R equal to 0.40, in agreement
with Hosking et al. [22].
From the results presented the author proposes that the addition of diamond introduces crack initiating flaws to the
cobalt matrix, and with increasing DC and diamond size it increases the chance of finding a fatal flaw thus reducing
the TRS and DICoMM ductility. Failure may occur from a defect within the test piece and not from the surface.
The true fracture stress is then rather lower than that calculated. Failure may occur away from the loading point in
three-point bending. Again, the true fracture stress is lower than that calculated, but this error can be corrected if
the position of the failure relative to the loading point is noted. Further investigations into this will be carried out and
findings will be published in due course.
4.5. Fractography - TRS Specimens
This section is going to show a range of photomacrographs of the fracture surfaces of the DICoMM materials found
during the TRS testing. Presented will be just a sample to indicate the typical variability found. Fracture surfaces
chosen are ones that the author thinks will be interesting to the reader and that will also aid understanding the
analysis of the results to be presented.
Figure 12 shows the fracture surface of a specimen which was hot pressed using a 30/35US Mesh size and a diamond concentration DC40. The diamond present can be seen as yellow/green in colour and also areas of showing a
strong reflection are pull-outs which are sockets where diamond has been pulled out of during the fracture process
and would be present in the opposing fracture surface of the fractured specimen. Another interesting feature is the
presence of clusters of diamonds which in high diamond concentrations and especially coarse sized US Mesh sizes
are very common, however are detrimental to TRS fracture strength of the specimen.
79

Figure 12. TRS specimen showing fracture surface of specimen 30/35 DC40 showing diamonds present on the
fracture surface. Run 134/1, mag. x 10 TRS Type Specimens showing Fracture Surfaces.
Figure 13. TRS specimen showing fracture surface of specimen 25/30 DC40 showing large clustering of diamonds present on the fracture surface. Run 146/2, mag. x 10.
Figure 13 shows a TRS fracture surface showing coarse diamonds of US Mesh size 25/30 and DC40, which have
large areas of clustering present throughout the specimen. This clustering of diamond behaves as a great source
of flaws to initiate fracture.
Figure 14. TRS specimen showing fracture surface of specimen 45/50 DC30 showing large clustering of diamonds present on the fracture surface. Run 179/2, mag. x 10.
Figure 14 shows the fracture surface of the TRS specimen with 45/50 US Mesh diamond size and a diamond concentration of 30. It shows a good distribution of diamond throughout the fracture surface which would be expected
because finer diamond generally gives better distribution than coarser diamond sizes.
5.0 Conclusions
(1) The addition of diamond to cobalt matrix lowers the percent theoretical density achievable resulting increased
in porosity level in diamond impregnated segments.
(2) The TRS results for DICoMM materials show a large variability due to the addition of diamond.
(3) The TRS of DICoMMs decreased with increasing diamond concentration. With increasing diamond concentration a shift downwards in TRS was found to occur.
(4) Increasing diamond size at constant diamond concentration reduces the TRS strength of DICoMM materials.
(5) It is proposed that the addition of diamond introduces a crack initiating flaw to the cobalt matrix, and with increasing DC and diamond size it increases the chance of finding a fatal flaw thus reducing DICoMM TRS.
REFERENCES
[1] James Dwan, Impact Properties of Diamond Impregnated Metal Matrices, Industrial Diamond Review, 2/2003.
[2] James D Dwan, Fracture Toughness Determination of Diamond Impregnated PM Cobalt, EPMA Euro PM2006,
22-25 Oct 2006, Ghent Belgium
[3] J. Dwan, Analysis of ASTM399 Fracture Toughness Testing of Diamond Impregnated Co Matrix, Euro PM 2009,
Copenhagen Denmark, October. 2009.
[4] D.OMahony, J. Dwan, Effect of Diamond on the Fatigue Properties of PM Cobalt, Euro PM 2006, Ghent, Belgium, 23-25 Oct. 2006.
[5] James Dwan, Impact Properties of Diamond Impregnated Cobalt Metal Matrix, EURO PM 2002, European
Conference on Hard Materials & Diamond Tooling, Lausanne, Switzerland October 7-9th, 2002. pp. 50-56.
80

[6] James D. Dwan, WEAR properties of diamond impregnated Cobalt Metal, EURO PM2008, 29th Sept. 1st Oct.
2008, Mannheim Germany.
[7] Y.Blake, J.Dwan, N. McClelland, M.J. Jackson, Investigation on wear process of diamond blade tools, Int. J.
Manufacturing Technology and Management, Vol. 15, Number 2, pp.228-237, 2008.
[8] Lin, Z., Queeney, R.A., Fracture Resistance of Diamond Reinforced Hot Pressed Cu/Ni Powders, Powder Metallurgy International, Vol 18, #12, 1986.
[9] Yu-Zan Hsieh , Jing-Fure Chen, Shun-Tian Lin, Pressureless sintering of metal bonded diamond particle composite blocks, J., Materials Science , Vol. 35 (2000), pp. 5383 5387] ]
[10] A. L.Majstrenko, The strength and fracture of composite diamond-bearing tool materials, Advances in Fracture
Research (Fracture 84), Proc. 6th Intl. Conf. Fracture (ICF6), New Delhi, India, 4-10 Dec. 1984.
[11] Ibrahim, F.A. Mohamed, E.J. Lavernia, Particulate reinforced metal matrix composites a review, J. Mater
Science Vol.26, (1991) pp. 1137-1156.
[12] Narula, P. Czubarow, D. Seyterth, Poly(borazinylamine): an excellent precursor for the preparation of low volume fraction metal-matrix composites containing metal borides and nitrides as ceramic phase, J. Mater. Sci. Vol.
33 (1998) pp. 1389-1397.
[13] W. Frazier, Particulate Materials and Processes, a navy overview, Advanced Particulate Materials and Processes 1997, Proc. Fifth Intl Conf. On Advanced Particulate Materials and Processes (APMP). April 7-9, 1997,
West Palm Beach .Florida.
[14] K.I. Parashivamurthy, R.K. Kumar, S. Seetharamu, M.N. Chandrasekharaiah, Review on TiC reinforced steel
composites, J. Mater. Sci. 36 (2001) pp. 4519-4530.
[15] P. Yih, D.D. Chung, Titanium diboride copper-matrix composites, J. Mater Science, 32 (1997), pp. 17031709.
[16] H. Reshetnyak, J. Kbarsepp, Resistance of hardmetals to fracture, Powder Metallurgy, 1998, Vol. 41. No.3
pp. 211-216.
[17] M.M Oliveira, J.D. Bolton, Mechanical properties of high speed steel base composites containing TiC and TiN
ceramic additions, ICCM/9, Madrid, 12-16th July, 1993, pp. 149-156.
[18] A. Chakraborty, S.B. Bhaduri, J.J. Reddy, Y.R. Mahajan, The effect of processing parameters on the mechanical properties of Al2O3 /SiCw composites, PMI Vol. 23, No.3, 1991. pp. 169-173.
[19] Manuela Oliveira, John D. Bolton, Effect of ceramic particles on the mechanical properties of M3/2 high Speed
Steel, The International Journal of Powder Metallurgy, Vol. 32, No.1, 1996. pp. 37-48.
[20] R. Vassen, M. Koldewitz, A. Ruder, Influence of binder content and particle size on green strength of WPP
parts, Powder Metallurgy, 1995 Vol.38, No. 1, pp. 55-58.
[21] SERIES-IX Software, Instron Corp., High Wycombe, UK.
[22] F M Hosking, F. Folgar Portillo, R. Wunderlin, R. Mehrabian, Composition of aluminium alloys: fabrication and
wear behaviour, J. Mater Sci. 17 91982) pp. 477-498.
81

STUDY ON THE EFFECT OF TiB2 CONTENT ON MICROSTRUCTRE

AND PROPERTIES OF Al-TiB2 NANOCOMPOSITE
Zohreh SADEGHIAN* and Behnam LOTFI**
*Department of Materials Science and Engineering, Faculty of Engineering,
Shahid Chamran University, Ahvaz, Iran, z.sadeghian@scu.ac.ir
** Department of Materials Science and Engineering, Faculty of Engineering,
Shahid Chamran University, Ahvaz, Iran, behnaml@scu.ac.ir
ABSTRACT
Al-TiB2 nanocomposite was synthesized by mechanical alloying of elemental powders. A double step process was
used to prevent the formation of undesirable phases. The resulting powders were consolidated by spark plasma sintering followed by hot extrusion. Microstructural characteristics of powder particles and consolidated samples were
studied by X-ray diffractometry, scanning electron microscopy and transmission electron microscopy. The obtained
powder showed a good thermal stability against grain growth and particle coarsening. Extruded Al-TiB2 exhibited
improved mechanical properties with values higher than those reported for similar composites made by other processes. Decreasing TiB2 content to 10 wt.% caused no extreme reduction in mechanical properties.
Keywords: Aluminum matrix nanocomposite, Mechanical alloying, In situ TiB2, Spark plasma sintering, Mechanical
properties.
1. INTRODUCTION
TiB2 is known as a suitable reinforcing phase for Al-base composites because of its thermodynamic stability, high
modulus, excellent refractory properties and a high resistance to plastic deformation even at high temperatures [13]. In the last decade in situ metal matrix composites (MMCs) have been developed, in which the reinforcements are
introduced in the metal matrix during fabrication, by a chemical reaction between the constituents. In comparison
to traditionally fabricated materials, in situ MMCs undergo less degradation at high temperatures. This is because
of their superior thermodynamic stability, stronger interface bonding resulting from the clean reinforcement-matrix
interfaces and finer and more uniform distribution [4]. Several techniques including mechanical alloying have been
developed to fabricate in situ MMCs [4-5]. MA has an advantage over other in situ fabrication routes as it is capable
of producing nanostructured composite powder with high uniformity [5].
In previous investigations it has been reported that during the in situ synthesis of Al-TiB2 composites from different
starting powder mixtures, Al3Ti intermetallic compound is also formed. This phase is brittle and has been reported
to considerably reduce the fatigue life of composites [6-7]. Therefore it is of interest to eliminate the formation of
Al3Ti intermetallic compound.
A challenge in processing of nanostructured materials is that long time exposure at high temperature sintering, often
results in severe grain growth. Several consolidation techniques such as hot-pressing, shock consolidation, sintering with the application of ac currents, pulsed electric current and spark plasma sintering (SPS) are introduced to
overcome these difficulties [8]. SPS provides fast densification with minimal grain growth in a short sintering time.
The aim of present study was to study the influence of second phase content at 10 and 20 wt.% on microstructure
and properties of the material. Consolidation of the powder by SPS and hot extrusion was conducted to obtain bulk
materials.
82

Elemental Al (63 m), Ti (40-60 m) and B (2 m) powders were used as starting materials. The aluminum powder
with an average particle size of 63 m was supplied from ECKA Granulate, Velden. The titanium powder with a
particle size of 40-60 m was obtained from GKN Sinter Metal Filters, Radevormwald, and the Merck boron powder
had a particle size of about 2 m. Powder mixtures were milled by a Fritsch planetary ball mill with a rotating speed
of 360 rpm. The ball to powder weight ratio was 10 and the diameter of the chromium steel balls was 15 mm. MA
was done under argon and 1 wt. % zinc stearate was added to the mixture as a process control agent.
A double step process was used to obtain an in situ Al-TiB2 metal matrix powder. In the first step Ti and B powders
were milled with the composition of Al- 62.01 wt. % Ti-27.99 wt. % B. This powder was then milled with additional
aluminum powder to achieve the tailored compositions of Al- 10 and 20 wt. % TiB2.
Powders were sintered by FCT HP D 250 spark plasma sintering (SPS) equipment. Powder was placed into a
graphite die with a diameter of 40 mm and compacted under argon atmosphere with an applied pressure of 35
MPa. The whole process lasted 600 sec and the maximum temperature was 550 C with the dwell time of 0 sec.
The changes of the SPS parameters during the consolidation process are shown in Fig. 1.
Figure 1. An example curve showing the evolution of SPS conditions during the consolidation process.
The density of the SPS materials was determined using Archimedes principle. The sintered samples were then hot
extruded by direct and backward extrusion in order to obtain suitable rods of composites for mechanical tests.
Investigation of the structural changes during mechanical alloying and after sintering was conducted by a SEIFERT
30033 PTS diffractometer employing monochromatic Cu K radiation (= 0.15406 nm). XRD scans were performed
with a step size of 0.05 in 2 and a dwell time per step of 20 s. The microstructures of the powder particles and
the sintered samples were studied by scanning electron microscope (SEM, LEO) and transmission electron microscopy experiments (TEM, FEI Tecnai G2 200 kV). The TEM samples were prepared by using focused ion beam
(FIB) technique. Tensile behavior at high temperature was studied by MTS 30/HS testing machine with a strain rate
of 0.008 mms-1.
Fig. 2 shows the X-ray diffraction patterns of the Al- 62 wt.% Ti- 28 wt.% B and Al with 10 and 20 wt.% TiB2 powders
after different milling times. After 20 hours of milling (Fig. 2-b) no evidence of remaining titanium or formation of
undesired phases could be detected on the XRD pattern. Milling of this powder with additional Al powder for 20 h
yields Al- 20 wt.% TiB2 and/or Al- 10 wt.% TiB2 compositions (Fig. 2-c and d). Detailed structural changes during MA
are presented elsewhere [10-11]. The grain size of the aluminum matrix and TiB2 was obtained from XRD analysis
using WilliamsonHall (WH) equation [12]. The grain size of both TiB2 particles and aluminum matrix after double
step MA was measured to be about 15 nm for Al- 20 wt.% TiB2.
83

Figure 2. XRD patterns of Al-62 wt.% Ti-28 wt.% B powder mixture, (a)asreceived, (b) as-milled for 20 h, (c) final
Al-20 wt.% TiB2 powder and d) final Al-10 wt.% TiB2 powder obtained from double step mechanical alloying.
The cross-sectional SEM micrographs of final powder particles of both compositions are shown in Fig. 3. A fine and
uniform distribution of TiB2 particles is observed in Al- 20 wt.% TiB2 (Fig.3-a). At higher magnification obtained from
scanning transmission electron microcopy (STEM), the average TiB2 particle size was found to be about 90 nm with
a distribution of 10 nm to 1 m (Fig. 3-b). The mean TiB2 particle size seems to be smaller than that of previous studies on in situ Al-TiB2 composite produced by MA [6]. As seen in Fig. 3-c in Al- 10 wt.% TiB2 the size of TiB2 particles
yield a wider distribution from a few nanometers to about 3 m. this can be attributed to the effect of Al matrix as a
ductile material to reduce TiB2 fragmentation during milling.
Final powders obtained from the double step mechanical alloying were sintered using SPS technique. A typical XRD
pattern obtained from SPSed Al-TiB2 samples is shown in Fig. 4-a. After SPS at 550 C no significant structural
change occurred in the consolidated nanocomposites. It can be concluded that by the double stage synthesis process, the formation of undesirable compounds even after exposure to sintering temperature, is prevented. Lu et al.
reported that during the high temperature exposure of as milled AlTiB powder mixture, Al3Ti phase was formed
in the aluminum matrix along with TiB2 [7]. The grain size of Al matrix after sintering increased to 30 nm, indicating
that Al matrix has a relatively good stability against grain growth.
Figure 3. Typical cross-sectional a) SEM, b) STEM images of Al- 20 wt.% TiB2 and c) SEM image of Al- 10 wt.%
TiB2 powder particles.
84

Final powders obtained from the double step mechanical alloying were sintered using SPS technique. A typical XRD
pattern obtained from SPSed Al-TiB2 samples is shown in Fig. 4-a. After SPS at 550 C no significant structural
change occurred in the consolidated nanocomposites. It can be concluded that by the double stage synthesis process, the formation of undesirable compounds even after exposure to sintering temperature, is prevented. Lu et al.
reported that during the high temperature exposure of as milled AlTiB powder mixture, Al3Ti phase was formed
in the aluminum matrix along with TiB2 [7]. The grain size of Al matrix after sintering increased to 30 nm, indicating
that Al matrix has a relatively good stability against grain growth.
Figure 4. XRD pattern of the samples, a) SPSed Al-20 wt.% TiB2, b) extruded Al-20 wt.% TiB2 and extruded Al-10
wt.% TiB2.
SPSed samples were hot extruded with a pre heating temperature of 400C and extrusion rate of 0.6 mm.s-1 to
produce rods of Al-TiB2 nanocomposites. X-ray patterns of Al-20 wt. % TiB2 and Al-10 wt. % TiB2 nanocomposites
after hot extrusion are shown in Fig. 4-b and c. No structural changes could be detected in the X-ray patterns. SEM
observations revealed that the size of TiB2 particles in Al-20 wt. % TiB2 after extrusion ranged from 30 nm to 2 m
(see Fig. 5). Therefore, the sample showed no considerable increase in particle size compared to that for SPS
compact as well as milled powder. Also Al grain size increased only slightly to 35 nm after extrusion. In Al-10 wt. %
TiB2 the maximum size of TiB2 particles was found to be about 3 m, which showed an acceptable stability against
growth compared to the powder.
Microhardness and hardness values of the samples at different stages are presented in Table 1. A significant decrease in the hardness values occurred after consolidation of the powders, which is caused by elimination of cold
work effects during annealing at high temperatures. Hardness values of the samples were further reduced slightly
after extrusion. Nevertheless even the hardness of Al-10 wt. % TiB2 is much higher than 84 VHN reported in the
literature for the same material prepared by different route [6]. According to the Table 1 by reducing the amount of
TiB2 in the composite from 20 to 10 % the hardness showed a small decrease of 3.8 %. This is in good agreement
with the findings of previous studies on other nanocomposite systems such as Al-Al2O3 [13] and Ni-SiC [14].
Figure 5. SEM images of extruded nanocomposites, a) Al-20 wt. %TiB2 and b) Al-10 wt. %TiB2.
85

Table 1. Hardness values of Al-20 wt. %TiB2 and Al-10 wt. %TiB2 nanocomposites at different processing stages.
Extruded sample hardness,
VHN
180
Sintered sample hardness,

VHN
206
Powder
microhardness, VHN
480
173
196
460
Sample
Al-20 wt.%TiB2
Al-10wt.%TiB2
Table 2 presents the tensile properties of Al-20 wt. %TiB2 and Al-10 wt. %TiB2 nanocomposites at ambient temperature. Both compositions showed much higher yield and tensile strength than those reported for composites with
similar compositions [1, 6]. The improved yield strength in the present study can be explained by Orowan strengthening, caused by the resistance of closely spaced fine, hard TiB2 particles for passing of dislocations. Al-TiB2 composites produced in this study showed a brittle behavior in tensile test. Decreasing the TiB2 content in this system
caused only 5 % reduce in strength. Similar results have been reported for metal matrix nanocomposites, previously
[13,14]. It is well known that particles smaller than 100 nm are responsible for the Orowan strengthening. When in
a metal matrix nanocomposite the content of reinforcement at high values like 20 wt. % is reduced, this may cause
a reduction in the number of larger particles. Despite the fact the matrix is still saturated with nano particles which
are acting as Orowan resistors [15].
Fig. 6 shows the effect of temperature on tensile properties of bulk nanocomposites up to 400 C. In both compositions tensile strength did not decrease drastically up to 300 C. Hence, it can be concluded that even at high
temperatures Orowan strengthening is the dominant mechanism. As presented in Fig. 7 Al-TiB2 nanocomposites
produced in the present study showed higher tensile strength than those fabricated by other techniques at high
temperatures. On the other hand the composites exhibited brittle behavior even at high temperature of 400 C.
Table 2. Tensile properties of Al-20 wt. %TiB2 and Al-10 wt. %TiB2 nanocomposites at room temperature.
Elongation, %
1.4
1.8
Tensile strength, MPa

543
514
Yield strength ,MPa

483
456
Sample
Al-20 wt. % TiB2
Al-10 wt. % TiB2
Figure 7. A comparison between the tensile strength of Al-TiB2 nanocomposites prepared in this study and Al
matrix composites presented in the literature.
86

4. CONCLUSIONS
Al TiB2 nanocomposite powder was synthesized by a double-step MA process of elemental powders. Microstructural observations showed formation of TiB2 particles with a relatively uniform distribution in the Al matrix after a
total milling time of 40 h. No traces of undesirable phases such as titanium aluminides were observed even after
consolidation of the powder by SPS. Al-TiB2 nanocomposite showed a tensile strength of 543 MPa with 20 wt. %
and 514 MPa with 10 wt. % TiB2, which is much higher than those reported for similar composites made by other
processes. Al-TiB2 nanocomposites showed a brittle behavior in tension. Al-TiB2 nanocomposites presented a good
microstructural and mechanical stability at elevated temperatures. It was revealed by the results that reducing the
TiB2 content frome 20 to 10 wt.% caused only a 5% reduction in tensile strength of the nanocomposite.
REFERENCES
1. Tjong, S. C., Lau, K. C., Properties and abrasive wear of TiB2/Al-4%Cu composites produced by hot
isostatic pressing, Composites Science and Technology, Vol. 59 , pp. 2005-2013,1999.
2. Chen, Z. Y., Chen, Y. Y., Shu, G. Y., Li, D., Liu, Y., Microstructure and properties of in situ Al/TiB2 composite fabricated by in-melt reaction method, Metallurgical and Materials Transactions A, Vol. 31A, pp.
1959-1964, 2000.
3. Yi, H., Ma, N., Li, X., Zhang, Y., Wang, H., High-temperature machanics properties of in situ TiB2p reinforced Al-Si alloy composites, Materials science and Engineering A, Vol. 419, pp. 12-17, 2006.
4. Tjong, S. C., . Ma, Z. Y, Microstructural and mechanical characteristics of in situ metal matrix composites, Materials Science and Engineering A, Vol. 29, pp. 49-113, 2000.
5. Suryanarayana C., Mechanical alloying and milling, Progress in Materials Science, Vol. 46, pp.
1-184, 2001.
6. L, L., Lai, M. O., Su, Y., Teo, H. L., Feng, C., F., In situ TiB2 reinforced Al alloy composite, Scripta
Materialia, Vol. 45, pp. 1017-1023, 2001.
7. Lu, H. Lai M. O., Wang, Y., Synthesis of titanium diboride TiB2 and Ti-Al-B metal matrix composites,
Journal of Materials Science, Vol. 35, pp. 241-248, 2000.
8. Viswanathan, V., Challenges and advances in nanocomposite processing techniques, Materials Science and Engineering R, 54, pp. 121-285, 2006.
9. Mamedov, V., Spark plasma sintering as advanced PM sintering method, Powder Metallurgy, Vol. 4
(45), pp. 322-328, 2002.
10. Sadeghian, Z., Enayati, M. H. Beiss, P., Characterization of in situ Al-TiB2 nanocomposite powder synthesized by mechanical alloying, Powder Metallurgy, Vol. 54, pp. 4649, 2011.
11. Sadeghian, Z., Enayati, M. H. Beiss, P., In situ production of AlTiB2 nanocomposite by double-step
mechanical alloying, Journal of Materials Science, Vol. 44, pp. 2566-2572, 2009.
12. Suryanarayana, C., X-ray diffraction: a practical approach, Norton MG: Plenum Press, New York,
USA, 1998.
13. Kang, Y. and Chan, S., Tensile properties of nanometric Al2O3 particulate-reinforced aluminum matrix
composites, Materials Chemistry and Physics, Vol. 85, pp. 438-443, 2004.
14. Zimmerman, A.F., Palumbo, G., Aust, K. T., Erb, U., Mechanical properties of nickel silicon carbide nanocomposites, Materials Science and Engineering A, Vol. 328, pp. 137146, 2002.
15. Rabiei. A., Vendra. L. and Kishi. T.,Fracture behavior of particle reinforced metal matrix composites,
Composites: Part A, Vol. 39, pp. 294300, 2008.
16. Vedani. M., Errico. F. D., Gariboldi. E., Mechanical and fracture behaviour of aluminium-based discontinuously reinforced composites at hot working temperatures, Composites Science and Technology, Vol.
66, pp. 343349, 2006.
87

DRY SLIDING WEAR RESISTANCE AND DESIGN CRITERIA FOR

POWDER METALLURGY STEELS
Ibrahim METINOZ*, Ilaria CRISTOFOLINI**, Alberto MOLINARI*
*Department of Materials Engineering and Industrial Technologies, University of Trento,
Trento (Italy), ibrahim.metinoz@ing.unitn.it, alberto.molinari@ing.unitn.it
**Department of Mechanical and Structural Engineering, University of Trento,
Trento (Italy), ilaria.cristofolini@ing.unitn.it
ABSTRACT
The wear coefficients of two diffusion bonded sintered steels was used as knowledge base to implement the model
of the dry sliding wear. The difference in the wear resistance of the two steels has a noticeable influence on the
working life of a component subject to this kind of wear. The effects of changing geometry or microhardness were
compared.
Keywords: Powder Metallurgy, Wear, Design Criteria
1. INTRODUCTION
Many parts produced by Powder Metallurgy (PM) are subject to wear in application. Wear occurs by different mechanisms depending on the contact conditions (relative motion, load, environment) and on the materials involved. In
the case of dry sliding contacts, wear occurs mainly by either adhesion or triboxidation [1].
Among the PM materials used in structural applications, the diffusion bonded Fe-Mo-Ni-Cu steels are widely utilized. They can be hardened by either through hardening or carburizing, but the final microstructure contains a
Fe-Ni constituent which cannot be hardened by heat treatments. It may constitute a weak part of the microstructure,
because of its lower microhardness in comparison to the martensitic areas formed in the Ni-free zones. Its effect
on wear resistance of these steels has been demonstrated in previous works [2]. An alternative to this class of
materials is represented by the diffusion bonded Ni-free Fe-Mo-Cu steels, which can be sinterhardened, obtaining
a homogeneous martensitic microstructure just after sintering. In this case, post-sintering heat treatments can be
avoided.
In the present work, the results of dry sliding wear tests on these two types of sintered steels are elaborated to
define some design guidelines for specific applications where this kind of wear may seriously damage the parts
performance. The wear which is observed during tests is the so called low-sliding velocity oxidative wear proposed
by Stott [3]. It occurs in the tribosystems characterized by a sliding velocity lower than 1 m/s [4]. Wear tests were
carried out in a disk-on-disk apparatus, and tests were carried out at different loads. To generalize the results, the
mean pressure was determined and the wear coefficient was calculated from the wear rate. A failure criterion was
then defined with reference to the wear thickness, and the performance of the two steels was compared.
Since the wear thickness depends on the hardness of the materials and on the geometry of the parts involved, the
influence of these two parameters was evaluated.
Table 1 shows the code and the nominal chemical compositions of the materials investigated; TH and SH mean
through hardening and sinter hardening, respectively.
88

Table 1. Chemical composition of the investigated materials

Material Code
TH
SH
Nominal Chemical Composition of the Steels (wt %)

93.4Fe-4Ni-0.5Mo-1.5Cu-0.6C
95.9Fe-1.5Mo-2Cu-0.6C
Discs 10 mm in height, with an external diameter of 40 mm and an internal hole of 16 mm diameter were compacted
in a double action uniaxial press and sintered at 1120C in endogas; the as sintered density is 7.2 g/cm3. The production process was carried out in industrial plant.
The microstructure of the materials was investigated at optical microscope after etching: it differs for the presence of
the Ni-rich constituent in the TH material, in addition to martensite [2]. Hardness was measured on the compaction
surface of the disks; it is 357 HV30 and 407 HV30 for TH and SH, respectively.
2.1 Dry Sliding Wear Test
The dry sliding tests were carried out on an Amsler trybotester. The test configuration was disc on disc, with the
PM disc rotating against the fixed counterface disc, made of a 100Cr6 steel hardened to 62 HRc. The loads during
the tests were 200, 500 and 1000 N; the sliding speed was 0.314 m/s, which corresponds to 150 rev/min. Wear
tests were interrupted each 15 minutes and the weight loss was measured after ultrasonic cleaning with acetone to
remove wear debris entrapped into the pores. While measuring the weight loss of the discs, the width of the contact
area was also measured.
3.1 Wear Test

The mean pressure during the wear tests is calculated from the equation (1)
P0=F/A (1)
where P0 [Pa] is the mean pressure, F [N] is the applied force and A [mm2] is the contact area given by A = lb where
l is the contact length (10 mm) and b is the contact width, which was measured as described above..
At the beginning of the tests there is a line contact [1], and width is calculated from the theory of the elastic contact
by equation (2)
b= (4FR / lE )1/2 (2)
where R [m] is the reduced radius of curvature of the two discs, R=(1/R1+1/R2)-1; E [Pa] is the reduced Youngs
Modulus, E=(1/E1+1/E2)-1. The Youngs Modulus of the materials is 140 x 109 Pa for the PM specimens and 210 x
109 Pa for the counterface disc.
The mean pressure P0 is calculated from equation (3)
P0=0.78 Pmax (3)
where Pmax is the maximum contact pressure given by the equation (4)
Pmax= F/(bl) (4)
Figure 1 shows the plot of the mean pressure P0 as a function of the sliding distance. The mean pressure is very
high at the beginning due to the line contact and after a while decreases dramatically due to the enlargement of
the contact area. It can be seen that the mean pressure can be considered as constant after a certain distance for
each load.
Figure 1. The relation between mean pressure and sliding distance.
89

The wear rate, calculated from the wear tests [5] can now be correlated to the mean pressure. Table 2 reports the
data, which are also plotted in Figure 2.
Table 2. Wear Rate of the Materials
Figure 2. Wear Rate vs. Pressure

On increasing the mean pressure wear rate increases in both materials. Moreover, SH has lower wear rate than
TH under the same pressure; this was attributed to the effect of the Ni-rich constituent on the load bearing capacity
of the surfaces [2].
The graph which illustrates the wear rate vs. mean pressure is shown in figure 2.
From the Archard Law [6] the wear coefficient K was calculated by equation (5)

K=WH/F (5)
where W [mm3/m] is the wear rate, H [N/mm2] is hardness and F [N] is the applied force. The wear coefficient K as
a function of mean pressure is shown in figure 3.
Figure 3. Wear Coefficient vs. Pressure

Material SH still maintains a better wear resistance than TH.
3.2 Failure Criteria and Design Guidelines
In the selection of wear model, wear thickness is the most convenient parameter [5]. Wear thickness is calculated
from equation (6)
h=(KFN)/(HL) (6)
where h is the wear thickness, K is the dimensionless wear coefficient, F [N] is the applied force, H [N/mm2] is the
hardness of the material, L [mm] is the length of the contact area and N is the number of cycles.
90

As a failure criterion the maximum acceptable wear thickness has to be defined. The maximum acceptable wear
thickness can be defined with reference to the tolerance required for the dimension perpendicular to the surface
exposed to wear. In this way a maximum wear thickness hl is defined, to which the wear thickness calculated with
equation (6) has to be related.
The classes for dimensional tolerances are defined by the Internal Organization for Standardization, ISO. In the
case of a Powder Metallurgy part having a diameter of 40 mm the ISO IT9, IT10 and IT11 classes may be considered and the relevant values are reported in table 3.
Table 3. Classes of dimensional tolerance
IT 9
IT 10
IT 11
0.031 mm
0.05 mm
0.08 mm
Given that the tolerance is applied to a diameter, the maximum acceptable wear thickness will be derived considering half of the values reported in Table 3.
As an example, figure 4 shows the wear thickness as a function of the number of cycles N for the mean pressure
of 3.67 MPa. The maximum acceptable wear thickness according to IT9, IT10 and IT11 requirements is reported
as well.
Figure 4. Wear thickness vs. Number of Cycles at 3.67 Mpa

It can be seen that material TH is not able to operate for 106 cycles in any acceptable range. On the other hand,
material SH can operate 106 cycles if IT11 classes is required, whilst it operates up to 6.5x105 and 4x105 cycles if
the IT10 and IT9 class are required, respectively.
If the mean pressure on the tribosystem is increased from 3.67 up to 8.22 MPa the new trend for the wear thickness
can be seen in figure 5.
Figure 5. Wear thickness vs. Number of Cycles at 8.22 MPa

The increase in the pressure causes an increase in the wear thickness in both materials, then the maximum number
of cycles to reach the acceptable wear thickness decreases. Both of materials cannot operate 106 cycles in all the
cases; the material SH can operate 6x105 cycles if IT11 ISO class is required by the failure criterion.
91

If the mean pressure of the tribosystem is increased to 13.71 MPa the wear thickness is shown in figure 6.
Figure 6. Wear thickness vs. Number of Cycles at 13.71 MPa

Wear thickness further increases, and material SH operates 4x105 cycles if IT11 ISO class is required by the failure
criterion.
Equation (3) shows that the wear thickness depends on hardness of the material and on the length of the contact
area L. The length of the contact area in Powder Metallurgy may be increased by increasing the height of the disk,
by simply filling more powder without changing the die geometry and the compaction strategy significantly. An
increase in L changes the mean pressure (decrease) and the wear coefficient, accordingly. For instance, figure 7
shows the wear thickness in the case of a 30% larger contact length: the wear coefficient in this new situation was
extrapolated by the available data base.
Figure 7. h vs. N at 2.82 MPa (length of the contact area is increased of 30%)
The comparison between figures 4 and 7 shows that the increase in the length of the parts results in a decrease of
the wear thickness for both TH and SH. The material TH is still not able to operate for 106 cycles in any case. On
the other hand, material SH can operate 106 if the IT11 is required by the failure criterion.
As an alternative, hardness may be increased by increasing the carbon content of the material. For instance, an
increase of 60 HV in hardness can be obtained by either increasing the carbon content up to 0.7-0.8% (in the case
of TH the sintering temperature should be increased, as well, to enhance hardenability thanks to the homogenization of the Ni distribution). In this case, the wear thickness decreases, as shown by figure 8, relevant to the lowest
pressure considered. Again, the material TH is still not able to operate for 106 cycles in any case. On the other
hand, material SH can operate 106 even if the IT10 is required by the failure criterion. The increase in hardness is
equivalent to the 30% increase in the height of the parts. The most attractive solution seems to be the increase in
hardness. The increase in carbon content slightly decreases compressibility of the powder mix but, on the other
side, the increase in height increases the part weight correspondingly. Even from the viewpoint of the cost effectiveness, the increase in the carbon content has to be preferred.
92

Figure 7. h vs. N at 3.67 MPa (the hardness is increased by 60 HV)

4. CONCLUSION
In this paper the wear coefficients of two different PM steels was used as knowledge base to implement the model
of the dry sliding wear. The steels are both diffusion bonded: one contains Ni and was through hardened, the other
one is Ni free and was sinter hardened. Due to the presence of the Ni rich areas which are softer than the martensitic matrix the former has a lower wear resistance than the latter. A failure criterion was defined based on the
comparison between the wear thickness and the tolerance required on the dimension perpendicular on the wear
surface. The difference in the wear resistance of the two steels has a noticeable influence on the working life of a
component subjected to this kind of wear. By means of the same model the effects of changing geometry or microhardness were compared.

REFERENCES
1. Straffelini G., Attrito e Usura, Metodologie di progettazione e controllo, ed. Tecniche nuove 2007, 2-7
2. Muterlle P. V., Straffelini G., Molinari A., and Pahl W., Microstructural effects in wear of hardened sintered
steels produced by diffusion bonded and prealloyed powders, Powder Metallurgy 2010; 53(3):201-207
3. Stott FH. The Role of oxidation in the wear of materials. Tribol Int 1998; 31:61-71
4. Lim SC, Ashby MF. Wear mechanism maps. Acta Metall 1987; 35(1):1-24.
5. Cristofolini I., Molinari A., Straffelini G. and Muterlle P. V., A systematic approach to design against wear
for Powder Metallurgy (PM) steel parts: The case of dry rolling-sliding wear, Materials and Design 2011;
32:2191-2198.
6. Archard JF. Contact and rubbing of flat surfaces. J Appl Phys 1953;24:981-8
93

MICROSTRUCTURAL CHARACTERIZATION OF POWDER

METALLURGICAL TOOL STEELS ETCHED BY DIFFERENT TECHNIQUES
. Hakan ATAPEK*, eyda POLAT*, Serap GM*,
Ersoy ERR* and Gzde S. ALTU*
Kocaeli University, Faculty of Engineering,
Department of Metallurgical and Materials Engineering, 41380, Kocaeli, Turkey hatapek@kocaeli.edu.tr,
seyda@kocaeli.edu.tr, sgumus@kocaeli.edu.tr, eerisir@kocaeli.edu.tr, gsultan.altug@gmail.com
*
ABSTRACT
In this study, several commercial grades of powder metallurgical tool steels are investigated, in hardened and soft
annealed conditions, to determine the types, morphologies and distributions of the carbides present. Prior to the
microstructural characterization by scanning electron microscope, all samples are prepared using standard grinding and polishing steps and etched by using different techniques, including immersion into % 3 nital and Beraha
solutions and also electroytic etching.
The examinations reveal that the steels have fine, aligned or dispersed, carbides in their matrix with globular and
facetted morphologies and in light/dark gray contrast. Microanalysis using energy dispersive x-ray spectrometer is
carried out to determine carbide types and the results show that the globular carbides are typical W-Mo rich M6C
and V-rich MC type carbides, as expected.
Keywords: Tool Steels, Powder Metallurgy, Etching, Microstructure, Carbides.
1. INTRODUCTION
It is well known that the processing technique has a strong influence on the properties and performance of materials. Engineers and researchers spend most of their time to develop new techniques for the materials that have high
level functionality and can be produced by low cost. In the field of materials for tool applications, there are three
processes that allow the processing of tool steels (e.g. cold work, hot work and high speed tool steels): conventional
casting, powder metallurgy and spray forming [1-5].
The need for high-performance tool steels has grown dramatically because of the demand for high quality parts and
low cost high performance tooling per part produced. In this concept, production of powder metallurgical tool steels
gains importance. In traditionally melted tool steels, molten metal is poured into moulds and the resulting ingots are
forged, rolled and then annealed. In this way, steel bars are formed. During the solidification of the ingot, carbide
networks are formed and they weaken the cracking resistance of the matrix. T
ype, morphology and also distribution of the carbide play an important role on the mechanical properties of a given
tool steel and especially a change of morphology/distribution of the carbide is desired for many tooling applications.
The extremely fine carbides and uniform microstructure of powder metallurgical tool steels greatly increase the
mechanical properties (hardness, wear resistance, ductility etc.) in all directions. This is in contrast to conventionally
produced steel where increased ductility can only be gained at the expense of reduced wear resistance/hardness
[6-10].
In this study, the microstructural characterization of several commercial grades of powder metallurgical tool steels
were carried out after etching, by using light microscope (LM), scanning electron microscope (SEM) and energy
dispersive x-ray spectrometer (EDS) to determine the morphology, type and distribution of carbides in the their
matrices.
94

2. EXPERIMENTAL STUDY
2.1. Materials
Several commercial grades of powder metallurgical tool steels, in hardened and soft annealed conditions were used
for the characterization. Table 1 shows the chemical compositions of the steels used in this study. The steels were
received from the supplier in soft annealed condition and then hardening heat treatments were carried out. The
heat treatment parameters are given in Table 2. The steels used in the study are commonly treated at 1000-1200C
for hardening. The sizes of the samples are 10 x 10 x 15mm and the duration for the solution treating was selected
according to both sample size and also alloy content in the steel. As it is seen from Table 1, DIN 1.3207 tool steel
includes higher W and Co content than DIN 1.3394 and DIN 1.3395 tool steels.
Table 1. Chemical compositions of the experimental steels (wt.%).
Materials
DIN 1.3207
DIN 1.3395
DIN 1.3394
C
1.34
1.30
1.30
Si
0.30
-
Mn
0.21
-
Cr
3.36
4.20
4.20
Mo
3.17
5.00
5.00
V
2.50
3.10
3.10
W
9.66
6.40
6.40
Co
10.30
8.50
Fe
balance
balance
balance
Table 2. Heat treatment conditions for the experimental steels.

Materials
DIN 1.3207
DIN 1.3395
DIN 1.3394
Austenization
1100C, 30 min.
1000C, 15 min.
1000C, 15 min.
Quenching
Water quenching
Water quenching
Water quenching
2.2. Metallographical preparations and microscopic examinations

After standard metallographical preparations consisting of grinding and polishing, the steels were initially etched
by using % 3 nital and Beraha solutions (100 ml H2O +20 ml HCl + 0.30.6 g of potassium metabisulfite). However,
these solutions were not adequate to characterize the matrix phase that formed after hardening treatment. Thus,
the steels were electrolytically etched by using AC2-I solution and applying 5V for 1 minute. The steels were characterized by using Zeiss Axiotech 100 model light microscope and Jeol JSM 6060 scanning electron microscope.
3.1. Light microscope examinations
The high-speed steel produced by powder metallurgy contains primary carbides that are rich in vanadium, tungsten and molybdenum. These carbides play an important role in the mechanical properties of the steel, including
hardness, wear resistance and temperature resistance. Hence, the types, morphologies, distributions and also the
amounts of these carbides must be determined [11].
Figures 1, 2 and 3 show the final microstructures of the investigated steels revealed by light microscope examinations. Hardened DIN 1.3207 high speed tool steel includes typically primary carbides within a martensitic matrix
which is very hard and also brittle (Figure 1). In the etched steel, aligned primary carbides can be seen and there
is no significant evidence of the austenite grain boundaries as seen in Figure 1a. Upon over etching with % 3 nital
solution, the grain boundaries appear due to more anodic dissolution characteristic of the boundaries with chemical reactions. However, etching by nital is not adequate to determine the matrix phase. As-quenched martensite is
described as having a tetragonal structure, but this is only true when the carbon content exceeds about 0.6 wt.%.
Lower carbon martensites retain the body-centered cubic structure of ferrite. High-carbon martensites typically
have lens-shaped martensite plates which contain fine-scale deformation twinning. Low-carbon martensites consist
of laths, separated by low- or high-angle boundaries but also containing high densities of dislocations within them
[12].
(a)
(b)
Figure 1. LM images of the microstructures of hardened DIN 1.3207 steel ; (a) as etched and (b)
over etched by % 3 nital.
95

In Figure 2, the microstructures of DIN 1.3395 steel are given to compare the etchant effect on the matrix for soft annealed and hardened conditions. A ferritic matrix including primary carbides takes place in soft annealed steel and
the matrix consists of globular carbides (Figure 2a). In electrolytically etched case, the carbides and their morphologies appear clearly within the matrix and a very fine, homogenous distribution of the carbides can be seen (Figure
2b). Hardening treatment is applied to the steel to form martensitic/bainitic matrix for high mechanical requirements.
Hardened microstructures in steels require the generation of the parent phase austenite, the formation of martensite
crystals by diffusionless, shear-type martensitic transformation, and adjustment of final strength and toughness by
tempering [13]. Figure 2c and 2d show the microstructures of hardened DIN 1.3395 steel. At first, the steel is etched
by % 3 nital solution but a high level reaction between etchant and matrix phase cannot be attained. On the other
hand, the matrix phase interacts with Beraha solution and it is possible to examine the steel in detail with scanning
electron microscope at higher magnifications which will be discussed in the next section.
A number of etchants have been reported in the literature to selectively outline, outline and color, or attack specific
types of carbides in steels. These etchants have been developed during the first half of the 20th century but have not
been studied since the development of modern analytical techniques. Although they are believed to be selective,
that is qualitative in nature, their value for quantitative measurements of the carbides has not been determined [1417]. Figure 3 shows the microstructures of soft annealed and hardened DIN 1.3394 steel. As seen from Figure 3a,
etching with % 3 nital solution results in low contrast to observe the type and morphology of the carbides and also
the matrix phase and also grain boundaries in soft annealed steel. Electrolically etching provides more contrast in
soft annealed matrix to evaluate the carbide features as shown in Figure 3b. On the other hand, etching with Beraha
solution gives a detail, in hardened steel, for the matrix components. A network type carbide distribution within the
matrix is observed (Figure 3c).
(a)
(b)
(c)
(d)
Figure 2. LM images of the microstructures of DIN 1.3395 steel ; (a) soft annealed sample etched by
% 3 nital solution (b) soft annealed sample as electrolytically etched , (c) hardened sample etched by % 3 nital
solution, (d) hardened sample etched by Beraha solution.
3.2. SEM examinations
After using various etchant and etching techniques followed by LM examinations, the steels were also characterized
by SEM. Figure 4a shows the general matrix of hardened DIN 1.3207 tool steel. Similar to the light microscope
examinations, aligned carbides are observed. At higher magnification, it is obvious that the matrix phase consists of
typical plate type martensite with globular carbides mostly at the grain boundaries (Figure 4b).
96

Etched microstructures of DIN 1.3395 tool steel are given in Figure 5. Soft annealed steel exhibits a homogeneous
distribution of fine carbides within the ferritic matrix after electroytic etching (Figure 5a). In hardened steel, both
globular and facetted carbides having different contrast, as bright and dark grey, are observed within the plate type
martensitic matrix after etching with Beraha solution (Figure 5b). The type of carbide will be emphasized in the
carbide analysis section. Plate type martensite phase is observed as acicular form due to the effect of electrolytical
etching with high level anodic dissolution of ferrite (Figure 5c).
(a)
(b)
(c)
Figure 3. LM images of the microstructures of DIN 1.3394 steel ; (a) soft annealed sample etched by % 3 nital solution (b) soft annealed sample as electrolytically etched, (c) hardened sample etched by Beraha solution.
(a)
(b)
Figure 4. SEM images of the microstructures of DIN 1.3207 steel as electrolytically etched ; (a)
aligned carbide distribution in martensitic matrix after hardening treatment, (b) carbides in the grains and
also at the grain boundries.
(a)
(b)
(c)
Figure 5. SEM images of the microstructures of etched DIN 1.3395 steel; (a) a homogeneous distribution of fine
carbides within the matrix, in soft annealed sample, (b) globular and facetted type carbides within the
matrix etched by Beraha solution, in hardened sample, (c) plates as acicular form of martensite phase after
electrolytical etching in hardened sample.
In tool steels, the improvement in the cutting performance with the addition of cobalt is indisputable. The more difficult the material is to machine, the more effective the addition of cobalt to the tool steel. Cobalt dissolves in iron
(ferrite and austenite) and strengthens it at the same time imparting high temperature strength. During solution heat
treatment to dissolve the carbides, cobalt helps the resist grain growth so that higher solution temperatures can
97

be used to ensure the dissolution of higher percentage of carbides. Steels are quenched after solution annealing
and a microstructure consisting of hard martensite with fine alloy carbides is obtained. Tempering will cause the
precipitation of ultrafine carbides still in solution and maximum hardness will be attained. Here, cobalt plays another
important role, in that it delays their coalescence. This is important as it means that during cutting, the structure
is stable up to higher temperatures. Thus, cobalt-containing tool steels are capable of retaining strength at higher
temperatures [18-20]. The microstructure given in Figure 6a explains the cobalt effect on the matrix with the comparison of DIN 1.3395 to 1.3394 steel. In electrolytically etched steel, carbides are observed in soft annealed matrix
with skeleton morphology due to cobalt wetting. At higher magnification given in Figure 6b, both globular and also
facetted carbides within the martensitic matrix, formed after hardening, appear in different sizes.
(a)
(b)
Figure 6. SEM images of the microstructures of DIN 1.3394 steel as electrolytically etched; (a)
carbides in the matrix with skeleton morphology, in soft annealed sample (b) plates of martensite phase and
carbides in hardened sample.
3.3. Carbide analysis
The microstructure of high speed tool steels, in annealed condition, consists of martensitic or ferritic matrix and
blocky MxCy type carbides, called primary carbides, formed during casting. After heat treatment (annealing, quenching and tempering), this matrix is strengthened by secondary precipitation of extremely fine carbides. The function
of the blocky carbides is to protect the matrix against wear and the secondary carbides help to provide high hot
strength. Besides, the high speed steel requires high fracture toughness. It is very important to control the type of
existing carbides. Hence, the size, distribution, type and fraction of the carbide phase to a large extent determine
the properties of powder metallurgical tool steels. Thus, a large number of studies had been undertaken to find
ideal tool steel microstructures. Depending on the steel composition several types of carbides (mainly MC, M2C,
M6C) are precipitated in high speed steels. During hot working, the primary carbides, formed during solidification,
change their as-cast structure to a more spherical one. They have an incoherent interface to the matrix and are
a few micrometers in size. In the finished tool, the primary and also secondary carbides formed due to tempering
effect are responsible for the high wear resistance, in addition to the high hardness of the matrix [21-25].
In DIN 1.3207 material there are globular carbides in bright contrast and facetted ones in gray contrast. Figure 7
and 8 show the typical carbides observed in DIN 1.3207 tool steel. The spot analysis was carried out to determine
the elementel concentration of carbides and it was found that globular type carbides were typically M6C carbides
which were W and Mo-rich (Figure 7), and facetted carbides were typically MC carbides in which vanadium was the
major element (Figure 8). Both DIN 1.3395 and DIN 1.3394 steels have Cr, Mo, V and W which are strong carbide
formers. The examinations revealed that the steels had similar carbide morphologies and types.
(a)
(b)
Figure 7. Characterization of globular carbides in DIN 1.3207 tool steel; (a) SEM micrograph, (b) spot analysis
giving the elementel spectrum of globular carbide marked in micrograph (a).
98

(a)
(b)
Figure 8. Characterization of facetted carbides in DIN 1.3207 tool steel; (a) SEM micrograph, (b) spot analysis
giving the elementel spectrum of facetted carbide marked in micrograph (a).
4. CONCLUSION
In this study, the microstructures of hardened DIN 1.3207, soft annealed and also hardened DIN 1.3394, DIN
1.3395 powder metallurgical tool steels are investigated. In the first stage, % 3 nital and Beraha solutions were
used to determine the matrix phase and the carbides present within the matrix. In the second stage, the steels
were electrolytically etched due to the insufficiency of immersion technique to reveal matrix phase and also the
interface of carbides. Aligned carbides are observed in DIN 1.3207 tool steel having martensitic matrix after hardening treatment. Fine dispersed carbides take place in both DIN 1.3395 and DIN 1.3394 tool steels having plate
type martensitic matrix. In DIN 1.3207 tool steel, there are globular carbides in bright contrast and facetted ones in
gray contrast. EDS analysis shows that globular type carbides are typically M6C carbides which are W and Mo-rich
carbides, and facetted carbides are typically MC carbides in which vanadium is the major element. DIN 1.3395 and
DIN 1.3394 steels have Cr, Mo, V and W which are strong carbide forming elements and their matrices also consist
of typical M6C and MC carbides similar to DIN 1.3207 tool steel.
References
1. German, R. M., Powder Metallurgy Science, MPIF, Princeton, NJ, USA, 1994.
2. Schatt, W., Wieter, K. P., Powder Metallurgy Processing and Materials, EMPA, Shewsbury, 1997.
3. Matula, G., Dobrzaski, L. A., Herranz, G., Vrez, A., Levenfeld, B., Torralba J. M., Structure and Properties of
HS6-5-2 Type HSS Manufactured by Different P/M Methods, Journal of Achievements in Materials and Manufacturing Engineering, Vol. 24(2), pp. 71-74, 2007.
[4] Mesquita, R. A., Barbosa, C. A., High Speed Steel Produced through Conventional Casting, Spray Forming and
Powder Metallurgy, 6th International Tooling Conference, Karlstad-Sweden, pp. 387-402, 2002.
5. Schneider, R., Schulz, A., Bertrand, C., Kulmburg, A., Oldewurte, A., Uhlenwinkel, V., Viale, D., The Performance
of Spray-Formed Tool Steels in Comparison to Conventional Route Material, 6th International Tooling Conference, Karlstad-Sweden, pp. 1111-1124, 2002.
6. Rosso, M., Ugues, D., Grande, M. A., The Challenge of PM Tool Steels for the Innovation, Journal of Achievements in Materials and Manufacturing Engineering, Vol. 18(1-2), pp. 175-178, 2006.
7. Nurthen, P., Bergman, O., Hauer, I., Carbide Design in Wear Resistant Powder Materials, PM2008 World Congress, Washington-USA, pp. 1-15, 2008.
8. Karaaslan, A., Aka, C., The Influence of Carbide Distribution on the Properties of Hot Work Tool Steels, METAL
2009, Hradec nad Moravic-Czech Republic, pp. 1-4, 2009.
9. Therkildsem, K. T., Dahl, C. V., Analysis of Carbide and Inclusion in High Speed Tool Steels, Report no : RisR-1360(EN), Ris National Laboratory, 2002.
10. Hetzner, D. W., Van Geertruyden, W., Crystallography and Metallography of Carbides in High Alloy Steels,
Materials Characterization, Vol. 59, pp. 825-841, 2008.
11. Godec, M., Batic, B. ., Mandrino, D., Nagode, A., Leskovek, V., kapin, S. D., Jenko, M., Characterization
of the Carbides and the Martensite Phase in Powder-Metallurgy High-Speed Steel, Materials Characterization,
Vol. 61, pp. 452-458, 2010.
12. Hutchinson, B., Hagstrm, J., Karlsson, O., Lindell, D., Tornberg, M., Lindberg, F., Thuvander, M., Microstructures and Hardness of As-Quenched Martensites (0.1-0.5 %C), Acta Materialia, Vol. 59(14), pp. 5845-5858,
2011.
99

13. Krauss, G., Martensite in Steel : Strength and Structure, Materials Science and Engineering A, Vol. 273-275,
pp. 40-57, 1999.
14. Schumann, H., Metallographie, VEB Deutscher, Verlag fr Grundstoffindutrie, Leipzig, 1974.
15. Petzow, G., Metallographisches, Keramographisches, Plastographisches etzen, Editions Gebrder
Borntraeger, Berlin, 1994.
16. Van der Voort, G. F., Manilova, E. P., Michael, J. R., Lucas, G. M., Study of Selective Etching of Carbides in
Steel, Microscopy and Microanalysis, Vol. 10, pp. 76-77, 2004.
17. Van der Voort, G. F., Lucas, G. M., Manilova, E. P, Michael, J. R., Study of Selective Etching of Carbides in
Steel, Praktische Metallographie, Vol. 36, pp. 255-262, 2004.
18. ASM Handbook, Machining, Vol. 16, pp. 51-59, ASM International, Ohio-USA, 1989.
19. Moiseev, V. F., Geller, Y. A., Effect of Cobalt on Structure and Properties of Fast-Cutting Steel, Metal Science
and Heat Treatment, Vol. 7(4), pp. 245-249, 1965.
20. Gulyaev, A. P., Kupalova, I. K., Effect of Cobalt on the Structure and Properties of High-Speed Steels, Metal
Science and Heat Treatment, Vol. 12(8), pp. 666-671, 1970.
21. Bochnowski, W., Leitner, H., Major, L., Ebner, R., Major, B., Primary and Secondary Carbides in High-Speed
Steels after Conventional Heat Treatment and Laser Modification, Materials Chemistry and Physics, Vol. 81(2-3),
pp. 503-506, 2003.
22. Karagz, ., Andren, H. O., Secondary Hardening in High Speed Steels, Zeitschrift fr Metallkunde, Vol.
83, pp. 386-394, 1992.
23. Fischmeister, H. F., Riedl, R., Karagz, ., Solidification of High Speed Tool Steels, Metallurgical Transactions A, Vol. 20, pp. 2133-2148, 1989.
24. Dobrzanski, L. A., Matula, G., Vrez, A., Levenfeld, B., Torralba,J. M., Fabrication Methods and Heat Treatment
Conditions Effect on Tribological Properties of High Speed Steels, Journal of Materials Processing Technology,
Vol. 157-158, pp. 324-330, 2004.
25. Trabadelo, V., Gimnez, S., Iturriza, I., Development of Powder Metallurgy T42 High Speed Steel for Structural
Applications, Journal of Materials Processing Technology, Vol. 202(1-3), pp. 521-527, 2008.
100

Foil 1: Topic Overview

1.
2.
3.
4.
5.
6.
7.
8.
9.
Press Procedure
Adapter Systems
Press Tooling
Filling
Powder Transfer
Pressing
Pressure Relief
Demolding
Summary
1. Press Procedure
Next to the withdrawal method (fixed bottom punch with movable die), the application of the ejection method (fixed
die with movable top- and bottom punches) also becomes more established when using hydraulic presses. The
withdrawal method is still predominantly applied with mechanical- and hybrid presses. The main advantage when
using the withdrawal method lies in the simple applied load of the top punch during demolding of the press part,
which will be discussed at a later point.
Since the control technology has become considerably more efficient in the last few years, the ejection method is
applied more frequently today with hydraulic presses.
By synchronous ejection of the press part between top- and bottom punch, materials can also be pressed which
tend to stockpile during the removal process. One of the advantages of the ejection process is that there is only one
constant removal height, also if there are different bottom punch lengths. Another advantage is that the mass in the
101

fill system is only moved in horizontal direction during the fill process which significantly decreases the segregation
of the press mass.
Furthermore, the programming during the ejection process is easier to understand, due to a similar course of movement of the top and bottom punch. All positions of the press axis relate to the fixed top edge of the die. Pressing
processes like the pressing from both sides are easy to realise, whereas in the withdrawal process you have to work
with relative movements between die and bottom punch.
2. Adapter Systems
Besides taking up the press tooling, the adapter systems of modern high capacity powder presses also take over
the precise guiding function of the tools.
Present-day adapter systems with up to 8 and more press axes demand very high requirements towards precision
and flexibility in regards to tool pick up and tool changing possibilities.
When pressing complex component geometries, the press tools were often changed together with the tool adapter
system. Simple press tools were already changed in the press because the change times were usually not above
the adapter change times. Today, the possibilities of an easy and precise movement of hydraulic press axes make
it possible to change even complex tooling within the presses.
Especially the electrical handwheel is of advantage with which each individually selected press axis can be easily
and accurately moved to any position. This kind of tool change offers specific benefits in regards to the withdrawal
pressing since mostly hydraulic drives of the additional axes are here integrated in the adapter.
An uncoupling of the hydraulic- and electric systems from the actual press is not applicable, which can often lead
to leakages of the hydraulic connections after a few cycles. This is not necessary when pressing according to the
ejection method because the hydraulic drives as well the measuring systems are part of the press and not of the
adapter. Even presses without separate adapter are applied for the last few years and were integrated into the
press.
3. Press Tooling
Depending on the producible part geometry, the press tools are getting more and more complex with the increase
of shape variations in the product.
In order to achieve a widely even density distribution, it is necessary to also separate in cross section changes,
press axes and tool axes.
With some products it is possible that up to 8 and more press levels and therefore tool splittings are required. On
one hand, this serves to produce the required filling spaces, on the other hand it enables the necessary powder
transfer in the compaction start position before the actual densification begins.
If these requirements can be met by the press tooling, only the forces that build up by the press travel and speed
must be transferred from the tool to the press part during the densification process. Since the divided press tools
can also be placed on different adapter levels, often only tool distance pieces can be used from each press level in
the adapter to the press tools in order to construct the tools as short as possible.
4. Filling
The filling process has an essential influence on the quality of the final product.
Mistakes that are made in this process cannot be compensated during the subsequent pressing procedure. Therefore, the filling process is an essential task which has a critical influence on the final product quality. Hereby, especially with stepped tooling, fill density deviations caused by air can lead to density differences in the press part
segments (Video).
Through venting systems on the fill shoe, such fill density differences can be decreased and simultaneously shorten
the fill times. Another important point that should be considered, especially during the compaction of higher density
materials, is the decoupling of the supply storage (big bag) from the actual fill hopper.
Here, a constant force of the powder mass should be reached; from the hopper via the hose and the fill shoe to
the empty cavity. This prevents fill density deviations between full and depleting supply tanks. Any issues at the
process start that should be taken into consideration during filling can already have a positive influence on the final
product.
5. Powder Transfer
Oftentimes it becomes necessary, especially with complex part geometries, to bring the press mass via the parted
bottom punch in such a position before the densification that, at the later press process, the same density ratio
102

exists in each part cross section. This shall prevent, that material displacements of higher density zones in lower
density zones take place. It is also possible to transfer press mass out of the filled cavity to the top punches that are
positioned above the die in order to press conical geometries upwards as well.
6. Pressing
The compaction of the press mass occurs through the top- and bottom punch movement, or through the top punch
and die movement (withdrawal principal) which moves relatively to the bottom punch. Thereby, the press mass is
compressed with such forces that green parts are created according to the tool shape. This way, specific press
forces of up to 100 kN/cm and more can act upon the press mass.
Special attention should be paid to the even density gradient over the entire press part cross section to eliminate
marginal powder shifting during the press process.
This means that different single pair of punches must move with different speeds during the densification process so
they reach their press position at the same time. The calculation and monitoring of such travel- and speed profiles
is carried out automatically by the control elements of modern powder presses.
7. Pressure Relief
After all press axes have reached their press position, a defined relief of the green part takes place. Here it is important, especially with stepped parts, that an even relief of all press axes occurs.
Complex part geometries which require multiple top- and bottom punch levels have press punches of different
length due to the adapter- and machine construction.
Here, the springback forces of punch surface and punch length have a corresponding effect on the green part. With
presses that work with fixed stops of the bottom punches, a punch relief downwards is not possible because these
fix positions cannot be changed anymore. This results in different forces upon the green part during the relief of the
top punch and oftentimes leads to cracks in the cross section variations of the component. At this point, an important advantage of the hydraulic hold of the press axes in press position comes in. Through a controlled relief of all
punch axes top- and bottom punches, according to the punch compression, a crack formation can be specifically
countered.
8. Demolding
After the green part only shows forces in radial direction due to the prior described relieve process, it can be ejected
by the bottom punch in overcoming the friction forces. Press mass (for example; ceramic mass) which tend to axial
pile-up by pressed-in air, are weighed down during the removal process through application of programmable slight
force of the top punch(es). This prevents a total axial relief and the green part can radially relax after demolding.
9. Summary
Since the components produced by powder press technology become more and more complex, the demands on
the press systems also increase steadily.
Here, the production process of such components has to be considered in its entirety, as you can see in the above
described procedural steps.
KOMAGE took on the challenge to face these great demands and to successfully put them into practice by applying
more than 100 years of experience in powder press construction as well as continuous innovative advancement in
hydraulic, control technology and tool design make KOMAGE your qualified partner in the powder press technology.
103

Prealloyed Molybdenum Low-Alloy Steel

Powders and the Flexibility of Hybrid Alloys based
on these Powders
W.B. James, Bruce Lindsley, Kalathur S. Narasimhan
Hoeganaes Corporation Cinnaminson, NJ USA
Abstract
The introduction in 1990 of a water atomized low-alloy steel powder that used molybdenum as the
principal alloy addition (Ancorsteel 85 HP) opened the doors to the development of numerous hybrid
low-alloy steels based on the molybdenum-steel powder.
Today, there are a number of water atomized prealloyed molybdenum-steel powders that contain different amounts of molybdenum; the appropriate one may be used depending on the hardenability needed
for the intended application.
The prealloyed molybdenum-steels are ideally suited for quench-hardening and tempering applications
where their excellent compressibility and good hardenability may be utilized, along with their consistent
dimensional change response.
These molybdenum steel powders also form the basis for many hybrid low-alloy steels where the various molybdenum contents available provide great flexibility in alloy design.
This paper will review the performance characteristics of these materials and illustrate their great flexibility.
Keywords: low alloy, prealloyed powders, sinterhardening, Quench and Temper, heat treated
1. Introduction
Water atomized prealloyed powders that use molybdenum as their principal alloy addition, were introduced commercially in 1990 [1]. They were developed via a design of experiments and the composition
with 0.85% molybdenum was selected for commercialization because it offered excellent compressibility
coupled with good hardenability. When mixed with graphite the material is well suited for applications
that require quench-hardening and tempering.
Because of its good compressibility, the powder was soon the base for hybrid alloys in which the base
was combined with additions of nickel, copper, or both nickel and copper [2]. A powder with higher
molybdenum content (1.5%) was introduced in Europe as both a prealloyed powder and the base for
diffusion-alloyed powders [3]. The lower compressibility (see Figure 1) and higher cost of the 1.5%
molybdenum powder (even at that time) resulted in little interest in the North American market but the
diffusion alloys were used for some applications in Europe and Asia.
In recent years, the considerably higher cost of molybdenum has led to the commercialization of prealloyed powders with lower molybdenum contents (both 0.5% and 0.3% Mo) and these powders now form
the base for various hybrid alloys. Hybrid alloys based on 0.5% molybdenum are now standard materials in MPIF Standard 35 Materials Standards for PM Structural Parts [4]. These materials were first
introduced in 1999 [5 and 6]. Subsequent developments based on prealloyed molybdenum steels
104

Figure 1: Compressibility of some water atomized, prealloyed powders.

(FL-4400 = 0.85% Mo; FL-4900 = 1.5% Mo; the others are Ni-Mo prealloys)
include PM-Cr steels and PM-Mn steels [7-12]. This paper will provide an overview of the performance
of these prealloyed powders that use molybdenum as their principal alloy addition. The flexibility of
these materials will be highlighted along with the current trend towards materials that contain lower
percentages of molybdenum.
2. Quench-Hardened and Tempered Properties
Prealloyed powders that use molybdenum as their principal alloy addition are particularly well suited
for applications where the PM parts need to be oil-quenched and tempered. The hardenability of the
materials is a function of their molybdenum content Figure 2.
Lindsley has shown that a 25 mm diameter compact, 25 mm high, made using a prealloyed powder with
0.3% molybdenum, through hardens at graphite addition levels as low as 0.6% [13] see Figure 3. At
lower levels of graphite, the compacts no longer through harden but have a hardness profile with a high
surface hardness (martensite) and a softer core (mixed martensite/bainite/unresolved pearlite).
As the molybdenum content is increased, the graphite addition required to through harden the 25 mm
diameter compacts is reduced Figure 4. The average microindentation hardness level for each molybdenum-graphite combination in these through hardened compacts is also listed in Figure 4. The
decrease in microindentation hardness as the graphite addition decreases is apparent; martensite hardness is a function of its carbon content. The compact made from a base iron powder (0% Mo) did not
through harden so the microindentation hardness of its case is shown. The samples in the referenced
study were 25 mm in diameter. Part size should be kept in mind when determining the molybdenum
content that is needed to through harden at a given carbon content. Smaller parts would not require the
same molybdenum content for them to through harden. Larger parts would need greater hardenability
and higher molybdenum content leads to increased hardenability - Figure 2.
Figure 2: The effect of molybdenum content on the

Jominy end-quench hardenability for materials with
0.6% graphite.
Figure 3: Microindentation hardness profiles of oil

quenched 25 mm diameter compacts with 0.3%
molybdenum and various graphite additions.
105

Figure 4: Minimum graphite contents required for through hardening oil quenched cylindrical compacts of 25
mm diameter made using various molybdenum prealloys. The average microindentation hardness is given for
each Mo-graphite combination. * Note that the material with zero molybdenum did not through harden at 0.9%
graphite and the microindentation hardness value listed is from the surface hardened case.
There is little difference in the compressibility of the prealloys with 0.3, 0.5, and 0.85% Mo but the compressibility of the powder with 1.5% Mo decreases by about 0.08-0.1 g/cm3.
Although copper steels are the workhorses of the powder metallurgy industry, they have limited hardenability and little ductility after heat treatment. When the microindentation hardness of a quenchhardened 25 mm diameter compact made from FC-0208 was compared with that for compacts made
from a 0.3% Mo prealloyed powder the difference in hardenability is readily apparent [13] Figure 5.
The FC-0208 compact has a hard case to a depth of less than 2 mm whereas the compacts made from
the prealloyed powder through harden. Hanejko has shown that the dimensional change of the 0.3%
Mo prealloyed material is less sensitive to density variation than FC-0208 [14]. Heat-treated PM gears
made from FC-0208 showed greater scatter in dimensional change compared with the same gears
made using a 0.3% prealloyed Mo steel powder.
Figure 5: Microindentation hardness profiles from the edge (distance = 0) toward the center of oil quenched,
25 mm diameter compacts with 0.9% graphite.
3. Hybrid Analogs of Diffusion Alloys Based on an Iron Powder
Hybrid alloys based on 0.5% molybdenum were first introduced in 1999 [5 and 6]). They are now standard materials in MPIF Standard 35 Materials Standards for PM Structural Parts [4]. At the same sintered carbon content, these hybrid materials have higher tensile strength than the diffusion alloys based
on an iron powder in the as-sintered condition Figure 6. While the materials have the same chemical
composition, the hybrid alloys, made with a prealloyed powder base, have greater hardenability than their
106

diffusion-alloyed analogs Figure 7 [4,15]. This makes them much better than the diffusion alloys
based on an iron powder for applications where the PM parts need to be heat treated.
In light of the good performance of the hybrid alloys based on a prealloyed powder with 0.5% molybdenum, it was decided to evaluate hybrid alloys with the same nickel and copper additions based on a
prealloyed powder with 0.3% molybdenum. The samples were sintered at 1120 C for 13 minutes at
temperature in a nitrogen:hydrogen atmosphere (90 v/o :10 v/o). No accelerated cooling was used. The
oil-quenched and tempered specimens were tempered at 200 C for 1 h. The results are summarized
in Figure 8 [15].
In the as-sintered condition, the yield strength of the hybrid alloy with 0.5% Mo exceeds that of the
diffusion-alloyed material of similar chemical composition. This was expected
Figure 6: (a) As-sintered and (b) heat-treated tensile properties of diffusion-alloyed materials based on iron
powder and their hybrid analogs based on a 0.5% Mo prealloy.
from the data presented in Figure 6. It is interesting to note that each of the materials with 0.3% Mo has a similar yield strength to that of the comparable diffusion-alloyed material. This should be reflected in actual PM parts as the materials based on the prealloyed powder with 0.3% Mo have a hardenability that should be similar to that of the
diffusion-alloyed materials.
Figure 7: Jominy hardenability comparison between diffusion-alloyed materials based on iron powder FD-0205
and FD-0405) and hybrid low-alloy powders based on a prealloyed powder with 0.5% Mo (FLN2C-4005 and
FLN4C-4005)
In general, the ultimate tensile strength of the quench-hardened and tempered lower nickel content
materials is better than that of the materials with 4% nickel. This is due to higher amounts of retained
austenite in the material with 4% nickel. The only reason for selecting the diffusion-alloyed material with
4% nickel would be for its better hardenability or slightly better impact energy. As the hardenability of the
hybrid alloy with the lower nickel content is similar to that of the diffusion-alloyed material with 4% nickel,
the hybrid alloy with the lower nickel content would be a more cost-effective choice.
107

4. PM Chromium Steels
Alloy additions such as chromium and manganese present difficulties when they are used in prealloyed
water atomized powders due to their high affinity for oxygen. Once formed,
Figure 8: As-sintered [(a) and (b)] and heat-treated [(c) and (d)] tensile properties for hybrid and diffusionalloyed materials of the same chemical composition compared with the tensile properties of a hybrid low-alloy
steel with the same nickel and copper additions but a lower prealloyed molybdenum content. All the materials
had a 0.6% graphite addition and a density of 7.0 g/cm3.
their oxides are extremely hard to reduce and if the alloy addition is not in solution it
does not contribute to the hardenability of the material. A hybrid PM chromium steel alloy based on a 0.85% molybdenum prealloyed powder (Ancorsteel 4300) has been shown
to have extremely good mechanical properties [7,8]. While the material may be sintered at |
1120 C in a 90 v/o: 10 v/o nitrogen:hydrogen atmosphere, a full 30 minutes are required at that temperature to develop optimum properties and it has been shown that high temperature sintering is more
practical in light of the 10 to15 minutes more typically allowed at temperature during commercial sintering practice [13].
A key attribute of this PM chromium steel is the fact that it sinter hardens at conventional sintering
furnace cooling rates (about 0.7 C/s) without the need for an addition of copper; something generally
needed with many sinter-hardenable materials. The absence of copper improves the robustness of
the material less sensitivity of the dimensional change of the material to density, carbon content, and
cooling rate.
The high cost of molybdenum in recent years led to the evaluation of hybrid PM chromium steels based
on prealloyed powders with lower molybdenum contents and a lean version of the material has been developed based on a prealloyed powder that contains 0.3% molybdenum (Ancorsteel 4300L) [10]. While
the hardenability of the hybrid PM chromium steels is lower that that of the hybrid sinter-hardenable
108

alloys that contain copper additions, their hardenabilities are comparable to those of other commercial
products Figure 9.
Figure 9: Jominy distance to 65 HRA for various PM materials

The chemical composition of the hybrid PM chromium steel alloys is listed in Table 1, and the effect of
cooling rate on the mechanical properties of both of the materials with a 0.6% graphite addition is summarized in Table 2 [10].
Table 1: Chemical composition of the hybrid PM chromium low-alloy steels
Material
Chemical Composition (mass %)

Si
Ni
0.6
1
0.6
1
Cr
1
1
Ancorsteel 4300
Ancorsteel 4300L
Mo
0.8
0.3
Mn
0.1
0.1
Table 2: Mechanical properties of the hybrid PM chromium low-alloy steels as a function of cooling rate
(cooling rate measured between 650 and 315 C) graphite addition of 0.6%.
Material
Ancorsteel
4300
Ancorsteel
4300L
Cooling Rate
(C/s)
Yield Strength
(MPa)
UTS
(MPa)
0.7
1.6
2.2
0.7
1.6
2.2
752
896
1069
690
738
827
1062
1172
1241
986
1020
1055
Total
Elongation
(% in 25 mm)
1.9
1.5
1.3
2.4
1.9
1.5
Impact
Energy
(J)
19
18
15
20
18
16
Apparent
Hardness
(HRA)
66
69
71
62
65
67
For the material that is based on a prealloyed powder with 0.85% molybdenum, increasing the cooling
rate from 0.7 C/s to 2.2 C/s improved the yield strength by 42%. For the leaner alloy (0.3% Mo), the
corresponding improvement in yield strength was 20% for the same change in cooling rate. The yield
strength of the leaner alloy is about 80 to 90% that of the other material depending on the cooling rate.
5. PM Manganese Steels
The ferrous PM industry continues to develop and expand its use of non-traditional PM alloying elements. Price, environmental, and recyclability concerns with Mo, Ni and Cu have driven this expansion.
Manganese is a relatively inexpensive, yet effective, alloying element in wrought steels. Nevertheless,
109

oxygen sensitivity has limited the use of manganese in PM steels in the past. The current nitrogenhydrogen sintering atmospheres with low partial pressures of oxygen now permit its use. The combination of Mn with a moderate level of Mo results in PM steel alloys with mechanical properties approaching
those of FD-0405.
Figure 10: Microstructures of the two PM manganese steels. Conventional cooling rate (0.7 C/s) for (a) and
(b) and accelerated cooling (1.6 C/s) for (c) and (d). ANCORBOND FLM-4005 = (a) and (c)
ANCORBOND FLM-4405 = (b) and (d)
Equally important, these alloys can be processed under typical, industrial sintering conditions. At higher
carbon contents these manganese steels can be used as lean alloy, sinter-hardening grades as has
been demonstrated by Lindsley and James [11, 12]. The microstructures of two PM manganese steels
are presented in Figure 10. The ANCORBOND FLM-4405 material has a greater hardenability than the
ANCORBOND FLM-4005 and this is reflected in the microstructures; there is a higher percentage of
martensite present in the ANCORBOND FLM-4405 at both cooling rates.
6. Conclusions
Since their introduction twenty years ago, prealloyed water atomized powders with molybdenum as
their principal alloying element have become the widely used prealloyed low-alloy steel powders. They
provide great flexibility in ferrous PM material design. They are used not only for their quench-hardened
and tempered properties but also serve as the base for a wide range of hybrid low-alloy PM materials;
analogs of the diffusion alloys that are based on iron, analogs of the diffusion alloys that are based on
molybdenum prealloys, in PM chromium steels, and in PM manganese steels.
7. References
1. J.J. Fulmer and R.J. Causton, Tensile, Impact, and Fatigue Performance of a New Water Atomized
Low-Alloy Powder Ancorsteel 85 HP, Advances in Powder Metallurgy,1990, Volume 2, compiled
by E.R. Andreotti and Patrick J. McGeehan and published by MPIF, pp. 459.
2. Hoeganaes Corporation, Technical Data Sheet for Ancorsteel 85 HP, February 1991.
3. Hgans AB, Iron and Steel Powders for Sintered Components PM 94-2.
4. MPIF Standard 35, Material Standards for PM Structural Parts 2009 edition.
5. F.J. Semel, Ancorloy Premixes: Binder_Treated Analogs of the Diffusion-Alloyed Steels, Advanc-
110

es in Powder Metallurgy & Particulate Materials, 1999, compiled by Charles L. Rose and Martin
Thibodeau and published by MPIF, Princeton, NJ, Vol. 2, pp. 7-93.
6. W. Brian James, The Development of Engineered Binder-Treated Alternatives to Diffusion-Alloyed
Powders, presented at 2nd International Latin American Conference on Powder Technology, November 10-12, 1999, Foz do Iguacu, Brazil.
7. Patrick King, Chromium Containing Materials for High Strength-High Fatigue Applications, Proceedings of the PM2004 World Congress, Vol. 3, published by EPMA, pp. 164-169.
8. Patrick King and Bruce Lindsley, A New Cr-Bearing Alloy for High Performance
Applications,
Advances
in
Powder
Metallurgy
&
Particulate
Materials 2005, compiled by Candido Ruas and Ted A. Tomlin, published by MPIF, Part 7,
pp. 12-21.
9. Bruce Lindsley, Sintering of Chromium Containing PM Steels Processed to High Density, Advances in Powder Metallurgy & Particulate Materials 2008, compiled by Roger Lawcock, Alan Lawley,
and Patrick J. McGeehan, published by MPIF, Part 5, pp. 150-160.
10.
Patrick King and Bruce Lindsley, Chromium Steels for High Performance PM Applications, Advances in Powder Metallurgy & Particulate Materials 2007, compiled by John Engquist and Thomas F. Murphy, published by MPIF, Part 7,
pp. 1-11.
11.
Bruce Lindsley and W. Brian James, PM Steels that Contain Manganese, Advances in Powder Metallurgy & Particulate Materials 2010, compiled by Matthew Bulger and Blaine Stebick,
published by MPIF, Part 10, pp. 36-49.
12.
Bruce Lindsley and W. Brian James, PM Steels that Contain Manganese, proceedings of
PM2010 Powder Metallurgy World Congress, Florence, Italy, October 2010, Volume 3, Sintered
Steels, pp. 151-158.
13.
Bruce Lindsley and Howard Rutz, Effect of Molybdenum Content in PM Steels, Advances in
Powder Metallurgy & Particulate Materials 2008, compiled by Roger Lawcock, Alan Lawley, and
Patrick J. McGeehan, published by MPIF, Part 7, pp.26-34.
14.
Francis G. Hanejko, A Comparison of FC-0208 to a 0.3% Molybdenum Prealloyed Low-Alloy
Powder with 0.8% Graphite, Advances in Powder Metallurgy & Particulate Materials 2009, compiled by Thomas J. Jesberger and Stephen J. Mashl, published by MPIF, Part7, pp. 59-72.
15.
W. Brian James, Bruce Lindsley, Howard G. Rutz, and Kalathur S. Narasimhan, Lean Hybrid
Low-Alloy PM Molybdenum Steels, proceedings of Euro PM2009, October 12-14, 2009, Copenhagen, Denmark, published by EPMA.
111

COMPACTION AND
MECHANICAL
PROPERTIES
www.turkishpm.org
112

HIZLI KATILATIRILMI MONEL 400 TOZUNUN PRESLENME

DAVRANIININ NCELENMES
Sultan ZTRK*, Blent ZTRK*, Fatih ERDEMR* ve Yksel PALACI**
Karadeniz Teknik niversitesi, Mhendislik Fakltesi, Metalurji ve Malzeme Mhendislii Blm, 61080,
Trabzon, suozturk@ktu.edu.tr
**
Nide niversitesi, Mhendislik Fakltesi, Makine Mhendislii Blm, 51240, Nide, ypalaci@nigde.edu.tr
*
zet
Bu almada su jeti soutmal dner disk atomizasyonu ile retilen Ni-Cu esasl Monel 400 tozlar kullanlarak,
ortalama toz boyutu ve boyut dalmnn preslenen paralarn ham younluklarna etkileri incelenmitir. Bu
amala 125/tava, -180/125, -250/180 ve -355/250 m elek aralklar ile bunlarn farkl oranlardaki katklaryla
oluturulan sekiz farkl boyut dalmna sahip fraksiyonlar denenmitir. Ayrca, presleme basncnn ham younlua
etkisini incelemek amacyla 150, 250, 350, 450 ve 600 MPa basnlar kullanlmtr. En yksek ham younluk
600 MPa presleme basncyla % 83 olarak elde edilmi ve artan presleme basncyla sertliin, tozlardaki plastik
deformasyonun, paracklar aras temas alannn ve koordinasyon saysnn artt, porozitenin azald tespit
edilmitir.
Anahtar Kelimeler: Monel 400 Alam, Presleme, Ham Younluk.
INVESTIGATION OF PRESSING BEHAVIOUR OF RAPIDLY SOLIDIFIED

MONEL 400 POWDER
ABSTRACT
In this study, the effect of mean particle size and size distribution on the green strength of compacts produced
by Monel 400 alloy powders which were obtained by water jet cooled rotating disc atomization have been
investigated. Eight group samples were prepared by using sieve fractions of 125/pan, -180/125, -250/180
and -355/250 m, for this aim. Also, compacting pressures of 150, 250, 350, 450 and 600 MPa were used to
investigate the effect of pressure on the green density. The experimental results showed that the highest green
density of 83% was obtained with the compacting pressure of 600 MPa. The properties of hardness, plastic
deformation of particles, the contact areas among the particles and the coordination number of particles increased
and the porosity decreased with increasing compacting pressure.
Key words: Monel 400 Alloy, Pressing, Green Density.
1.GR
Tozlarn bir kalp ierisinde basnla deforme edilerek, aralarnda ba oluturma ilemine toz sktrma denir.
Sktrma sonras elde edilen younlua ham younluk, mukavemete ise ham mukavemet denir. Sktrma ilemi
ile parann tanabilecek kadar bir mukavemet kazanmas amalanr. Tam younluk ise sinterleme sonras elde
edilir[1,2]. Eksenel sktrma; tozlarn sert bir metal kalpta tek eksende basn uygulayarak sktrlmasdr.
Basncn tek bir zmbadan uygulanmas tek hareketli sktrma olarak ifade edilirken, basncn alt ve st zmbalarn
her ikisinden ayn anda uygulanmas ilemi ift hareketli sktrma olarak adlandrlr. Ayn etki st zmbann basn
113

uygulamas srasnda kalbn hareketli olmas ile de elde edilebilir. Sktrma genellikle souk olarak uygulanmakla
birlikte, ham younluun artrlmas amacyla lk olarak da uygulanabilir. Sktrma ileminin balang aamasnda
kalp ierisindeki toz grnr younluktadr ve her bir toz tanesi ortalama olarak 4-6 aras komu tane ile temastadr
[3-5].
Presleme ileminin balangcndan sonuna kadar olan safhalar e ayrmak mmkndr. Presleme ileminin ilk
aamasnda tozlar konumlarn deitirerek gevek durumdan sk paket durumuna gemeye balar. Bu aamada
paracklarn elastik deformasyonu sz konusudur. kinci aamada younlamada ani bir art meydana gelir. Bu
aamada tozlar birbiri zerinden kayarak yeniden konumlanrken, paracklar arasnda meydana gelen kenetlenme
ile geri dn olmayan bir pozisyona girilmi olur. Kenetlenen paracklar plastik deformasyona uradklarnda
son aama balam olur. Basn arttka tanecikler aras temas alan artar. Son aamada younlama komu
paracklarn karlkl olarak bir araya gelmesiyle salanr. Balangta 4-6 olan parack koordinasyon says son
aamada 10-12 gibi rakamlara ulaabilir. Sktrma ilemi devam ettike paracklar aras temas alan byyerek
ham younlua ulalr. Son aamada paracklarn plastik deformasyonla sertlemelerinden dolay younlama
hznda bir azalma grlr [6-8].
Preslemenin balang aamasnda tozlar grnr mukavemete sahiptir. Presleme sonunda elde edilen mukavemet
ise ham mukavemettir. Bir sonraki aamada uygulanacak sinterleme ileminde maksimum mukavemete ulaabilmek
iin sinterleme ncesi ham mukavemetin yksek olmas gerekir. Elde edilecek ham mukavemetin deeri, presleme
basnc yannda esas itibariyle tozun birtakm zelliklerine baldr. Bunlar; tozun kimyasal bileimi, ortalama toz
parack boyutu, boyut dalm, toz ekli ve tozlarn sertliidir. Presleme ileminde tozlar deformasyonla birlikte
sertletikleri iin hesaplanandan daha fazla basnca gerek duyulur. Younlamaya sebep olan ortalama basn
her zaman uygulanan basntan daha azdr ve toz para geometrisi, radyal basn dalm ve toz-kalp duvar
srtnmesi deikenlerine baldr [9,10].
Yksek ham younluk ksa ve byk apl paralarda elde edilir. Toz boyutu ve ekli hem grnr younlua hem
de preslenebilirlie etki eder. Kk ve kresel tozlarn grnr younluklar byk ve dzensiz tozlara gre daha
yksektir. Kresel tozlarn grnr younluklar teorik younluun %60n bulurken, titreime tabi tutulduklarnda
bu deer %64e kadar kabilmektedir. Bu her parack iin 6-7 temas noktas anlamna gelmektedir. Dzensiz
ekilli tozlarda paketleme younluu teorik younluun %30u olurken, dzensiz ekilli ve sngerimsi tozlarda ok
daha dk olmaktadr. Paracklar aras srtnme, biri dierini kayarak geen paracklarn sergiledii direnci
ifade eder. Bu srtnme, nemli lde toz yzey alan, yzey przll ve yzeyin bileimi tarafndan belirlenir.
Toz boyutu kldke (yzey alan arttka) paracklar aras srtnme artar. Dier taraftan, kresel tozlarn
sktrlabilme kabiliyetleri, keli yapya sahip tozlarnkinden daha dk olmaktadr[11-13].
Bu almada ortalama toz boyutu, boyut dalm ve presleme basncnn preslenen paralarn ham younluuna
etkisi incelenmitir. Bu amala, Monel 400 alamndan su jeti soutmal dner disk atomizasyonu yntemiyle
retilmi farkl elek aralna ve ortalama boyuta sahip tozlar kullanlmtr. Presleme ilemi tek eksenli ve ift tesirli
preste gerekletirilmi olup, presleme basncnn ham younlua etkisi 150, 270, 360, 480 ve 600 MPa basnlar
kullanlarak incelenmitir. Ortalama toz boyutu ve boyut dalmnn ham younlua etkisi farkl elek aralndaki
tozlarn 480 MPa sabit basnta preslenmesiyle aratrlmtr.
Bu almada, bileimi izelge 1de verilen Ni-Cu alamndan (Monel 400) su jeti soutmal dner disk atomizasyonu
yntemiyle retilen tozlar kullanlm olup, retilen tozlar tek eksenli ift tesirli preste preslenerek; ortalama toz
boyutu, boyut dalm ve presleme basncnn ham younlua etkileri incelenmitir.
izelge1. Monel 400 alam kimyasal bileimi (% A.)
Element
Ni
Cu
Mn
Fe
Si
66.8
31.45
1.33
0.97
0.38
0.1
0.013
0.002
Monel 400 alamndan toz retimi KT Metalurji ve Malzeme Mhendislii Blmnde mevcut bulunan su jeti
soutmal dner disk atomizasyon nitesinde gerekletirilmitir. ematik resmi ekil 1de verilen atomizasyon
114

nitesinde, Monel 400 alam indksiyon stma sistemiyle grafit bir potada ergitilmi olup, potann dip ksmndaki
delikten serbest dme ile yksek hzda dnmekte olan su jeti soutmal bakr disk zerine aktlarak atomize
edilmitir. Buradan alnan tozlar eleme ilemine tabi tutulmu ve 355 m elek altna geen tozlar bu almada
kullanlmtr.
Atomizasyon nitesi dzgn dairesel st ksm ve konik dairesel alt ksmdan olumaktadr. Dzgn dairesel
ksmn ap 2500 mm, ykseklii ise 600 mmdir. Alt ksm, tozlarn toz toplama blgesine kolaylkla ulaabilmesi
iin konik olarak tasarlanmtr. Konik olan alt ksmn ykseklii ise 1500 mmdir. retilen tozlara herhangi bir
kirliliin bulamamas iin atomizasyon nitesinin tamam AISI 304 paslanmaz elik sacdan imal edilmitir. Yaplan
almalarda, disk malzemesi olarak s iletim katsays yksek olan elektrolitik bakr seilmi olup, disk ap 100
mm, et kalnl 0,5 mmdir. Ayrca, su ile soutmann yaplabilmesi iin disk, ters kap eklinde tasarlanmtr. Diskin
kanatk says 4 olup kanatk profili dikdrtgen ekillidir (34 mm). Disk soutma suyunun sv alamla ve retilen
tozlarla temasn engellemek iin metal sac koni kullanlmtr. Atomizasyon esnasnda sv metal disk merkezinden
yaklak 35 mm uzaa aktlarak disk kenarndan maksimum hzla atomize olmas salanmtr. Disk dnme hz,
kontrol nitesinden 0-24000 d/d aralnda istenen devir saysna ayarlanabilmektedir. Atomizasyon esnasnda disk
zerine aktlan sv alam diskin kenarnda maksimum hza ulaarak atomize olmaktadr. Bu bakmdan, diskin
evresel hz olarak en d apa (100 mm) karlk gelen hz alnmtr. Bu almada, toz retimi 14400 d/d disk
devir saysnda yaplm olup, bu devir saysna karlk gelen disk evresel hz 75 m/sdir.
ekil 1. Su jeti soutmal dner disk

atomizasyonu nitesi ematik resmi.
1- Atomizasyon odas, 2- atomizasyon
diski motoru, 3- atomizasyon diski,
4- sac koni, 5- grafit pota, 6- seramik
tka, 7- indksiyon bobini,
8- indksiyon stma sistemi,
9- pota ve tka motoru, 10- hidrolik
piston-silindir, 11- disk soutma suyu
girii, 12- disk soutma suyu k,
13- soygaz girii, 14- soygaz k,
15- toz toplama blm,
16- kontrol nitesi, 17- soutma nitesi.
retilen tozlarn ortalama toz boyutu ve boyut dalmnn hesaplanmasnda Malvern Mastersizer 2000 model
parack boyut analiz cihaz kullanlmtr. Yaplan analiz neticesinde tozlarn ortalama boyutu (d10), (d50 ) ve (d90)
hesaplanm ve boyut dalm grafikleri izilmitir. Bu ilem iin her bir deneyde retilen tozlardan konilemedrtleme yntemiyle yaklak 5-7 g numune alnmtr. Ayrca, tozlarn boyutlarna gre snflandrlmas amacyla
Retch marka titreimli eleme cihaz kullanlmtr. Tozlar 25, 36, 45, 63, 90, 125, 180 ve 250 mluk elek serisinde
20 dakika sreyle elenmitir.
retilen Monel 400 alam tozlarn morfoloji ve mikroyaplar ile tozlardan presleme ile retilmi paralarn mikroyap
incelemeleri Zeiss EVO LS10 marka taramal elektron mikroskobunda (SEM) yaplmtr. Monel 400 tozlarnn
morfoloji incelemeleri ift tarafl yapkan karbon band kullanlarak gerekletirilmitir. Mikroyap incelemeleri iin
tozlar, bir kalp ierisinde souk sertleen epoksi reine ile yataklandrlmtr. Dalama ilemi, taze hazrlanan 8
g FeCl3, 25 mL HCl , 100 ml H2Odan oluan dalama ayrac kullanlarak 20 s srede gerekletirilmitir. SEM
incelemeleri ncesinde, reine kalba yataklanm tozlar iletkenlik salanmas amacyla altn kaplanmtr.
Monel 400 alamndan toz retme ilemi esnasnda, tozlar yksek scaklkta olmalarndan dolay havada bulunan
oksijenle tepkimeye girerek yzeyleri ince bir oksit tabakasyla kaplanmtr. Bu oksit tabaka hem ok sert hem de
ergime scakl yksek bir bileiktir. Bu bileiin sert olmas, presleme ileminde tozlarn plastik deformasyona
urayarak ekil deitirmesini, dier bir ifade ile tozlar arasnda mekanik kilitlemeyi engelleyerek presleme ile ham
para elde edilmesine mani olur. Belirtilen bu olumsuzluktan dolay tozlardaki yzey oksit tabakasnn presleme
ncesi indirgenmesi gerekir. ndirgeme ilemi atmosfer kontroll bir sinterleme frnnda gerekletirilmitir. Monel
400 alam tozlar PLC kontroll sinterleme frnnda 550 oCde, nce azot gaz ile frn ortam temizlenerek, sonra
yksek saflkta (%99,999 saflkta) hidrojen gazyla 10 dak. sre ile indirgenmitir. ndirgeme ileminin tam olarak
gerekleip gereklemedii XRD cihazyla yaplan faz analizi ile kontrol edilmitir.
115

Hidrojen atmosferinde indirgenmi ve elemeye tabi tutularak tasnif edilmi tozlardan ham younlukta para retmek
amacyla PLC kontroll, tek eksenli ve ift etkili 50 ton kapasiteli hidrolik toz kalplama presi kullanlmtr. Tozlar
ASTM 8M04 standardnda ekme numunesi formunda bir kalpta preslenmi olup, kullanlan kalp tel erozyon
yntemiyle hassas bir ekilde retilmitir. Presleme basncnn ham younlua etkisini incelemek amacyla 150,
270, 360, 480 ve 600 MPa basnlarda presleme yaplmtr. Tozlarla kalp yzeyi srtnmesini en aza indirmek
amacyla presleme ncesi kalp ve zmba yzeyleri inko stearat ile yalanmtr. Kullanlan presin ematik resmi
ekil 2de gsterilmitir.
ekil 2. ift tesirli tek eksenli presin

ematik resmi.
1-Kauuk ayak, 2- kolonlar, 3-klavuz
silindir, 4- st silindir piston, 5- alt silindir,
6- pres tablas, 7- alt zmba ve kalp
boluu, 8- st zmba, 9- PLC kontrol
nitesi, 10- hidrolik devre elemanlar,
11- motor, 12- pompa, 13- hidrolik ya
tank.

Deiik elek aralklarna ait Monel 400 alam tozlarn SEM fotoraflar ekil 3te verilmitir. ekilden de
grlebilecei gibi, tozlarn tamam kresel ekilli olup, toz boyutuna bal olarak toz ekli deimemitir.
Genellikle 90 mdan byk boyutlu olan tozlarn yzeylerinde ekilme boluu olumutur. Toz boyutu
bydke ekilme boluu miktarnn artt tespit edilmitir. ekilme boluklarnn nispeten byk apl tozlarda
daha fazla olmas, toz boyutunun bymesiyle souma hznn azalmasna iaret etmektedir.
ekil 3 Monel 400 tozlarn morfolojisi. Elek aralklar: a) -25 m/tava, b) -45/25 m,
c) -63/45 m, d) -90/63 m.
116

Bu almada deiik elek aralklarna ait tozlar farkl oranlarda katlarak sekiz farkl rnek hazrlanmtr. Bylece,
ortalama toz boyutu ve boyut dalmnn preslenmi numunenin ham younluuna etkisi aratrlm ve en optimum
deerler ortaya konmutur. Bu amala, retilmi olan tozlar elenerek, -125/tava, -180/125, -250/180, -355/250 m
elek aralklarndaki tozlar ayrlmtr. Deiik elek aralklarndan farkl oranlarda katlarak oluturulmu sekiz farkl
rnek izelge 2de, bu rneklerin master sizer parack boyut cihaznda elde edilen toz boyut dalmlar ise ekil
4te gsterilmitir.
izelge 2. Hazrlanan toz numunelerin elek aral oranlar ve ortalama toz boyutlar
rnek
kodu
Elek aral
(%)
-125/tava
(m)
MN 1
-180/125
(m)
Ortalama toz boyutu

(m)
-250/180
(m)
-355/250
(m)
d10
d50
d90
29,96
69,72
139,62
74,75
128,605
207,81
147,87
209,99
299,74
199,81
305,99
457,81
55,25
97,97
183,12
52,45
110,79
267,45
40
55,98
152
362
40
53,35
107,61
342,27
100
MN 2
100
MN 3
100
MN 4
100
MN 5
30
70
MN 6
30
30
MN 7
30
MN 8
30
40
30
30
ekil 4. Farkl elek aral tozlardan oluturulmu rneklerin toz boyut dalmlar.
Tozlardaki yzey oksit tabakas presleme ve sinterleme zelliklerini olumsuz etkilemenin yannda, grnr younluk
ve ak hzn da olumsuz ynde etkiler. Grnr younluk ve ak hz preslemeye dorudan etki eden zelliklerdir.
Bunlarn dk olmas, elde edilecek parann ham younluunun da dk olmasna sebep olur. Bu almada
kullanlan Monel 400 alam tozlarnn oksit indirgeme ncesi ve sonras Hall ak aparatyla llen grnr
younluk ve ak hz lm sonular izelge 3 ve izelge 4de verilmitir. izelgelerden de grlebilecei gibi,
indirgeme sonrasnda grnr younlukta ve ak hznda nemli artlar meydana gelmitir.
izelge 3. Monel 400 alam tozlarn indirgeme ncesi grnr younluk ve ak hz deerleri.
rnek kodu
Grnr
younluk (g/
cm3)
Ak sresi (s)
MN 1
MN 2
MN 3
MN 4
MN 5
MN 6
MN 7
MN 8
3,27
3,01
2,96
2,90
3,31
3,34
3,47
3,43
6,35
6,39
7,96
8,3
5,25
5,77
6,28
5,88
117

izelge 4. Monel 400 alam tozlarn hidrojen atmosferinde indirgeme sonras

grnr younluk ve ak hz deerleri.
rnek kodu
MN 1
MN 2
MN 3
MN 4
MN 5
MN 6
MN 7
MN 8
Grnr
younluk (g/cm3)
3,46
3,17
3,14
3,12
3,34
3,39
3,49
3,54
Ak sresi (s)
5,03
5,40
6,10
6,90
4,90
5,14
5,40
5,00
Ortalama toz boyutu ve boyut dalmnn ham younlua etkisini incelemek amacyla izelge 2de elek aralk
oranlar verilen MN 1-8 kodlu toz numuneler 480 MPa sabit basnta preslenmitir. Elde edilen ham younluk
deerleri izelge 5te gsterilmitir.
izelge 5. Ortalama toz boyutu ve boyut dalmnn ham younlua etkisi.
rnek kodu
MN 1
MN 2
MN 3
MN 4
MN 5
MN 6
MN 7
MN 8
Ham younluk (%)
77
80
79
79
78
79
80
77
Presleme basncnn ham parann younluuna ve sertliine etkisini incelemek amacyla MN 6 rnek kodlu Monel
400 alam tozlar 150, 270, 360, 480 ve 600 MPa basnlarda preslenmitir. Presleme ncesi, tozlarn homojen
karmn salamak ve younluk gradyan oluumunu engellemek amacyla toz numuneler trbila tipi kartrcda
55 d/d dnme hznda 30 dak. sre ile kartrlmtr.
Presleme basncnn ham younlukla deiimi ekil 5te verilmitir. Artan presleme basncyla para younluunun
artt aka grlmektedir. Presleme balangcnda gevek halde olan tozlar, artan presleme basncyla birbiri
zerinden kayarak yeniden konumlanrlar. Basn uygulamas devam ettike tozlar arasndaki boluklar azalr ve
mekanik kilitlenme meydana gelir. Tozlarda plastik deformasyonun balad aama son aamadr. Bu aamada
younluk art tozlarn deformasyonuyla salanr; ancak tozlar plastik deformasyona urarken ayn zamanda
sertleerek mukavemet kazanrlar. Bu sebeple, son aamadaki younluk art hz balang ve ara aamalara
gre daha yavatr. ekil 5deki veriler de bunu dorulamaktadr. Grnr younluklar teorik younluun %38i olan
tozlar 150 MPa basnla preslendiklerinde, hzl bir younluk artyla ham younluk %60a ykselmektedir. 270
MPa presleme basncnda ham younluk %71e ulamaktadr. 270 MPa presleme basncndan sonra younluk art
hznda bir yavalama ortaya kmaktadr. 360, 480 ve 600 MPa basnlarda yaplan presleme ilemleri sonucu elde
edilen ham younluk deerleri srasyla %75, %79 ve %83tr. Bu durum, tozlarn plastik deformasyonla mukavemet
kazandklarn gstermektedir.
Preslenmi numunelerin presleme basncyla mikrosertliklerinin deiimi ekil 6da gsterilmitir. Mikrosertlik lme
ilemi Struers Duramin mikrosertlik lme cihaznda, 10 g ykn 10 s sre ile tatbik edilmesiyle gerekletirilmitir.
ekil 6dan da aka grld gibi, artan presleme basncyla Vickers sertlik deeri artmtr. Toz paracklarn
artan presleme basncyla daha sk paketlenmelerinin sertlii artrd anlalmaktadr. 150, 270, 360, 480 ve 600
MPa basnlarda yaplan presleme ileminde elde edilen mikrosertlik deerleri srasyla 160, 180, 205, 255 ve 270
Vickersdir. Artan presleme basncnn tozlarn daha sk paketlenmesi salayarak sertlik artna sebep olmasnn
yannda, tozlar plastik deformasyona uratarak sertliklerinin artmasn da salamaktadr.
ekil 5. Presleme basncyla ham younluun deiimi.
118

ekil 6. Preslenmi ham parada presleme basncyla mikrosertliin deiimi

Preslenmi ham haldeki paralarda, presleme basncna bal olarak porozite ve toz parack deformasyonu deiimi
elektron mikroskobunda incelenmi olup, 270, 360, 480 ve 600 MPa presleme basnlar iin mikroyaplar ekil
7-10da gsterilmitir. ekillerin incelenmesinden, artan presleme basncyla porozitenin azald, tozlardaki plastik
deformasyonun, paracklar aras temas alannn ve temasta olan parack saysnn artt aka grlmektedir.
ekil 7. Preslenmi ham paradaki porozite ve parack deformasyonu (presleme basnc 270 MPa).
119

4. SONULAR
Yaplan deneysel almalardan ve bulgularn deerlendirilmesinden elde edilen sonular aada verilmitir:
1. retilen Ni-Cu alam (Monel 400) alam tozlarn tamam kresel ekilli olup, toz boyutuna bal olarak
toz ekli deimemitir. 90 mdan byk boyutlu tozlarn yzeylerinde ekilme boluu meydana gelmitir. Toz
boyutu bydke ekilme boluklarnn artt tespit edilmitir.
2. Monel 400 alamndan retilen tozlarnn yzeylerindeki oksit tabakas yksek saflkta (%99,999 saflkta)
hidrojen atmosferinde 550 0C scaklkta 10 dak. sre ierisinde indirgenmitir.
3. ndirgeme sonrasnda grnr younlukta ve ak hznda nemli artlar meydana gelmitir.
4. Artan presleme basncyla ham younluk artmtr ve en yksek ham younluk 600 MPa presleme
basncyla %83 olarak elde edilmitir.
5. Artan presleme basncyla sertlik deerinin artt, porozitenin azald, tozlardaki plastik deformasyonun,
paracklar aras temas alannn ve temasta olan parack saysnn artt tespit edilmitir.
KAYNAKLAR
1. German, R.M., Toz Metalurjisi ve Parackl Malzeme lemleri eviri Editrleri: S. Sarta, M. Trker, N.
Durlu, Trk Toz Metalurjisi Dernei Yaynlar:05, 2007,Ankara.
2. Gimenez, S., Vagnon, A., Bouvard, D., Biest, O. V., Influence of The Green Density on The Dewaxing Behaviour
of Uniaxially Pressed Powder Compacts, Materials Science and Engineering A, 430, 277-284, 2006.
3. nl, N., avusoglu, L., Toz Metalurjisinin Yaygn Kullanm Alanlar, Metal Dnyas,Teknik Yaz, say:11-12,
stanbul, 1995.
4. Rahman, M.M., Nor, S.S.M., An Experimental Investigation of Metal Powder Compaction at Elevated
Temperature, Mechanics of Materials, 41, 553-560, 2009.
5. Fischmeister, H.F., Arzt, E., Densification of Powders by Particle Deformation, Powder Metallurgy, vol.26,
n. 2, 1983.
6. Poquillon, D., Lemaitre, J., Carles, V., Tailhades, Ph., Lacaze J., Cold Compaction of Iron Powders-Relations
Between Powder Morphology and Mechanical Properties Part I: Powder Preparation and Compaction,
Powder Technology, 126, 65 74, 2002.
7. Ng, L.S, Loh, N.L., Boey, F.Y.C., Cold-Hot Isostatic Pressing of Mar M200 Superalloy Powders, Journal of
Materials Processing Technology, 67, 143-149, 1997.
8. Al-Qureshi, H.A., Galiotto, A., Klein, A.N., On The Mechanics of Cold Die Compaction For Powder Metallurgy,
Journal of Materials Processing Technology, 166, 135-143, 2005.
9. Park, S.J., Han, H.N., Oh, K.H., Lee, D.N., Model For Compaction of Metal Powders, International Journal
of Mechanical Science, 41, 121-141, 1999.
10. Yamaguchi, K., Takakura, N., Imatani, S., Compaction and Sintering Characteristics of Composite Metal
Powders, Journal of Materials Processing Technology, 63, 364-369, 1997.
11. Hyoung, S., K., Yield and Compaction Behavior of Rapidly Solidified AlSi Alloy Powders, Materials Science
and Engineering A, 251, 100105, 1998.
12. Iveson, S.M., Page, N.W., Dynamic Strength of Liquid-Bound Granular Materials: The Effect of Particle Size
and Shape, Powder Tecnology, 152, 79-89, 2005.
13. Smith, L.N., Midha, P.S., Graham, A.D., Simulation of Metal Powder Compaction, For The Development of a
Knowledge Based Powder Metallurgy Process Advisor, Journal of Materials Processing Technology, 79,
94-100, 1997.
120

COMPOSITES
www.turkishpm.org
121

The effect of amount of methanol on the properties of

Al-Al2O3 composite powders
Aykut Canakci1, Temel Varol1, Cihad NAZK1
Department of Metallurgical and Materials Engineering, Karadeniz Technical University, Trabzon, Turkey
aykut@ktu.edu.tr, tvarol@ktu.edu.tr
Abstract
Mechanical alloying (MA) of elemental powder mixtures of Al- Al2O3 was performed in an argon atmosphere at
various amount of methanol using a planetary ball mill. The effect of amount of methanol on production of Al-Al2O3
composite powder were evaluated. A process control agent (PCA) which the balance between cold welding and
fracturing is controlled by the addition of a surface additive. Different amounts of methanol were used to study the
effect of the process control agent on synthesis and properties of the Al-Al2O3 composite powders. The microstructural evolution of the milled powders was characterized by X-ray diffraction (XRD) and scanning electron microscopy (SEM). Results indicated that varition amount of PCA during milling process led to a significant change in
morphology, particle-size distribution of milled powders. Morever, different microhardness values were obtained for
different amount of PCA at same milling time.
Keywords: Composite powders, mechanical alloying, Process control agent (PCA)
1. Introduction
Mechanical alloying (MA) is a useful powder processing technique that can produce a variety of equilibrium and
non-equilibrium alloy phase. The advantage of this process technology is that the powder can be produced in large
quantities and the processing parameters can be easily controlled, thus it is a suitable method for commercial applications [1]. By using MA, it is possible to produce a fine and homogeneous distribution of hardening particles
be difficult or even impossible with most molten material techniques. The amount that dispersoids strengthen the
composite depends on particle type, size, morphology, volume fraction and distribution [2]. In this process, two essential processes are involded, namely, cold welding between particles under high energy collosion. Cold welding
and fracturing enable powder particles to be always in contact with each other with atomically clean surfaces and
with minimized diffusion distance. Without cold welding, the particles will not be bonded together for interdiffusion,
while too much cold welding will lead to an increase in particle size and no formation of clean surfaces for diffusion.
Therefore the balance between cold welding and fracturing is essential for a successful MA. The alloying process
can only be continued if the rate of welding balances that of fracturing and the average particle size of the powders
remains relatively coarse. However, for most material systems, the balance between cold welding and fracturing
does not ocur naturally. The balance has to be controlled by the addition of a surface additive, in most cases, called
a process control agent (PCA). Several PCAs, such as cyclohexane, hexane, stearic acid, methanol, ethyl acetate
or polyethylene glycol are often used in MA [3-6].
To successful attain products with fine dispersion and good homogeneity; it is essential to establish a balance between cold welding and fracturing. However, for ductile systems, as in the milling of aluminum particles, this balance
does not ocur naturally, resulting in non-uniform microstructures and properties. One of the effective methods to
avoid excessive cold welding reported in the literature is the addition of surface-active substances, known as process control agents (PCAs). These surfactants are mostly organic compounds and are usually added to the powder
charge in proportions that vary from 1 to 5wt.% [7].
In this work we have investigated the effect and the role of different amount of methanol on the morphology, particle
size and microstructure of a Al-Al2O3 composite powder produced by MA.
122

2. Experimental Procedure
The initial materials used in this research work were Al powders and Al2O3 particles with a composition corresponding to Al-10wt.%Al2O3. The as-atomized Al alloy powders (Gndodu Exotherm Company, Turkey) with an average
powder particle size of 127m and Al2O3 particles (99,7 % purity, Wacker Ceramic Company, Germany) with an
average particle size of 13m are used as raw materials. The chemical composition of the as-atomized Al alloy (in
wt. %) is 1.230Fe, 1.000Si, 1.000Pb, 0.710Cu, 0.530Zn, 0.116Mn, 0.071Ti, 0.050Mg and Al (balance). Fig. 1a and
1b show the morphologies of the as received Al alloy matrix powder and Al2O3 particles. The Al alloy matrix powder
particles are ligamental shape and the Al2O3 particles are polygonal in shape. Methanol was used as the process
control agent in varying amounts of 1, 2 and 3 wt% to study the effect of amount of methanol. The powders were
milled in two vials of 80ml using a Fritsch Pulverisette 7, Premium line planetary ball mill at a rotation speed of
400rpm. The mixture of Al-Al2O3 powders was milled for 0.5, 1, 2, 4, 6, 8, 10h. The balls used were 10 mm in diameter and ball-to-powder weight ratio was 10:1.
The morphology and microstructure of milled powders was analyzed by scanning electron microscopy (SEM). The
size distribution of as-received and milled powders was quantified by a laser particle size analyzer (Malvern, model
Mastersizer Hydro 2000). Apparent density of composite powders were measured using a Standard Hall Flowmeter. The microhardness of as-received and milled powders was measured by a microhardness tester (Struers
microhardness tester) at 10gr load.
(a)
(b)
Table 1. The amount of PCA (methanol) and coded process.
Coded Process
Amount of PCA (wt.%)
Process 1
Process 2
Process 3
3. Results and Discussions

3.1. Effect of the processes with amount of PCA on milling process
Milling process is given in Table 2. Processes are summarized in the Table 2 for better understanding of the stages
of milling. Table 2 shows the effect of the processes with amount of PCA on the mechanical alloyed Al-Al2O3 powders.
Table 2. The shapes of milling during the mechanical alloying.
Process
0.5
1
P1
Flake +irregular Flake
2
Irregular
4
6
Semi Equiaxial Equiaxial
8
Equiaxial
10
Equiaxial
P2
Ligamental
Ligamental
+ Flake
Flake+irregular
Flake+ Semi
Equiaxial
Semi
Equiaxial
Equiaxial
Equiaxial
P3
Ligamental
Ligamental
Ligamental +
Flake
Flake
Flake+
Flake+ Semi
Semi
Equiaxial
Equiaxial
Semi
Equiaxial
123

3.2. Effect of the processes with amount of PCA on the powder morphology
In order to understand the effect of methanol on the morphology of Al-Al2O3 powders during mechanical alloying,
Al-10wt.%Al2O3 powder mixtures were milled with different amounts of methanol (1, 2, and 3 wt.%) for 10h. Figs.
2(a-k) show the SEM images of the powders milled for different times (0.5, 1 and 2h). Figs. 2(a-c) are SEM images
with process 1 (1 wt. %), Figs. 2(d-f) are SEM images with process 2 (2 wt. %), and Figs. 2(g-k) are SEM images
with process 3 (3 wt. %) for different times. The initial morphologies of both Al and Al2O3 powders are shown in Fig.
1a and 1b, respectively. As it is shown in these Figures, the Al2O3 particles are angular or poligonal in shape while
Al powders has a distribution of ligament or irregular. It is clear that particle morphology changes with increasing
milling time. After 0.5h of milling time (Fig. 2a), the particles were severely deformed plastically by MA and exhibited
a shape changes from nearly ligament to flake in milling made by wt. %1 PCA (at process 1). In other words, plastic
deformation of the soft matrix powder starts quickly in a short milling time which results in changing its morphology
from ligamental to flattened shape. As shown Fig. 2d (at process 2), with increasing amount of methanol, particle
deformation decreased and particle morphology showed little change. By increasing the amount of methanol significant changes werent observed in morphology of initial powders, as shown in Fig. 2g (at process 3). There is an
important observation in milling made by 3 wt.% PCA. As can be seen Fig. 2g, alumina particles (Al2O3) were not
embedded into the Al powders because of amount of excess methanol. In other words, excess amount of methanol
decreases the effectiveness of ball-powder collisions. When the amount of methanol is less than 3 wt.% during
milling time, such as 1 and 2 wt.%, work hardening becomes more dominant in the mechanical alloying process.
As shown from SEM images of 2h of milling (Figs. 2c, 2f, 2g) fracturing effectiveness decreased with increasing
amount of methanol. It can be easily observed that finer as-milled Al-Al2O3 powder particles are achieved with increasing milling time. If the critical PCA value is exceeded (3 wt.%), the particle morphology and particle size varies
from less than other process (1 and 2 wt.%) with the increasing milling time. Fracturing process seems dominant
in the powders using 1 wt.% methanol (Fig. 2c).
Fig. 2. Variation of the powder morphology with milling time at different process:
(a-c) process 1, (d-f) process 2, and (g-k) process 3.
124

When particle morphology was examined at the end of 4h of milling it can be seen, cold welding process is more
than fracturing process for 1 wt.% methanol (Fig. 3a). In addition to particle morphology has started to convert into
a equiaxial morphology. Morphology change for P2 process (2 wt.% methanol) are almost the same as P1 process
(1 wt.% methanol). However, flake morphology was reached at the end of 4h of milling for P3 process (3 wt. %
methanol) (Fig. 3g). At longer milling time, work hardening of powders causes them brittle and fracturing effectiveness becomes significant and the changing trend of particle morphology is observed.
Fig. 3. Variation of the powder morphology with milling time at different process:
(a-c) P1 process , (d-f) P2 process, and (g-k) P3 process.
Fig. 4 shows the powder morphologies after 10h of MA. The particle morphologies of P1 and P2 processes have
semi equiaxed morphology and similar morphology but the particle size are different because of amount of methanol used in mechanical alloying process. Both cold welding and fracturing process were observed in P3 process.
Fig. 4. Variation of the powder morphology with different processes at 10h milling time:
(a) P1 process, (b) P2 process, and (c) P3 process.
125

3.3. Effect of the processes with amount of PCA on the apparent density
When apparent densities were examined for P1, P2, and P3 processes, it can be seen, apparent density values increased at the beginning of milling process and then decreased but again towards the end of milling process
increased. The change in values of apparent density closely related to powder morphology. When powder morphology compared with apparent densities values it can be seen easily, flake morphology increases the value apparent
density. Flake morphology provides better packed. To the contrary, reduces the value of the apparent density with
increases fracturing process because of deterioration from equiaxed morphology. In addition, it was observed that
apparent density decreases with increasing amount of methanol because of increases the ability of powder agglomeration with increasing amount of methanol. The various stages of a ductile-brittle system during mechanical
alloying are shown in Fig. 5.
Fig. 5. The various stages of a ductile-brittle system during mechanical alloying [8].
Table 3 and Fig. 6 are shown the effect of the processes with amount of PCA on the apparent density milled Al-Al2O3
powders.
Apparent
density
(gr/cm3)
Amount of
PCA
(wt.%)
1
2
3
Table 3. Effect of PCA content on the apparent density.

Milling time (h)
0
0.5
10
1.038
1.038
1.038
1.055
1.207
1.148
0.965
1.216
1.165
0.807
0.715
1.128
0.995
0.822
0.672
1.248
0,911
0.712
1.276
1,031
0.795
1.278
1.136
0.959
Fig. 6. Variation of the apparent density as a function of milling time at different processes for amount of PCA.
126

3.4. Effect of the processes with amount of PCA on the particle size
Table 4. The relationship between particle size and milling time at different processes for amount of PCA.
Milling time (h)
Particle
size
(m)
0.5
10
P1
127
132
130
65
33
103
112
115
P2
127
121
116
60
38
33
35
28
P3
127
126
124
133
116
42
45
37
Fig. 6. shows effect of PCA content and milling time on the average the particle size of ball milled powders. Al
powders in their initial stage are predominantly irregular and ligamental in shape. During high energy milling, plastic
deformation, cold welding and fracture are predominant factors, in which the deformation leads to a change in particle shape, cold welding leads to an increase in particle size and fracture leads to decrease in particle size. Table
4 presents average particle size values after 0h, 0.5h, 1h, 2h, 4h, 6h, 8h, 10h of milling times for all processes. The
effect of milling time on the particle size of ductile powders has been studied separately by previous researches in
the case of monolithic and composite powders [9,10-12]. In the all cases a similar trend was observed an increase
in the particle size followed by a decrease and then steady state in the previous investigations [13-15]. However,
the average particle size (d0.5) of the Al alloy-10 wt.% Al2O3 composite powders in this study decreased continously
with the increasing milling time (Fig. 6). This can be attributed to the initially used Al alloy powders having ligamental
shape. These powders can be easily deformed by high energy collisions of balls and they can be quickly fractured
weakness regions.
Unlike most of the work related to mechanical alloying [9,16,17], in this study, this particle morphology because of
initial powders have ligamental shape. Powders are deformed due to high energy collisions of balls and they are
fractured from fine regions. Flatten shape occurs after this fracturing process so particle size decreases unlike increasing at early stage of milling. With increasing milling time, work hardening of powders causes brittle of powders
and fracturing process becomes effective process. It was observed that amount of PCA has a significant effect on
the particle size of composite powders.
Fig. 6. Effect of milling time on the average particle size of composite powders
3.5. X-ray diffraction analysis of milled composite powders
Al alloy powders underwent deformation and cold welding caused by continuous collision and split between balls
and powders. As can be seen in Fig. 7, ball milling makes diffraction peaks become wide and the peaks intensities
decrease. These observations were found in agreement with the reported for other Al alloy composites [11,14,18,19]
(Abdoli et al., 2008; Razavi et al., 2006; Parvin et al., 2008; Abdoli et al., 2009). The concept of X-ray peak broadening related to the crystallite size is widely accepted in the study of mechanically alloyed powder particles. Fig.
7 shows the XRD patterns as a function of milling time. Due to the mechanical deformation introduced into the
127

powder, crystallite refinement occurs and the lattice strain increases. The unmilled powder already presented a very
refined crystallite since the high cooling rate imposed using the gas atomization method, and the milling process
reduced its size. This result show that the mechanical alloying is an effectiveness process to produce nanostructure
materials [20].
Fig. 7 shows the XRD patterns of composite powder that were mechanical alloyed with 1 and 3 wt.% methanol
(2h and 4h) and initial Al alloy (0h) powders. Ball-impact energy of balls decreases because of increasing amount
of PCA so work hardening of particles decreases and there is no significant change in peaks wide and the peaks
intensities for P3 process which used 3 wt.% methanol. In other processes (1 wt.% methanol), Peaks wide and
peaks intensities as well as particle size significantly changed due to deformation occurred at the end of 4h of milling. Increasing methanol content prevented particle deformation and reduced effectiveness of milling process.
Fig.7. XRD patterns of Al alloy and Al-Al2O3 composite powders for some milling times.
3.6. Microhardness
The change of microhardness of milled powders as a function of milling time and PCA content is given in Fig. 8.
Generally, increasing milling time increases the deformation and work hardening of powders. As can be seen in Fig.
8, there is a continuous increase in microhardness of all process with increasing milling time and increasing rate of
microhardness values decreases with the increasing amount of PCA. As can be seen increasing milling time causes
a raise in microhardness of particles. The main factor effecting the microhardness of powders is work hardening of
powders. Up to 5h of milling the rate of increasing of microhardness, for P1 process (1 wt.% methanol) is more
than P3 process (3 wt.% methanol) but this rate decreases with increaing milling time and microhardness values of
P3 proces is more than these P1 process at the end of 10h in process (Fig. 8).
128

Fig. 8. The change in microhardness of Al-Al2O3 composite powders with different amount of PCA and milling time.
4.Conclusion
The effect of amount of methanol on production of Al-Al2O3 composite powder were investigated. It was observed
that amount of PCA has a great effect on the powder characteristics. The increase of the amount of PCA reduced
mechanical alloying process effectiveness up to 6h of milling and the steady-state time was delayed. Moreover, The
process which used 2 wt.% methanol gave the best results within three process. Consequently, the results indicate
that amount of PCA considerable effects on the particle size as well as on the structural behavior of the as milled
powders.
Acknowledgement
The authors are grateful to Karadeniz Technical University Research Fund for the financial supporting of this research work (No: 2007.112.10.2). The researchers would also like to thank to Gundogdu Exotherm Service for
providing Al 2024 powders.
References
1. Shokrollahi H, Materials and Design 30 (2009) 3374-3387
2. Estrada-Guela I, Carreno-Gallardo C, Mendoza-Ruiz DC, Miki-Yoshida M, Rocha-Rangel E, Martnez-Snchez
R, Journal of Alloys and Compounds 483 (2009) 173177
3. Lu L, Zhang YF, Journal of Alloys and Compounds 290 (1990) 279-283
4. Juarez R, Sunol JJ, Berlanga R, Bonastre J, Escoda L, Journal of Alloys and Compounds 434-435 (2007) 472476
5. Pilar M, Sunol JJ, Bonastre J, Escoda L, Journal of Non-Crystalline Solids 353 (2007) 848-850
6. Long BD, Zuhailawati H, Umemoto M, Todaka Y, Othman R, Journal of Alloys and Compounds 503 (2010) 228232
7. Gonalves VS, Rocha CJ, Leal Neto RM, Sixth International Latin-American Conference on Powder Technology,
2010, Rio de Janerio, Brazil
8. Fogagnolo JB, Velasco F, Robert MH, Torralba JM, Materials Science and Engineering A342 (2003) 131/143
9. Razavi Tousi SS, Yazdani Rad R, Salahi RE, Mobasherpour I, Razavi M, Powder Tech 192 (2009) 346351
10. El-Eskandarany MS (2000). Mechanical Alloying for Fabrication of Advanced Engineering Materials. William
Andrew Publishing, New York.
11. Abdoli H, Farnoush H, Salahi E, Pourazrang K, Mater. Sci. and Eng. A (2008) 486: 580584.
12. Arik H, Turker M, Mater. and Design. (2007) 28: 140146.
13. Hashim J, Looney L, Hashmi MSJ, J. of Mater. Process. Tech. (1999) 92:1-7.
14. Razavi Hesabi Z, Simchi A, Seyed Reihani SM, Mater. Sci. Eng. A(2006) 428:159-168.
15. Adamiak M, J. Achiev. Mater. Manuf. Eng. (2008) 31(2): 191196.
16. Rodrigues JA, Gallardo JM, Herrera EJ, Journal of Materials Science 32 (1997) 3535-3539
17. Fuentes JJ, Rodriques JA, Herrera EJ, Materials Characterization 61 (2010) 386-395
18. Parvin N, Assadifarda R, Safarzadeha P, Sheibanib S, Marashi P, Mater. Sci. and Eng. A (2008) 492: 134140.
19. Abdoli H, Asgharzadeh H, Salahi E, J. of Alloys and Compounds (2009) 473: 116-122.
20. Fogagnolo JB, Amador D, Ruiz Navas EM, Torralba JM, Materials Science and Engineering A 433 (2006)
45-49
129

Effect of The AlxNiy Phases On The Mechanical Properties Of

The AlCuSiMg/SiC(Ni)p Composites

Judit PZMN*, Viktor MDAI**, Zoltn GCSI*, Alz MOLNR*, rpd KOVCS*
*
University of Miskolc, Institute of Materials Science, 3515 Miskolc-Egyetemvros, Hungary;
femjuju@uni-miskolc.hu; femtangz@uni-miskolc.hu; alizmolnar27@gmail.com; femkov@uni-miskolc.hu
**
University of Miskolc, Department of Mineralogy and Petrology, 3515 Miskolc-Egyetemvros;
askcesar@uni-miskolc.hu
Abstract
In our research work AlCuSiMg/SiC(Ni)p composite was produced by powder metallurgy. The reinforcing phase
(SiC) was surface coated by electroless nickel plating. The ceramic particles with inert surface had to be activated
by acidic pre-treatment or surface oxidation or palladium chloride activation before surface coating. The quality of
formed metal layer depends on the pre-treatment methods. The nickel layer of the silicon carbide particles and
matrix react together during the sintering, and AlxNiy compound forms on the interface of AlCuSiMg-SiC. This compound effects on the mechanical properties of the composite. In our research work the compressive yield point,
compressive strength and micro hardness were determined. The effect of the phase arrangement was studied
on the mechanical properties. The microstructure of the samples was examined by SEM, optical microscopy and
XRD.
Keywords: Surface modification, Silicon carbide particles, Aluminium-nickel compounds, Powder Metallurgical
Composite
1.Introduction
To improve the interfacial bonding between the matrix and the reinforcing phase, the surface of the reinforcing
phase is coated with different metal layers. Mostly the particles are surface treated with copper [1-3] or nickel [4-6].
These metal layers can improve not only the interfacial bonding but the properties of the matrix. These metal layers
can be formed by different surface treating methods, for example by galvanization [7], mechanical alloying [8] or
electroless plating [9]. The last method can be used simply in a laboratory conditions and it provides equal layer
thickness, but the catalytic active surface is need to form the deposit. It is not simple to coat with metal the silicon
carbide particles. The surface of the silicon carbide particles must be activated before surface coating. Different
pre-treatment methods can be applied as a surface activation (Table 1), for example acidic pre-treatment, surface
oxidation or palladium chloride activation [10-11].
Table 1 The main parameters of the pre-treatment methods
Type of pre-treatment
Chemical composition
Acidic pre-treatment
Sodium hypophosphite
(NaH2PO2H2O) 30 g/l
Lactic acid 98%
(CH3CH(OH)COOH) 20ml/l
T=358K (85C), 35
min.
The development of a thin

hypophosphite layer can be
expected on the surface.
In an air atmosphere in a
heat-treatment furnace
At 1100C for 3h
heat treatment,
oxidation
According to the Deal-Grove model,

a continuous, compact oxide layer
(SiO2) develops on the surface of
ceramic particles.
Surface oxidation
Applied parameters
130
Mechanism

Sensitization
Activation
Stannous chloride
15g/l
SnCl2
Hydrochloric acid
HCl (cc. 37%) 55cm3/l
PdCl2
0,5 g/l
HCl (cc. 37%) 2ml/l
T= 298K (25C),
t=10 min
Sn2+ ions adsorb on the surface of

silicon carbide particles.
T=298K (25C),
t=25 min
The Sn2+ ions oxidize further

into Sn4+ ions on the surface of
sensitized particles, and the Pd2+
ions reduce to Pd0. Palladium
nuclei form on the surface of SiC
particles.
The applying of each pre-treatment method determines the quality of the developing deposit (Fig. 1). Particular
surface activation can be realized by the acidic pre-treatment method. Consequently, only one part of the surface
of the silicon carbide particles can be covered with metal layer. Mostly, nickel caps form on the edge of the ceramic
particles after the electroless nickel plating. Coherent silicon oxide layer develop on the surface of the SiC particles
after the surface oxidation. The oxide layer is able to activate the inert surface, so nickel nuclei with homogeneous
arrangement form on the surface of the substrate after the electroless nickel plating. Elemental palladium nuclei can
be created on the surface of the silicon carbide particles after the two steps activation process. These metal nuclei
work as nucleus forming places and they give the possibility to form continuous metal layer.
Figure 1. The SEM photos of the electroless nickel plated SiC particles [9]
a) Nickel cap formed on the edge of the SiC particles after the acidic pre-treatment and EN plating
b) Nickel nuclei with homogenous arrangement on the SiC particles after the surface oxidation and EN plating
(a) c) SiC particles electroless nickel plated
(b) using palladium chloride activation (c)
AlxNiy phases develop in the Al/SiCp composites using the surface treated reinforcing particles. In our research work
the surface treated ceramic particles were used as a reinforcing phase in the powder metallurgical composite. This
producing process is three steps. First the mixing of the powder (matrix and reinforcing phase), second the pressing of the power mixture and third is the sintering of the green product. The matrix and the nickel layer of the silicon
carbide particles can react with each other due to the acceptable high temperature and long time of the sintering
and AlxNiy phases form around the particles. The aim of our research work was to study aluminium-nickel phases
and to determine the mechanical properties of Al/SiC(Ni)p composites.
2. Experimental
2.1. Starting materials
The silicon carbide powder was chosen as a reinforcing phase. The powder was delivered by Saint Gobain Grains
& Powders. Particle size distribution was established by computer image analysis (Fig. 2). Specific surface was
determined by BET method. The powder is characterised by relatively low specific surface of SBET,77K=0.14 m2/g
which is confirmed by SEM observations (Fig. 3). The X-ray diffraction spectrum (Fig. 4) clearly show that the used
SiC powder is not homogenous in terms of phases content and its atomic stoichiometry (Mean atomic stoichiometry
is 54,38 atom% C; 45,62 atom% Si).
Aluminium based powder mixture signed as Alumix 123 was delivered by ECKA Granules. This powder was applied
as a matrix in the production of the composite samples. Except aluminium the powder mixture contains 4.5-wt%
Cu, 0.7-wt% Si, 0.5-wt% Mg and 1.5-wt% of Microwax C as a lubricant (Figure 5, a). The composition of the powder
makes the sintered products heat-treatable (Figure 5, b).
131

Figure 2. Particle size distribution of SiC powder

Figure 4. XRD spectrum of SiC powder

3. Results
Figure 3. SEM photomicrograph of SiC particles
Figure 5. XRD Spectrum of Ecka granulate

a) before the sintering

b) after the sintering
According to the Al-Ni binary phase diagram (Fig. 6.) different compounds (Al3Ni, Al3Ni2, AlNi and AlNi3) form during
the reaction of the nickel layer of the silicon carbide particle and the aluminium alloy matrix. The chemical composition and arrangement of the AlxNiy phases have a connection with the quality of the pre-treatment and the arrangement of the pre-treatment layer. Namely, nickel deposit forms only such part of the particles, where the surface
of the particles was activated. So the arrangement of the nickel coating determines the arrangement of the AlxNiy
phases formed during the sintering (Fig. 7.).
The hypophosphite layer sticking with weak adhesion covers the surface of the silicon carbide particles after the
acidic pre-treatment. This pre-treatment layer is not compact. The electroless nickel deposit is situated only on
the edge of the SiC particles. AlxNiy phases can form in two places in the electroless nickel plated SiC particles
reinforced powder metallurgical composites (using acidic pre-treatment as a surface activation method). One part
Figure 6. Al-Ni binary diagram
132

Figure 7. The arrangement of the AlxNiy phases in AlCuSiMg/SiC(Ni)p composites

a) using the acidic pre-treatment (AP-MMC)
b) using the surface oxidation (SO-MMC)
c) using the palladium chloride activation (PCA-MMC)
of the electroless nickel deposit is able to separate from the surface of the silicon carbide particles due to the
weak adhesion during the mixing and pressing of the powder mixture. These separated coating parts react with
the aluminium alloy and AlxNiy phases can be formed far from the SiC particles (Fig. 7. a). The shape of the AlxNiy
phases is like a reservoir. Otherwise, the deposit part sticking to the particles react with the matrix, consequently
AlxNiy phases develop around the reinforcing particles. At the sintering temperature (5755C) AlNi phase with 50%
nickel concentration forms around the silicon carbide particles and AlNi3 with 75% nickel concentration far from the
SiC particles [11].
Similar AlxNiy phases can be created by applying of the surface oxidized and electroless nickel plated SiC particles
(SO-MMC). But the arrangement of AlxNiy phases in the SO-MMC is different in the acidic pre-treated and EN plated
SiC reinforced composite (AP-MMC), because the compact oxide layer is situated on the full surface of the silicon
carbide particles. So the activation of the surface is more successful in SO-MMC than the earlier acidic pre-treatment. The nickel nuclei formed on the surface of the SiC particles activated by surface oxidation do not separate,
so the above-mentioned nickel reservoirs is not able to develop in the matrix. The AlxNiy phases are situated in an
island shape around the ceramic particles (Fig. 7. b). The full nickel quantity can be found near the silicon carbide
particles, so the AlNi3 phase with high nickel concentration surrounds the reinforcing particles. As the nickel concentration is different around the particles, so the thickness of the AlxNiy yard too. Mostly, Al3Ni2 phases with 40% nickel
concentration can be formed by the reaction of the matrix and nickel layer of the silicon carbide particles [11]. The
successful surface activation provides compact deposit in the case of the palladium chloride activation. When the
silicon carbide particles EN plated after palladium chloride activation is used as a reinforcing phase in the production of the composites, the nickel concentration is equal around each particle. The nickel layer of the SiC particle
reacts with the aluminium alloy matrix and AlNi3 and AlNi phases surround the ceramic particles (Fig. 7.c).
3.1 Mechanical properties of the AlxNiy phases
Micro hardness (HV0.2) was measured on the AP-MMC composite samples (using the acidic pre-treatment for the
surface activation). The micro hardness (HV0.2) of the above-mentioned aluminium-nickel reservoirs was determined. The results centre round two data, exactly 140 HV0.2 and 220 HV0.2. These hardness results advert to the
AlxNiy phases with different nickel concentration. The
X-ray diffraction phase detection demonstrates the
different hardness data (Fig. 9.). The Al3Ni2 phase
has less nickel concentration and lower hardness
than AlNi and AlNi3 phases.
If the hardness of the aluminium alloy is collated with
the AlxNiy phases (Fig. 8), it can be seen that the compounds phase is very rigid. The AlxNiy phases show
double higher hardness (152 HV0.2) than the matrix
(82 HV0.2). The Standard Deviation (51 HV0.2) is
three times higher than the matrix (17 HV0.2).
3.2 Compressive test of the AlCuSiMg/SiC(Ni)p
composites
The surface modified silicon carbide particles reFigure 8. Hardness of the matrix and AlxNiy phases
inforced composite samples were studied by compressive test. The aim of the examination was to determine the effect of the rigid AlxNiy phases on the compressive properties of the composite. The composite samples
133

Figure 9. X-ray diffraction spectrum of the AlCuSiMg/SiC(Ni)p composite (using palladium chloride activation)
a) XRD specrtum of the composite b) XRD spectrum of the matrix powder mixture
were pressed by quenched steel plates with 5 tonnes load. The results of the compressive test (Fig. 10.) show that
the compressive properties of the composite are similar to the matrix, when the silicon carbide particles were pretreated by acidic pre-treatment (AP-MMC) or without the surface modification (10SiC-MMC). The SO-MMC and
PCA-MMC samples have lower compressive properties than the AP-MMC samples. According to the results it can
be said that the AlxNiy phases have the effect on the compressive properties in small extent.
4. Conclusion
The electroless nickel plated SiC reinforced aluminium alloy matrix composite was produced by powder metallurgy. The electroless nickel layer of the particles and the
matrix react with each other during the sintering, and AlxNiy
phases form in the interface of the reinforcing phase and the
matrix. The effect of the AlxNiy phases was determined on
the compressive properties by compressive test. The results
showed that the formed compounds phases have effect on
the compressive strength in a small extent.
5. ACKNOwledgement
This research was carried out as part of the TAMOP4.2.1.B-10/2/KONV-2010-0001 project with support by
the European Union, co-financed by the European Social
Fund.
Figure 10. Results of the compressive test in the

case of AlCuSiMg/SiC(Ni) p composite
6. References
[1] Sone, M., Kobayakawa, K., Saitou, M., & Sato, Y. (2004). Electroless copper plating using FeII as a reducing
agent. Electrochimica Acta 49 , 233-238.
[2] Tian, Q.-h., & Guo, X.-y. (2010). Electroless copper plating on microcellar poliurethane foam. Trans. Nonferrous Met. Soc. China 20 , 283-287.
[3] Zhao, H., Huang, Z., & Cui, J. (2008). Electroless plating of copper on AZ31 magnesium alloy substrates.
Microelectronic Engineering 85 , 253-258.
[4] Kretz, F. a. (2004). The electroless deposition of nickel on SiC particles for aluminum matrix composites.
Surface and CoatingsTechnology 180-181 , p575-579.
[5] Li, L., & An, M. (2008). Electroless nickelphosphorus plating on SiCp/Al composite from acid bath with nickel
activation. Journal of Alloys and Compounds , 8591.
[6] Li, L., An, M., & Wu, G. (2006). A new electroless nickel deposition technique to metallise SiCp/Al composites.
Surface & Coatings Technology , 5102 5112.
[7] Socha, R., Nowak, P., Laajalehto, K., & Vyrynen, J. (2004 ). Particle-electrode surface interaction during nickel electrodeposition from suspensions containing SiC and SiO2 particles. Colloids and Surfaces A:
Physicochem. Eng. Aspects , 45-55.
[8] Arik, H. (2008). Effect of mechanical alloying process on mechanical properties of a-Si3N4 reinforced aluminum-based composite materials. Materials and Design 29 , 18561861.
[8] Pzmn, J., Ferenczi, T., Trk, T., & Gcsi, Z. (2008). Metal Matrix Composite with Electroless Nickel Plated
SiC. Euro PM2008 International Powder Metallurgy Congress & Exhibition, Conference Proceedings , 179184.
[9] Pzmn, J., Ferenczi, T., Gcsi, Z., & Trk, T. (2008. oktber 8-12.). Improving the Interfacial Metal-Ceramics
Bond of Metal Matrix Composites with Electroless Nickel Plating. Gcsi Zoltn, Ankara, 5th International Powder Metallurgy Conference , Trkorszg.
[10]
Pzmn, J., Mdai, V., Tth, J., & Gcsi, Z. (2009). Electroless Nickel Plating with Different Pre-treatments on Silicon Carbide Particles. Euro PM2009 International Powder Metallurgy Congress & Exhibition;
Proceedings , 377-382.
[11] Pzmn, J., Mdai, V., Tth, J., & Gcsi, Z. (2010). Effect of the interfacial phases on the mechanical properties of Al/SiC(Ni)p composites. World PM 2010 (Proceedings Volume 4, 87-94;). Florence, Italy: EPMA.
134

PRODUCING OF STEEL CHIPS REINFORCED ALUMINUM COMPOSITES

WITH POWDER METALLURGY
Rashad GULUZADE*, Ahmet AVCI** and M. Turan DEMRC***
*Selcuk University, Faculty of Engineering,
Department of Mechanical Engineering, 42075, Konya, Turkey, rguluzade@hotmail.com
**
Selcuk University, Faculty of Engineering,
Department of Mechanical Engineering, 42075, Konya, Turkey, aavci@selcuk.edu.tr
***
Selcuk University, Faculty of Technology, Department of Metallurgical and Materials Engineering, 42075, Konya,
Turkey, turandemirci@selcuk.edu.tr
ABSTRACT
In this paper, recycling aluminum (Etial 65) and AISI 1040 steel chip composition were produced with powder
method. Aluminum and steel chip size were determined as 1000 m. Steel chips were used as reinforcement into
aluminum chip matrix. AISI 1040 reinforcement were added into 20, 30, 40% wt. ratios. The process was performed
in following steps; granulation of chips (1000um screening apparatus used ), using zinc stearate as lubricating for
press molding (under 200MPa pressure), sintering process at 650oC which contain new method for preventing
oxidation without vacuum and shielding gas. Compression test, hardness measurement were applied to ascertain
mechanical properties of composites. Compressive strength and hardness of the specimen with 40% of steel reinforcement is highest in 650oC sintering temperatures.
Keywords: Recycling method, aluminum and steel chips, new sintering method
1. INTRODUCTION
Manufacturing sintered products technology by powder metallurgy method has been developed gradually in recent
years. Especially, when the recycling technologies for manufacturing have been progressed account of low material
sources, the using of waste products in metal industries come into prominences [1-3].
In metal industries, waste and scrap metals that were manufactured end of metal products processes are chips
and discards. These waste materials are reutilized by returning to smelters. However, during melting processes of
materials for recycling, many metals are lost due to occurring oxidation and costs of labor, energy and environmental protection expenditures [4]. To overcome these disadvantages were mentioned on melting processes, there are
different ways of recycling metal chips, consisting in the direct conversion of chips into compact metal. One of them
contains granulation which gets from end of cutting process, then cold pressing and sintering processes. This type
of recycling can be applied to iron, copper, aluminum, to some extent to cast metals and their alloys [5].
In aluminum and aluminum-alloys melting process for recycling aluminum waste and scrap, approximately 10% of
it is burst and approximately 10% of it is lost on account of aluminum waste and scraps with the slag removed from
surface of the ladle [4-6]. The reason of substantial losses of aluminum and aluminum alloys waste and scraps during conventional due to which it stays rather long on the surface of the molten aluminum and oxidizes intensively
[1]. Therefore, powder methodology contains cold pressing and sintering process can be used to overcome all
disadvantages of recycling of aluminum waste like chips were mentioned above. Aluminum chips especially were
derived machining operation. For cold pressing and sintering chips size and irregular elongated spiral shapes make
them unsuitable for is important to define the cold pressing conditions. For obtaining optimum size and shape of the
chips, they must be broken into to small pieces by milling processes.
Gronostajski et al. investigated new methods for the aluminum and aluminum alloy chips recycling and compared
conventional and direct methods [1]. Chmura at al. studied the recycling of aluminum and aluminum-bronze chips
135

as the use of bearing. Bearing composites were produced by the cold compaction and hot extrusion. End of production processes of composite bearing samples, mechanical and tribological properties were determined and found
aluminum-based with aluminum bronze reinforcing phase have good frictional properties.[4-7]. Gronostajski et al.
in other study, used direct the recycling method which contains cold press molding and hot extrusion. As aluminum
alloys, they used Cu, Mg and W materials. As result of experiments, they determined that aluminum and its alloys
can be recycled by direct conversion method which characterized by low energy-consumption and large material
savings [2-3]. Gronostajski et al. investigated aluminum chips composites and used as a reinforcing phase the
FeCr powder. The reinforcement of FeCr showed very good mechanical properties at room and elevated temperatures [5]. Gronostajki at al. in other study, they produced Al and ALMg2 alloy composites by using direct recycling
method from chips [3]. Abdizadeh et al. studied on aluminum-zircon composites by powder metallurgy method. The
cold pressed composites were sintered two different temperatures at 600 and 650oC. Then produced composites
were carried out compressive and hardness tests. The best bonding temperature was obtained at 650oC [8]. They
reached that adding zircon particulates increased mechanical properties of composites. Zhao et al. produced AlNi composites by powder metallurgy and examined their mechanical properties such as microhardness, ultimate
tensile strength and elongation [9]. McKie et al. tried to find out mechanical properties of cubic boron nitride and
aluminum composites which were produced by powder methodology. In this methodology, they applied to high pressure and high temperature sintering methods. End of experiments, they reached the important issues that the grain
sizes effected the bonding of materials [10]. Showaiter and Youseffi examined the mechanical properties of 6061 Al
and Pb, Ag and Sn added 6061 Al composites. They determined optimum sintering condition that was temperature
of at 620oC and 1 h under pure nitrogen for compaction pressures of 340 and 510 MPa [11].
So far many researchers concentrated on studying powder materials such as Al, Cu etc and conventional sintering
conditions. However, waste materials in order to use recycling methodology have received little attention. The aim
of this work was to investigate the compaction, new sintering method and mechanical properties of composites
produced by aluminum chips and reinforcement materials of steel chips attained from manufacturing processes.
2.1. Raw Materials
Etial 65 Aluminum chips were used as matrix and AISI 1040 steel chips were used as reinforcing phase. Chemical
properties of these chips were given in Table 1. At the beginning of study, size reduction processes by using a cutting device and sieve shaker were applied to aluminum and steel chips that are waste materials. Then sizes of chips
were made smaller granular between 0.5 and 1 mm. Methyl alcohol was used to clean the chips from impurities and
cutting oils used as lubricants and coolant. Aluminum chips mixed with 30, 40, 50 wt% ratios of reinforcing phase
by mechanical stirrer for 15 min each (Table 2).
Etial 65
AISI 1040
Table 1. Chemical composition of Etial 65 aluminum and AISI 1040 steel chips
Si (%)
Fe(%)
Cu(%)
Mn(%)
Mg(%)
Al (%)
C(%)
0.67
0.74
0.123
0.138
1.26
96.7
0.2
0.65
0.4
P(%) S(%)
0.04
0.2
Table 2. Chips fraction used for this experiment.

AISI 1040 (wt)
21
28
35
%
30
40
50
Aluminum(wt)
49
42
35
%
70
60
50
2.2 Compaction and sintering

All mixture ratios given in Table 2 were pressed at
250 MPa by using cold press die which produced
in accordance with ASTM-B557. Zinc stearate
was used on the die wall and punches for lubrication before compaction to reduce die wall frictional
effects. A single acting hydraulic press was used
for compaction.
Figure 1. Compaction
die for producing
compressive specimens.
Sintering characteristics were investigated in a

laboratory furnace in 650oC and for 2 hours [8].
All composites were heated to sintering tempera-
136

tures at the heating rate of 5oC/min and furnace cooled to room temperature. Instead of pure nitrogen atmosphere,
sintering mold, molding sand and clay were used to prevent the oxidation of aluminum chips. In this new sintering
method, cold pressed composites put in sintering mold firstly. Secondly molding sand filled in mold and clay were
used to closed mold mouth finally. Molding sand provided to homogeneously heat to composites and prevented
oxidations. Funnel seen in fig. 2 deposited the gases were released from composites.
Figure 2. Sintering mold for compressive specimens.

Brinell hardness values of compressive specimens were measured on the polished surfaces of specimens using a
ball 5 mm diameter under a load of 250 kgf by holding 30 second [2-7]. For each specimens three hardness tests
on randomly selected regions were performed in order to eliminate the possible segregation effects and get a
representative value of the matrix material hardness. The compressive strength test was conducted in air at room
temperature according to ASTM-B557 and three specimens were tested each steel contents.
3. RESULTS
Increasing the weight of 1040 steel chips causes an increase in the density of specimens. The differences of
theoretical and sintered density of composites are very obvious, give in fig. 3. High sintering temperature provides
to the easier diffusion of atoms which helps the better ability of sintering the composites. Therefore the density of
composites reaches to a higher value [3-8].
Figure 3. Sintered density of composites.

The hardness of specimens has been tested with Brinell measure method. The results were presented at fig 4. The
hardness specimens increase by rising steel contents [8].
Figure 4. Hardness vs. steel contents.
137

Figure 5. Compressive strength of composites.

Compressive test were applied to three different composites and pure aluminum specimens and obtained measurement results give in fig. 6. According to tests results, the increasing of steel contents were enhanced the strength
of composites. As it could be seen in the fig.6, compressive strength of the specimen with 40% of steel reinforcement is highest in 650oC sintering temperatures. This situation could be associated to the highest density of this
specimen among the others. When reinforcement steel chips increases in composites, the distance between them
decreases. Therefore movement of dislocations is harder because of providing more barriers and then, dislocations
pile up occurs. These phenomena bring to an end of decreasing in elongation [4]. Fig 6. shows the elongation of
composites.
Figure 6 Elongation of composites.

While the steel contents are increased, the composites become denser (fig. 4.) as well as inflexible so that the
elongations of composites are lower values [12].
4. CONCLUSIONS

In this study, compressive tests, density calculation and hardness test were performed according to
ASTM. Conclusions from present study are given below;
With increasing steel chips contents in composites, the hardness of specimens increases to a maximum
value of 121 BHN.
650oC sintering temperatures provide to increase the sintered density. High temperatures under melting
point for aluminum causes decrease in porosities of specimens and high temperatures cause better bonding
between aluminum and steel chips, thus this improves the mechanical properties of composites.
Compressive strength enhances with increasing steel chips wt % contents. The maximum of compressive strength is approximately 640 MPa which contains 40 wt% steel chips.
In addition to all explanations, As know that the steel reinforcement is increase the compressive strength but to improve mechanical properties and decrease the porosity of composites, the cold pressing pressure can be increased
and the different sintering temperatures can be carried out to investigate the effects of sintering temperatures to
density, porosity and mechanical behavior.
5. ACKNOWLEDGEMENT
The authors would like to thank The Onallar Agricultural Machine Company for technical supports.
138

REFERENCES
1. Gronostajski J., Marciniak H., Matuszak A., New methods of aluminum-alloy chips recycling, Journal of
Material Processing Technology, Vol:106, pp. 34-39, 2000.
2. Gronostajski J., Matuszak A., The recycling of metals by plastic deformation: an example of recycling of aluminum and its alloys chips, Journal of Materials Processing Technology, Vol: 92, pp. 35-41, 1999.
3. Gronostajski J, Z., Kaczmar J. W., Marciniak H., Matuszak A., Production of composites from Al and AlMg2
alloy chips, Journal of Materials Processing Technology, Vol: 77, pp. 37-41. 1998.
4. Gronostajski J., Chmura W., Gronostajski Z., Bearing materials obtained by recycling of aluminum and aluminum bronze chips, Journal of Materials Processing Technology, Vol: 125, pp. 483-490, 2002.
5. Gronostajski J.Z., Marciniak H., Matuszak A., Samuel M., Aluminium-ferro chromium produced by recycling of
chips, Journal of Material Processing Technology, Vol: 119, pp. 251-256, 2001.
6. Gronostajski J., Kaczmar J. W., Marciniak H., Matuszak A., Direct recycling of aluminum chips into extruded
products, Journal of Materials Processing Technology, Vol: 64, pp. 149-156, 1997.
7. Chmura W., Gronostajski Z., Bearing composites made from aluminum and aluminum bronze chips, Journal
of Material Processing Technoloogy, Vol: 178, pp.188-193, 2006.
8. Abdizadeh H., Ashuri M., Moghadam P. T., Nouribahadory A., Baharvandi H. R., Improvement in physical and
mechanical properties of aluminum/zircon composites fabricated by powder metallurgy method, Materials
and Design, Vol: 32, pp. 4417-4423, 2007.
9. Zhao B., Zhu C., Ma X., Zhao W., Tang H., Cai S., Qiao Z., High strength Ni based composite reinforced by
solid solution W(Al) obtained by powder metallurgy, Material Science and Engineering A, Vol: 456, pp.
337-343, 2007.
10. McKie A, Winzer J., Sigalas l., Hermann M., Weiler L., Rdel J., Can N., Mechanical properties of cBN-Al
composite materials, Ceramic International, Vol: 37, pp. 1-8, 2011.
11. Showaiter N., Youseffi M., Compaction, sintering and mechanical properties of elemental 6061 Al powder with
and without sintering aids, Material and Design, Vol: 29, 752-762, 2008.
12. Baron R. P., Wert J., Gerard A., Wawner F. E., The prosessing and characterization of sintered metal-reinforced aluminum matrix composites, Journal of Materials Science, Vol: 32, pp. 6435-6445, 1997.
139

INVESTIGATING THE MICROSTRUCTURE OF HOT PRESSED SiC

REINFORCED AlCu and AlSi ALLOY COMPOSITES
BY ULTRASONIC TECHNIQUE
Evren TAN*, C. Hakan GR*, Andrea SIMON** and Zoltan GACSI**
* Middle East Technical University, Faculty of Engineering, Department of Metallurgical and Materials
Engineering, 06800, Ankara, Turkey etan@metu.edu.tr, chgur@metu.edu.tr
**
Institute of Materials Sciences, Univ. of Miskolc, Miskolc-Egyetemvaros, Hungary
femandi@uni-miskolc.hu, femtangz@uni-miskolc.hu
ABSTRACT
Al matrix composites are utilized in high-tech structural and functional applications including aerospace, defence,
automotive industries. Among them particle reinforced ones are widely utilized since they show isotropic behaviour,
and can be formed using the traditional metal working practices. Several challenges must be overcome in order to
intensify their utilization such as parameters affecting the microstructural integrity including agglomerates need to
be understood more thoroughly, and there is a need for developing simple, economical and portable non-destructive systems to control the product quality.
This study aims to understand the microstructure-ultrasonic velocity relationship in SiCp reinforced Al-alloy matrix
composites. Two specimen sets were fabricated by hot pressing of AlCu and AlSi powder mixtures containing
various amounts of SiC particles. The microstructures of the specimens were characterized by microscopy, X-ray
diffraction, hardness, and sound velocity measurements; and the results were correlated.
Keywords: Aluminum alloy matrix composites, SiC reinforcement, Microstructure, Characterization, Ultrasonics
1. INTRODUCTION
Metal matrix composites (MMCs) show an ability to blend high strength and high modulus with ductility and toughness, which leads to significant improvement in the performance of the composites over those of the metallic alloys. Due to relatively inexpensive reinforcements and the processes resulting in reproducible microstructures and
properties, MMCs are being increasingly sought for a wide range of applications in the electronics, automotive and
aerospace industries.
Particle reinforced MMCs have been synthesized using a number of different techniques that include solid phase
processes, liquid phase processes and two phase (solidliquid) processes [1]. In the case of powder metallurgy
method, powdered metal is blended with reinforcement particles, and then, densified by die pressing, canning, and
extrusion or canning and hipping.
The rate of increase in strength with volume fraction decreases beyond approximately 3040 vol.% SiC. However,
ductility, fracture toughness, formability, and machinability tend to decrease in value with increasing levels of reinforcement [2]. Strength clearly increases with reducing the particle size of the reinforcement. By reducing the
reinforcement size, the ability to perform a secondary deformation and machinability was also enhanced. Reinforcement distribution is thought to be the major parameter influencing ductility and fracture toughness of the MMC, and
hence indirectly strength.
Mechanical properties and stressstrain behavior for several commercial Al-matrix composites, containing up to
40 vol.% discontinuous SiC whisker, nodule or particulate reinforcement were evaluated [3]. The particle size of
SiC and Al material has an important role. If the particle size ratio is high, the particle size of them is very different
and the smaller SiC particles can cluster among the bigger Al particles [4]. If the reinforcement distribution is not
140

homogeneous, then clusters develop and pores appear among them. These clusters usually function as initial place
for cracks. In the composites made via powder metallurgy route the reinforcement distribution homogeneity can be
affected by the particle size ratio. To improve the homogeneity reinforcements with bigger particle size can be used.
However, this leads to worse mechanical properties [5].
Propagation of ultrasonic waves is sensitive to the variations in the microstructure and mechanical properties.
Therefore, establishment of the correlations between microstructure and nondestructive evaluations could be useful for process improvement and product quality control. It has been reported that the inhomogeneous distribution
of SiC whiskers in 7090 Al, that significantly degrades tensile and fracture toughness, is detectable by ultrasonic
measurement [6].
A theoretical model for the relationship between ultrasonic velocity and the microstructure has been established [7].
Multiple non-destructive techniques for determining the volume fractions of reinforcement in SiCp-reinforced 7091
Al-alloy matrix composites have been used [8]. Correlation of the ultrasonic velocity and specific surface area that
occur as a result of sintering for several oxide powder systems has been studied [9]. It has been reported that the
ultrasonic velocity increases with an increase in SiC content; however, it decreases owing to microporosity caused
by the segregation of SiC particles [10].
MMCs provide a challenge for conventional non-destructive evaluation methods because of their complex microstructural characteristics. The primary objective of this research is to use a systematic approach directed towards
microstructure characterization of various SiCp-reinforced Al matrix composites.
The compositions of powders used were given in Table 1. A hot press system composed of furnace, control unit
and a hydraulic press was used. Molykote P37 grease was applied on the die surfaces before placing the powder
samples for easy removal of the product.
Table 1. Chemical composition of the powders
Element, wt%
Cu
Si
Mg
Zn
Lubricant
Al
Mean
size m
AlCu
ECKA Alumix 123
4.5
0.7
0.5
1.5
Bal.
24
AlSi
ECKA Alumix 231
2.5
14
0.5
1.5
Bal.
17
Reinforcement
SiO2
Si
Fe2O3
Al2O3
CaO
SiC
SiC
0.08
0.15
0.04
0.015
0.004
0.003
Bal.
Matrix
14
Production sequence starts with powder mixing at 70 rpm in a 100 ml container with ZrO2 cylpeb balls for 1 h. The
mixed powders were poured in the die cavity which was previously placed in the furnace. While the system was being heated, a pressure was applied on the die punch. Furnace and control unit was designed in such a manner that;
the process temperature could be reached in 2 hours, and stay at that temperature within 5C variation. After 10
minutes under 25 MPa pressing pressure at 527oC for AlCu; 525oC for AlSi composites, the furnace was turned off
and the die was removed. Sample densities were measured via Archimedes principle. To find the overall porosity;
theoretical densities of the composites were calculated from rule of mixtures.
Vickers HV30 indentation was performed on the sample surfaces, and average hardness values were calculated.
X-Ray measurements were carried out to identify the intermetallic phases. Sound velocities were measured by
establishing wave transmission through the thickness of samples produced. 0.5 MHz, 1 MHz, 2.25 MHz and 5 MHz
longitudinal and transverse wave probes were used.
3. RESULTS
Figure 1 shows the representative micrographs of the unreinforced and 30% SiC reinforced AlCu and AlSi alloy
samples. Phases found in the X-ray diffraction analysis were Al2Cu in the AlCu composites, Al2Cu and Mg2Si in the
AlSi composites. In none of the samples brittle Al4C3 was not detected.
141

Figure 1. Selected SEM microstructures of the hot-pressed samples

The porosities were detected between SiC particles/clusters (irregular shape); at the Al-SiC interface (elongated
shape); and in the matrix (sphere-like/elongated shape). In AlCu samples no significant differences among the porosities were observed in the specimens containing 10 and 20% SiC. However, porosity content increased clearly
in the sample with 30% SiC although it did not reach the quantity detectable in the matrix. The distribution of SiC
seems to be the most uniform in the specimen containing 10% SiC; the SiC particles group in a greater extent at
the Al-boundaries in the other two specimen. The pores are distributed randomly there is not any typical appearance.
In the AlSi alloy specimens containing 10 and 20% SiC, porosity can be neglected. The extent of porosity increases
significantly in the specimen containing 30% SiC. While the presence of porosity can mainly be due to the eutectic
in the first two composites, it appears in the vicinity of SiC groups in the specimen containing a high quantity of SiC
(it can be caused by the preparing of powders i.e. their improper mixing). Figure 2 shows that the hardness of the
composite increases with increasing % SiC. Reinforcement is more effective for strengthening of AlSi composites
than AlCu ones.
Figure 2. Macrohardness
(HV30) of the samples
142

Reinforcement content is an important factor controlling the strength of AlSiC composites. It is known that for a
given matrix alloy and reinforcement, the yield and ultimate tensile strengths generally increase with increasing
reinforcement content, and a similar increase is expected for the stiffness of the composite [2,3].
Sound velocity measurement results are tabulated in Table 3. Figure 3 shows the variation of longitudinal and
transversal wave velocities with respect to the amount of SiC. The velocity of ultrasonic wave propagating in an
inhomogeneous medium depends upon the overall effective stiffness and density of the medium. The SiC is much
stiffer than the Al matrix while its density is comparable to that of the matrix. When SiC content increases, the stiffness and the elastic modulus increases. Thus, ultrasonic waves propagate faster in the SiC reinforced Al MMCs
than in those without reinforcement, and the propagation rate of the wave increases with increasing amount of SiC
reinforcement.
Set
AlCu
AlSi
Table 3. Velocities of longitudinal and transversal waves

SiC
theoretical
measured
VL (m/sec) VT (m/sec)
(wt.%)
0
2,56
3819
2660
2,78
10
2,65
5147
2986
2,81
20
2,80
6788
3566
2,85
7246
3719
30
2,85
2,89
0
10
20
30
2,68
2,72
2,77
2,82
2,39
2,40
2,60
2,77
3268
3770
6443
7385
2185
2858
3605
4086
Figure 3. Changes in the velocities of longitudinal and transverse waves with %SiC
143

It has been observed that the velocity of longitudinal waves increases with increasing amount of SiCp with a corresponding increase in the density. Due to the inverse relation between velocity and density, the increase in the velocity of the longitudinal wave must be related to increasing elastic moduli rather than increasing density. However, the
amount of the increase in both velocity and density is less than the theoretical values. It appears that the ultrasonic
velocities, that are lower than the theoretical values, are probably due to the higher amount of residual pores.
Microporosities in the specimens may affect the ultrasonic velocity. A relationship has been reported in the literature
where the ultrasonic velocity varies as a function of pore volume fraction [11,12].
V L / V L,0 = 1 P
where VL and VL,0 are the longitudinal ultrasonic velocity in porous and non-porous material, P is the pore volume
fraction and is constant.
Figure 4. Changes in the longitudinal velocity with pore volume fraction (P)
Figure 4 shows the variation of longitudinal wave velocities with respect to pore volume fraction. It was observed
that for AlCu composites, effect of porosity on longitudinal ultrasonic sound velocity could be easily fit to the linear
function with being 6.33. But for the AlSi composite case, a deviation from the linear function was found which
shows that variation in the retained porosities was not enough to explain the change in ultrasonic sound velocity
change. It was thought that for AlSi composites the density difference (16%) between reinforcement (3.21 g/cm3)
and matrix (2.68 g/cm3) could be the another parameter that should be taken into account.
4. CONCLUSIONS
This study aimed to understand the microstructure-ultrasonic velocity relationship in SiCp reinforced Al-alloy matrix
composites. Two specimen sets were fabricated by hot pressing of AlCu and AlSi powder mixtures containing various amounts of SiC particles. The following conclusions can be drawn from the results of this study:
Hardness increases with increasing SiC content.
For a given particle size combination, the velocity of ultrasonic longitudinal waves increases with increasing
reinforcement content.
The propagation rate of the ultrasonic waves is affected by porosity in the matrix.
Ultrasonic velocity measurement seems to be a promising technique for quality and process control purposes in the fabrication of SiCp-reinforced Al-alloy MMCs.
Acknowledgements
Financial support of Turkish-Hungarian project (TBTAK 106M328) is greatly acknowledged. Authors take this opportunity of thanking ECKA and Norton AS for providing Al and SiC powders.
REFERENCES
1. Lloyd, D.J., Particle Reinforced Aluminum and Magnesium Matrix Composites, International Materials Review, Vol. 39, pp. 1-22, 1994.
2. Begg, A.R., Metal matrix composites by powder metallurgy, Powder Metallurgy, Vol. 36, pp.107-110,
1991.
144

3. McDanels, D.L., Analysis of stress-strain, fracture and ductility behaviour of aluminium matrix composites
containing discontinuous silicon carbide reinforcement, Metallurgical Transactions A, Vol. 16, pp. 11051115, 1985.
4. Bhanu Prasad, V.V., B. Bhat, V. R., Ramakrishnan, P., Mahajan Y.R., Clustering probability maps for private
metal matrix composites, Scripta Materialia, Vol. 43, pp. 835-840, 2000.
5. Slipenyuk, A., Kuprin, V., Milman, Yu., Spowart, J.E., Miracle, D.B., The effect of matrix to reinforcement particle size ratio (PSR) on the microstructure and mechanical properties of a P/M processed AlCuMn/SiCp MMC,
Material Science and Engineering A, Vol. 381, pp. 165-170, 2004.
6. Mott, G., Liaw, P.K., Correlation of Mechanical and Ultrasonic Properties of Al-SiC Metal Matrix Composite,
Metallurgical Transactions A, Vol. 19, pp. 2233-2246, 1988.
7. Lu, Y., Liaw, P.K., Effects of Particle Orientation in SiC Particulate Reinforced Aluminium Matrix Composite
Extrusions on Ultrasonic Velocity Measurement, Journal of Composite Materials, Vol. 29, pp.1096-1115,
1995.
8. Jeong, H., Multiple NDE Techniques for the Measurement of Constituent Volume Fractions in Metal Matrix
Composites, Research in Non-Destructive Evaluation, Vol. 9, pp. 41-57, 1998.
9. Martin, L.P., Nagle, D., Rosen, M., Effect of Particle Size Distribution upon Specific Surface Area and Ultrasonic Velocity in Sintered Ceramic Powders, Material Science and Engineering A Vol. 246, pp. 151-160,
1998.
10. Gr, C.H., Investigation of MicrostructureUltrasonic Velocity Relationship in SiCp-reinforced Aluminium Metal
Matrix Composites, Material Science and Engineering A, Vol. 361, pp. 29-35, 2003.
11. Mukhopadhyay A.K., Phani, K.K., An analysis of Microstructural Parameters in the Minimum Contact Area
Model for Ultrasonic Velocity - Porosity Relation, Journal of European Ceramic Society, Vol. 20, pp. 29-38,
2000.
12. Kumar N., Panakkal, J.P., Analysis of Ultrasonic Velocity-Porosity Data in Polycrystalline Materials using
Rotation-Iteration Technique, Journal of Materials Science, Vol. 34, pp. 4811-4814, 1999.
145

THE EFFECT OF PROCESS PARAMETERS ON MECHANICAL AND DRY

WEAR BEHAVIOUR OF ALUMINIUM COMPOSITE
Yusuf AHN*, Kerim Emre KSZ**
* Gazi University, Faculty of Technology, Department of Manufacturing Engineering, Beevler-06500, Ankara,
Turkey, ysahin@gazi.edu.tr
** Cumhuriyet University, Faculty of Engineering, Department of Metallurgical and Materials Engineering, 58140,
Sivas, Turkey, emre.oksuz@cumhuriyet.edu.tr
ABSTRACT
Al2O3 particle-reinforced Aluminium composites were prepared by powder metallurgy (PM) method under different
temperatures and times. Wear behaviour of Al-Al2O3 reinforced composites were tested under dry conditions using
a pin-on-disc wear rig. Pure Al of average particle size of 45 m was reinforced with 10wt. %Al2O3 with average
particle sizes of 20 and 3 m. SEM examination showed a nearly uniform distribution of the Al2O3 particles within the
matrix. Improvements of hardness in comparison to matrix for 550C, 610C were achieved at about 44.52%, 50%,
respectively. These improvements were reached up to 62.6% at 120 min sintering time. Moreover, the wear rate of
the composites increased with increasing all applied loads, but wear rate decreased with increasing particle size.
Keywords: Al matrix Al2O3 particle, metal matrix composite, powder metallurgy, wear
1. INTRODUCTION
Metal matrix composites (MMCs) are relatively new class of advanced engineering materials characterized by
higher stiffness and hardness, lighter weight and greater wear resistance than those of conventional materials [1].
The reinforcing particles in the MMCs protect the matrix surface against destructive action of abrasive wear. In
producing MMCs; thus, C, SiC, TiC, B and Al2O3 in the form of continuous fibres, chopped fibres or whiskers and
particulates have been used as reinforcement materials, whereas, aluminium, magnesium, titanium and their alloys
have been used as matrix alloys [2]. The most commonly employed MMCs consists of aluminium alloy reinforced
with hard ceramic particles, as stated above. The MMCs can be produced through a number of routes including
casting and powder metallurgy (PM) including mechanical alloying (MA) [3-9, 10-13]. Some of the difficulties of
producing the MMCs using conventional casting method is to obtain non-uniform microstructures and particle
clustering [14, 15]. The PM routes like densification of mixtures of metal and ceramic powders or of composite
powders made by mechanical processing, followed by pressure and sintering. The PM is simple method and exhibit
excellent finished performance [16, 17]. MMCs, therefore, have been used for the automobile components such as
engine piston, brake drums, cylinder blocks, drive shaft, but they are also used in structural applications such as
helicopter parts, rotor vanes in compressors in aerospace industry [4, 18, and 19]. There have been a number of
studies on the fabrication of Al matrix composites. However, there are a few reports on wear behaviour of Al2O3/Al
composites with the effect of particle sizes at lower stress [2, 6, 15-16]. The purpose of the current study, therefore,
is to produce MMCs with different particle sizes by PM method, evaluate the effect of particle sizes and load on the
dry wear behaviour of MMCs.
2.1. Materials
Pure aluminium (Al) was fabricated by powder metallurgy as an unreinforced material. In order to produce Al2O3Al based composites, commercial aluminium powders with an average particle size of 45 m with 99.5% purity
and various particle sizes of Al2O3 powders have been provided from Akyol Turkish Company in Istanbul. For
manufacturing MMCs, the average particle sizes of 22 m, 3 m was evaluated, hereafter denoted as 22 m- Al2O3/
146

Al composite, 3 m-Al2O3/Al composite containing 10 weight fractions of Al2O3 particles. The mixtures of alloyed
powders were uniaxially cold compacted using a cylindrical die of 6.5 mm diameter and 20 mm height at a pressure
of 650 MPa. The compacts were then sintered in a pipe type of furnace under a control of argon gas. The mixed
powders were sintered at 550C, 610C for 45 min and 120 min. A similar subsequent experiment was conducted
for the development of Al powder specimens-only for comparison purposes.
Hardnesss of composites and matrix were measured by Vickers hardness method by applying 30kgf load after
polishing to a 3 m finish. Five samples were averaged at least.
A pin-on-disc type of apparatus was employed to evaluate the wear characteristics of MMCs and matrix. The
counter surface material,which was heat-treated to give a surface hardness of 59-63 HRC. The composite bars
were in the form of cylindrical shapes. The pin was then mounted in a steel holder in the wear machine so that it was
held firmly perpendicular to that of flat surface of the rotating counter disc when tested. The samples were loaded
against the hardened steel disc with the help of a cantilever mechanism. In the tests; normal load on the pin was
variable at a constant sliding speed of 1 m s-1.
3.1 Microstructure
Fig.1 shows the SEM micrographs of pure Al matrix and its composites reinforced with a 10 wt. % of Al2O3
composites with various particle sizes. Grain boundary can be seen in the pure Al matrix (Fig.1a). The darker region
in the microstructure is essentially Al2O3 particles. The distributions of Al2O3 particles in these composites seem
to be uniform. With the increment in the amount of particles, the size of -Al phase or grain boundary decreases
progressively. There are no agglomerations and porosity in this micrograph because of increased the pressure (see
Fig.1b). Grain growth during sintering changes the configuration of the grain boundaries relative to pores and thus
may markedly influence the shrinkage rate. The addition of Al2O3 particles will increase the sintering rate if they
increase diffusion rates, but they may also increase sintering rates by impeding grain-boundary movement. The
grain growth might proceed via solid-state atomic diffusion. The relatively homogenous microstructure leads to the
highest hardness in Fig.2.

a) C1

b) C3
Fig.1. Typical SEM micrographs of pure Aluminium matrix and its 10wt. % Al2O3 reinforced Al composite,
sintered at 550oC for 45 min. a) Pure aluminium (C1), b) 20 m-10wt. % Al2O3/Al composite, indicating
distributions of Al2O3 particles in the matrix (C3).
3.2 Hardness of The Composite

Hardnesss of composites produced at different temperatures and times were measured by taking at least 5
samples. The results showed that hardness increased with increasing temperature, as shown in Fig.2. This 600C
temperature promotes additional particle to particle bonding and more complete alloying because of higher diffusion
rates. On the other hand, it is necessary to reduce the oxides of these elements in order to promote bonding of
particles. However, sintering time is found to be more effective than that of the because of mechanism of neck
formation and neck growth of powders (Table 1).
Moreover, the hardness of the MMCs increased with increasing the size of particles (Fig.2). The achievement
of wettability of these materials decreased for 3m-Al2O3 reinforced composite than that of the 20m-reinforced
composite although the degree of liquid phase formation increases with temperature.
147

Table 1. The results of hardness of metal matrix composite.

Sintering times
45min
120min
Materials type
Hardness at
550C(HB1)
Hardness at
610C(HB1)
Hardness at
550C(HB1)
Hardness at
610C(HB1)
Al matrix (C1)
26.5
28
30
31.3
Al-3m-10wt.% Al2O3
reinforced MMCs (C2)
31.8
32.1
35.2
36.5
Al-20m-10wt.% Al2O3
reinforced MMCs (C3)
38.3
42
46
50.9
Fig.2. Variation
of hardness as a
function of type
of materials for Al
matrix and its 10wt.
% Al2O3 reinforced Al
composite.
a) Sintering time of
45min,
b) Sintering time of
120min
a) (b)
3.3. Wear Behaviour
The average volumetric wear rate of Al/Al2O3
reinforced composites are determined, and
are illustrated graphically in Fig.3 as a function
of different load. It is found that the wear loss
of the composites increase sharply with all
applied for both materials. The composite
shows a lower wear rate than that of the matrix
at lower loads due to increased hardness of
the samples (see Table 1). This is a good
agreement with previous studies on wear of
metal matrix composite by Lim et al. [13], and
Kumar et al. [17]. Furthermore, lower sizes
of particles in the MMCs give the highest
wear loss because small SiC particles in the
composite are more easily pulled-out from the
matrix, compare with higher sizes of particles.
As the Al2O3 particles size increases from 3
m to 20 m in a fixed sliding distance, the
composites wear rate tested at an average
load decreases to 52%. On the worn surfaces,
reddish-brown coloured transfer layers are
observed by naked eye. This layer may be
contained constituents from the counter face
like Fe, Si and Cr, which is Fe rich layer. It acts
as a solid lubricant and prevents direct contact
between the composites and counter face
during wear testing [23, 25]. However, there
Fig.3. Variation of average volumetric wear rate as a function

of applied load for 10wt. % Al2O3 reinforced Al composite,
sintered at 550C and 45 min.
148

are more conflicting reports on these issues. For example, some researchers show that the wear resistance of
Al2O3 or SiCp reinforced composites increases with increasing particle sizes and/or volume fraction of particles
[21-24]. On the contrary, other people report that the smaller sizes of particles lead to the more wear resistant
composites [26, 27].
4. CONCLUSIONS
The effects of particle size, applied load on the mechanical and dry wear behaviour of composites were
investigated.
1. Aluminium composites containing various particle sizes with 10wt. % Al2O3 particles were produced successfully
using PM method. SEM observation of the microstructure showed that homogenous distributions of Al2O3 particles
in the pure matrix seemed to be dominant.
2. Hardness of the composite sintered at 550C increased with increasing the size of particle in the matrix, average
hardness increased by approximately % 44.5 compared to unreinforced matrixes.
3. It was found that the composites wear rate decreased to 52% as the Al2O3 particle size increased from 3 m to
20 m in a fixed distance.
REFERENCES
1. Das, S., Mondal, D.P, Dixit, G., Correlation of abrasive wear with microstructure and mechanical properties of
pressure die-cast aluminium hard-particle composite, Metal. Mater. Transact., p. 633, 32A, 2001.
2. Zhang, Z.F., Zhang L.C., Mai, Y.W., Particle effects on friction and wear of aluminium matrix composites, J.
Mater. Sci., p.1999, 30 A, 1995.
3. Singh, M., Jha, A.K., Das, S., Yegneswaran, A.H., Preparation and properties of cast aluminium alloy-granite
particle composites, J. Mater. Sci., p.4421, 35, 2000.
4. Mandal, D.P., Das, S., High stress wear behaviour of aluminium hard particle composites effect of experimental
parameters, particle size and volume fraction, Tribol. Inter., p.461, 39-6 2006.
5. Zhiqiang, S., Di, Z., Guobin, L., Evaluation of dry sliding wear behaviour of silicon particles reinforced aluminium
matrix composites, Mater. Des. p.454, 26, 2005.
6. Bindumadhavan, P.N., Wah, H.K., Prabhakar, O., Dual particle size (DPS) composites effect on wear and
mechanical properties of particulate metal matrix composites, Wear. , p.112, 248, 2001.
7. Sahin, Y., Preparation and some properties of SiCp reinforced composites,
Mater.&Des., p.671, 24, 2003.
8. Mandal, D., Dutta, B.K., Panigrahi, S.C., Effect of wt.% reinforcement on microstructure and mechanical
properties of Al-2Mg base short steel fiber composites, J.Mater. Process. Tech., p.195,198, 2008.
9. Venkataraman, B., Sundararajan, G., Correlation between the characteristics of the mechanically mixed layer
and wear behaviour of aluminium, Al-7075 alloy and Al-MMCs, Wear. 22-38., p. 245, 2000.
10. Min, K.H., Lee, B.H., Chang, S.Y., Kim, Y.D., Mechanical properties of sintered 7xxx series Al/SiC composites,
Mater. Lett., p.2544, 61, 2007,
11. Zebarjad, S.M., Sajjadi, S.A., Microstructure evaluation of Al-Al2O3 composites produced by mechanical alloying
method, Mater. Des., p.684, 27,2006.
12. Zhang, J.T., Sheng, L., Liu, Zhai, P.C., Fu, Z.Y., Zhang, Q.J., Influence of heat treatment on interface of Cu/Al
bimetal composite fabricated by cold Rolling, Mater.Lett., p.443, 62, 2008.
13. Lim, C.Y.H., Lim, S.C., Gupta, M., Wear behaviour of SiCp-reinforced magnesium matrix composites, Wear,
p. 629-637, 255, 2003.
14. Wang, H., Zhang, R., Hu, X., Wang, C.A., Huang, Y., Characterization of a powder metallurgy SiC/Cu-Al
composite, J. Mater. Procesess.Tech., p.43, 197, 2008.
15. Wan, D.T., Hu, C.F., Bao, Y.W., Zhou, Y.C., Effect of SiC particles on the friction and wear behavior of Ti 3 Si(Al)
C 2 composites, Wear, p. 826, 262, 2007.
149

16. Rahimian, M., Parvin, N., Ehsani, N., Investigation of particle size and amount of alumina on microstructure
and mechanical properties of Al matrix composite made by powder metallurgy, Mater. Sci. Eng., p.1031, A527,
(4-5), 2009.
17. Kumar, A., Mondal, Chandra Rao, B.S.S., Kumar, S., Wear behaviour of AE42+20% saffil Mg-MMC, Tribol.
Inter., p.290, 40, 2007.
18. Shorowordi, K.M., Laoui, T., Haseeb, A.S.M.A., Celis, J.P., Froyen, L., Microstructure and interface
characteristics of B4C, SiC and Al2O3 reinforced Al matrix composites a comparative study, J.Mater. Process.
Tech., p.738, 142,2003.
19. Mondal, A., Murty, B.S., Chakraborty, M., Effect of TiB2 particles on sliding wear of composite, Wear, p. 865872, 266, 2009.
20. Kiourtsidis, G.E., Skolianos, S.M., Wear behavior of composites or of artificially aged AA2024/40 m SiCp
composites in comparison with conventionally wear resistant ferrous materials, Wear, p. 946, 253, 2002.
21. Deuis, R.L., Subramanian, C., Yellup, J.M., Dry wear of composites, A review, Comp. Sci.Technol., p.413,
57, 1997.
22. Sharma, S.C., Girish, B.M., Somashekar, D.R., Satish, B.M., Kamath, R., The study process and wear behaviors
in powder sintering 6061 Aluminum alloy composites, Wear, p.89, 224 1999.
23. Ahlatc, H., Koer, T., Candan, E., imenoglu, H., Wear behaviour of Al /(Al2O3p +SiCp ) hybrid composites,
Tribol. Inter., p.213, 39, 2006.
24. Angers,R., Krisnadev, M.R., Tremblay, R., Corriveau, J.F., Dube, D., Characterization of SiCp/2024 aluminum
alloy composites prepared by mechanical processing in a low energy ball mill, Mater.Sci.Eng., p.9, A262,1999.
25. Belmonte, M., Nieto, M.I., Osendi, M.I., Miranzo, P., Influence of the SiC grain size on the wear behaviour of
Al2O3/SiC composites, J.European Soc., p.1273, 26, 2006.
26. Straffeline G., Experimental observations of subsurface damage and oxidative
wear in Al-based metalmatrix composites, Wear, p.216, 245, 2000.
27. Sheu, S.Y., Lin, S.J., Particle size effect on the abrasion wear of 20 vol. %
SiCp/7075 Al composites, Scr. Mater., p.1271,11, 1996.
150

WEAR STUDIES ON DIAMOND-REINFORCED Fe-Co BASED METAL

MATRIX COMPOSITES
Kerim Emre KSZ*, Mehmet MR* and Yusuf AHN **
* Cumhuriyet University, Faculty of Engineering, Department of Metallurgical and Materials Engineering, 58140, Sivas, Turkey, emre.oksuz@cumhuriyet.edu.tr
* Cumhuriyet University, Faculty of Engineering, Department of Metallurgical and Materials Engineering, 58140, Sivas, Turkey, msimsir@cumhuriyet.edu.tr
** Gazi University, Faculty of Technology, Department of Manufacturing Engineering, Beevler-06500,
Ankara, Turkey, ysahin@gazi.edu.tr
ABSTRACT
Abrasive wear behaviour of diamond-reinforced Fe-Co composites produced using hot pressing method
was studied using a pin-on-disc wear rig where the samples slid against different SiC abrasives. Effects
of wear parameters like, abrasive size, load, sliding time and hardness on weight loss were investigated.
A plan of experiments in terms of Taguchi techniques was performed to acquire data in controlled way.
An orthogonal array and analysis of variance were employed to investigate the influence of process
parameters on the wear of composites. Furthermore, the confirmation of experiment was conducted to
verify the optimal testing parameters. The experimental results showed that the hardness was the major
parameter on the abrasive wear, followed by the applied load while the sliding time was found to have
a neglecting effect.
Key words: Fe-Co based matrix; Diamond; Powder metallurgy; Orthogonal Array; Taguchi method;
Wear; Analysis of Variance
1. INTRODUCTION
Diamond tools are widely used for sawing, drilling and grinding materials like stone, concrete and ceramics since the extreme hardness of diamond and strength of the diamond / matrix combinations [1].
The choice of the matrix material that bonds the diamond is vital to the eventual lifespan of these high
performance tools. The matrix used in the most diamond tool is a cobalt alloy since it combines with
diamond grits good chemical compatibility at the processing temperature. However, the price of Co is
subjected to great variations [2, 3]. It is the main reason behind efforts to replace Co with other metals
such as Co-bronze, Fe-bronze, Tin-Co, Fe-Co-Cu and Ni based materials [4-6]. In order to make sound
products of the diamond reinforced alloy, it is needed to select the composition of the alloy matrix, its
size, concentration of diamond grits, width and depth of ditches or diameter and depth of cell, location of
ditches and cells in a product [7-12]. On the other hand, in any process, a trial-and-error approach is an
expensive and time consuming way [13]. Therefore, several mathematical models based on statistical
regression techniques have been constructed to select the proper cutting or testing conditions [14-18].
The Taguchis design can simplify by expending the application of the traditional experimental designs
like full factorial or fractional factorial design to the use of orthogonal array [19-28].
The most of the study has been focused on processing and mechanical properties of hard and diamond
materials [1, 3-12]. However, no works related to abrasive wear properties of diamond reinforced metal
matrix composites by experimentally has been reported. The aim of the present study is, thus, to investigate the wear behaviour of diamond-reinforced composites based on the Taguchi method. Furthermore,
the analysis of variance is employed to investigate the wear behaviour of metal matrix composites under
different conditions.
151

2. TAGUCHI TECHNIQUE
Taguchi technique is a powerful tool for the design of the high quality system [18, 24]. To achieve desirable product quality by design, Taguchi recommends a three stage process such as system design, parametric design and tolerance design [25]. System design focuses on determining the suitable working
levels of design factors. It includes designing and testing a system based on the engineers judgement
of selected materials, parts and nominal process parameters. Parametric design seeks to determine
the factor levels that produce the best performance of the product/process. The optimum condition is
selected so that the influence of the uncontrolled factors (noises) causes minimum variation of the system performance. Tolerance design is used to fine tune the results of parameter design by tighting the
tolerance of factors with significant influence on the product [26].
The most important stage in the plan of experiment is selection of factors. The data collected from all
the experiments in the set are analyzed to determine the effect of various design parameters, which is
accomplished with the aid of orthogonal arrays [19, 21]. Taguchi recommends the use of the criteria he
call Signal-to-Noise (S/N)-ratios as performance statistics. The change in the quality characteristic
of a product in response to a factor introduced in the experimental design is the signal of the desired
effect. The effect of external factor (uncontrollable factors) on the outcome of the quality characteristic
under the test is termed noise. The S/N ratio measures the sensitivity of the quality characteristic being investigated in a controlled manner. A high value of S/N implies that signal is much higher than the
random effect of noise factors [26, 27].
Fe-Co based diamond reinforced composites were produced by hot pressing method. Diamonds were
used as reinforcement in the production of metal matrix composite while Co metal was a binder with
a good wet ability. Fe is also used as a filling material because of its lower-cost. The concentration of
diamond in the composite is kept constant as 20. The composites with various compositions [Fe-(15-3555wt. %Co)-bronze 10 wt. %-diamond 20 conc. with and without B4C powder (0.15 g)] were prepared.
Polycrystalline diamond grits of 40/+50 mesh (LS4750+, LANDS), a carbonyl iron powder with an
average particle less than 75 m (BaymetMetal Industry Inc.), a cobalt powder with an average particle
size of 400 mesh (Umicore), a bronze powder with 85/15 mesh (Pometon), and a B4C (H.C.Starck)
powder with average particle size less than 10m were selected as the starting materials for this study.
In the production of composites, Fe-Co-bronze-diamond- was blended in T2 turbula mixture at about 45
min. The mixture per composition was put in carbon moulds 24X10X10 mm dimension were cold compacted, and then hot zone was evacuated to remove the air from the chamber atmosphere, and sintered
by hot pressing of Fritsch DSP 510 type machine under nitrogen atmosphere. The sintering temperature
was about 900 oC under a compression of 25 MPa. Total sintering time was about 15 min. Three types
of samples were produced by this process, which is called as C1 (75Fe-15Co-10bronze-diamond), C3
(55Fe-35Co-10bronze-diamond), C5 (35Fe-55Co-10bronze-diamond) code.
A typical micrograph of MMC including diamond particles was examined by SEM microscopy. Macro
hardness tests, hardness Rockwell B, were carried out under 100 kgf in three samples for each composition and average of hardness values were calculated and presented.
3.1. Wear Tests
A pin-on-disc type of apparatus was employed to evaluate the wear characteristics of MMCs (Fig.1).
The counter surface material for the wear testing was a BS970 534A99 steel disc 160 mm diameter by
12 mm thick, which was heat-treated to give a surface hardness of 59-63 RC. The composite bars were
produced in the form of square shapes. The wear pin specimens made from MMCs are approximately
10X10 mm in dimension and 24 mm in length, too short to fit into a standard wear machine. To form a pin
necessary length the cylinders were bonded to a 60 mm long steel extension pin of the same diameter
using an epoxy adhesive, with a brass sleeve fitted over the joint for extra strength. The samples were
loaded against the hardened steel disc with the help of a cantilever mechanism. The specimens experienced to continuous motion in pre-determined time to complete the certain travel distances.
Wear tests were carried out at room temperature without lubrication at different times. In wear tests;
normal loads on the pin were 5, 15 and 25 N at a constant sliding speed of 1 m s-1. Each test was performed with a fresh SiC papers 400 grits and 180 grits, which is corresponds to ~18m and ~70 m,
152

respectively. The track radius has been kept at 90 mm in length. The width of the wear track was 6.5
mm. The track radius was measured to be the distance between the centre of the disc and the central
point of the track. A systematic view of the test procedure is shown in Fig. 1. The specimen surfaces
were ground well prior to initiating the wear tests and subjected to few runs against the counter surface
at different loads for establishing intimate contact between the two matting surfaces. All the samples
and the disc surface were cleaned by acetone and then dried under ambient condition prior to and after
tests. It was repeated for three times at least. Detail of the wear machine and wear process were given
in previous study [14].
Fig.1. Schematic view of the

pin-on-disc test procedure
3.2. Plan Experiments

The experiment was carried out to analyze the influence of testing parameters on weight loss of metal
matrix composites. In the present investigation, a standard Taguchi experimental plan with L18 (21X37)
was chosen. The wear parameters chosen were abrasive size, materials hardness, load, sliding time
and their levels, as indicated in Table 1. Experimental design is shown in Table 2. The first column in
Table 2 was assigned to abrasive size (A), second column was hardness (B), third column was applied
load (C) and forth column was assigned to sliding time (D) and the remaining columns were assigned to
their wear results. The response to be studied was the wear with the objective as smaller, as the better.
The experiments were conducted as per the orthogonal array with level of parameters given in each
array row. The abrasive dry wear test results were subject to the analysis of variance to see which tests
parameters are statistically significant.
Table 1. Control factors and their levels for diamond reinforced MMCs.
Levels
Abrasive size, m
Hardness, BHN
Applied load, N
Sliding time, s
18 m
88
30
2
3
70 m
-
93.4
97.2
15
25
60
90

4.1. Microstructure and Mechanical Test
A typical micrograph of MMC reinforced by diamond particles is shown in Fig.2. It indicated that no
evidence of the presence of cavities neither at interface nor in the matrix was observed using the SEM
microscopy. The distribution of diamonds in the matrix could be seen in this micrograph. The diamond
crystals were observed to be cube-octahedral in shape, but the diamond protrusions were also evidence. Fracture of different planes in diamonds was an indication of an enough bonding between the
diamond and the matrix alloy. Macro hardness tests by hardness Rockwell B were carried out under 100
kgf in three samples for each composition and average of hardnesss values were presented (Table 1).
The highest hardness was obtained for C5 samples because the hardness increased with increasing
Co content (55%).
153

Fig.2. Typical SEM micrograph of Fe-Co based MMC reinforced with only diamonds, showing
cube-octahedral diamond crystals set and distributions of diamonds in the matrix.
4.2. Analysis of Control Factors
Table 2 shows experimental design and results for weight loss of the composites and calculated S/N
ratios. Analysis of the influence of each control factor on the weight loss was performed using a Minitab
computer package. The control factor with the strongest influence is detected by differences values. The
selected quality characteristic, weight loss, is a lower the better type and the S/N ratio for lower the
better type of response is used as given below:

(1)
Where y1,y2....yn are the response of quality characteristic for a trial condition repeated n times. The
S/N ratio can be computed using Eq. (1) for each of the 18 trials and the values are reported in Table 2
along with the raw data.
Table 2. Experimental design and results for weight loss of MMCs and their calculated S/N ratios.
Main factors
Hardness, HB
Load,
(B)
N (C)
88
5
Sliding time,
s (D)
30
Diamond reinforced MMCs

Weight loss
S/N ratio (dB)
in g
0.00370
48.6360
Expert
no.
1
Abrasive size,
m (A)
18
18
88
15
60
0.00550
45.1927
18
88
25
90
0.01040
39.6593
18
93.4
30
0.00160
55.9176
18
93.4
15
60
0.00280
51.0568
18
93.4
25
90
0.00740
42.6154
18
97
60
0.00096
60.3546
18
97
15
90
0.00290
50.7520
18
97
25
30
0.00210
53.5556
10
70
88
90
0.00890
41.0122
11
70
88
15
30
0.01370
37.2656
12
70
88
25
60
0.01730
35.2391
13
70
93.4
60
0.00480
46.3752
14
70
93.4
15
90
0.00860
41.3100
15
70
93.4
25
30
0.00750
42.4988
16
70
97
90
0.00400
47.9588
17
70
97
15
30
0.00510
45.8486
18
70
97
25
60
0.00720
42.8534
154

12. Ko, Y.S., Tsurum, T., Fukunaga, Q., Yano, T., High pressure sintering of diamond-SiC composite,
J.Mater. Sci., p. 469-475, 36, 2001.
13. Rabinowicz, E.D., Friction and wear of work hardening in the design of wear resistant materials,
Wiley, New York, p.168, 1965.
14. ahin, Y., The prediction of wear resistance model for the metal matrix composites, Wear, p.17171722, 258, 2005.
15. Mondal, D.P., Das, S., Jha, A.K., Yegneswaran, A.H., Abrasive wear of Al alloy-Al2O3 particle
composite, Wear, p. 131-138, 223, 1998.
16. Prasad, B.K., Das, S., Jha, A.K., Modi, O.P, Dasgupta, R., Yegnaswaran, A.H.,Wear of Al2O3 particle composite, Composites, p. 301-308, 28A, 1997.
17. ahin, Y., Tribological behavior of the metal matrix and its composites, Mater. Des., p.1348-1352,
28, 2007.
18. Basavarajappa, S., Arun, K.V., Paulo Davim, J., Effect of fillers on dry sliding wear behaviour
of polymer matrix composites-A Taguchi approach, J.Miner.Mater. Charact.Eng. p. 375-391, 8,
2009.
19. Basavarajappa, S., Chandramohan, G., Paulo Davim, J., Application of Taguchi techniques to
study dry sliding wear behaviour of metal matrix composites, Mater.Des., p.1393-1398, 28, 2007.
20. Fernandez, J.E., Fernandez, M.R., Diaz, R.V., Navarro, R.T., Abrasive wear analysis using factorial
design, Wear, p.38-43, 255, 2003.
21. ahin, Y., Optimization of testing parameters on the wear behaviour of the metal matrix composites
based on the Taguchi method, Mater. Sci.Eng. p.1717-1722, A408, 2005.
22. Basavarajappa, S., Chandramohan, G., Wear Studies on Metal Matrix Composites A Taguchi Approach, J. Mater. Sci. Technol., p. 845-852, 21(6), 2005.
23. ahin, Y., Comparison of tool life between ceramic and cubic boron nitride (CBN) cutting tools
when machining hardened steels, J.Mater. Process. Technol. p.3478-3486, 209, 2009.
24. Yang, W.H., Tarn, Y.S., Design optimization of cutting parameters for turning operations based on
the Taguchi method, J.Mater. Process. Technol. p.121-129, 84, 1998.
25. Roy, R.K., A Primer on the Taguchi method, Van Nostrand Reinhold, New York, 1993.
26. Phadke, M.S., Quality Engineering Using Robust Design, AT&T Bell Laboratories Report, Prentice-Hall International Editions, New Jersey, 1989.
27. Montgomery, D.C., Experimental Design Analysis, 4th Edition, John Wiley Sons, New York,
1997.
28. Rose, P. J., Taguchi Technique for Quality Engineering, McGraw-Hill, New York, 1988.
158

THE EFFECT OF SINTERING AND NITRIDING PROCESSES

ON DISTALOY AE POWDER MATERIALS
smail AKBULUT*, Abdul Kadir EK**, Durmu Ali BIRCAN**, Murat DILEK** and hsan EFEOLU***
* Turkish Petroleum Corporation, Batman, Turkey, ismailakbulut61@yahoo.com
** ukurova University, Mechanical Engineering Department, Adana Turkey,
akeksi@cukurova.edu.tr, abircan@cukurova.edu.tr, mdilek@hotmail.de
*** Atatrk University, Mechanical Engineering Department, Erzurum, Turkey, iefeoglu@atauni.edu.tr
ABSTRACT
In this work, Distaloy AE metal powders have been chosen for study due to widely used in industrial applications.
First, Distaloy AE powders were pressed at 500 MPa pressure and room temperature. Then, pressed specimens
were sintered at 1120 C for 30 minutes. In order to examine the effects of sintering operation on density, densities of each specimen have been measured separately. After sintering operation, nitriding was applied to a group
of specimen at 520 C temperature during 16 hours. To investigate mechanical properties of sintered and nitrided
Distaloy AE powders were performed. In addition, fractured specimens after tensile tests were used for microhardness tests.
Key Words: Distaloy AE, Sintering, Nitriding, Fatigue
1. INTRODUCTION
The Powder Metallurgy (PM) process is a near-net or net-shape manufacturing process that combines the features
of shape-making technology for powder compaction with the development of final material and design properties
(physical and mechanical) during subsequent densification or consolidation processes (e.g., sintering). It is critical
to recognize this interrelationship at the outset of the design process because a subtle change in the manufacturing
process can cause a significant change in material properties. Powder metallurgy has a wide range of applications
ranging from automotive, building and contraction, hardware, heat treatment, medical and dental, to advanced
aerospace components, etc. PM components have established themselves as an economic alternative to components made from other manufacturing processes as well as the only means to procedure some components which
cannot be made other methods [1].
This process is a very suitable technique for manufacturing. Especially, this process contains blending or mixing,
pressing or compacting, sintering and finishing. An important step is sintering for this process. Sintering reduces
the porosity and enhances properties such as strength, translucency and thermal conductivity; yet, in other cases,
it may be useful to increase its strength but keeping its gas absorbency constant. During the firing process and as
it continues; grain size becomes smaller and more spherical [2, 3].
The most important thing after producing the material by using PM is to increase the mechanical and physical
properties of the material. This especially can be done by nitriding. Nitriding is low temperature, low distortion
thermochemical heat treatment carried out to enhance the surface properties of finished or near finished ferrous
components. It is different in terms of suitable materials, processing conditions, the nature of the surface layers
imparted and the property improvements conferred. Nitriding, conducted in gas (490C - 560C) or plasma (400C
- 590C) for treatment times ranging up to 90 hours, involves the diffusion of nitrogen into the surface to produce
a controlled depth of hard alloy-nitrides. Unlike the high-temperature, a case-hardening treatment, hardening is
achieved without the need for quenching [4, 5].
159

Nitriding process has some advantages to improve qualified for part properties. These are high torque, high wear
resistance, abrasive wear resistance, corrosion resistance and high surface compressive strength.
This paper presents the influence of sintering and nitriding process on Distaloy AE PM. The main aim of these processes is to improve physical and chemical characteristic of Distaloy AE. To do this, one should know the properties
of the material well, adjust the temperature of the thermal process, choose a process increasing the surface quality
and suitable for sample and perform a good fatigue design.
2. MATERIAL and METHOD
2.1. Material
The Distaloy AE based on additions of Iron (Fe), Nickel (Ni), Copper (Cu), Molybdenum (Mo) and Carbon (C) is a
high strength alloy. High Ni content and good compressibility makes it possible to produce materials with a sintered
tensile strength increased. Distaloy AE exhibits good hardenability and dimensional stability.
The chemical composition of Distaloy AE powder, from Hganas in Sweden, is given in Table 1.
Table 1.Chemical composition of Distaloy AE powder
Chemical Analysis of Distaloy AE %
Iron (Fe)
Nickel (Ni)
Copper (Cu)
Molybdenum (Mo)
Carbon
94
1.5
0.5
0.01
2.2. Method
Firstly, the components of Distaloy AE powder (4% Ni, 1.5% Cu , 0.5% Mo ,%0.01 C); which are approximately
weight of 37 g are mixed to put into blanks which a die in sizes of 10x10x55 mm, together with lubricant, until a
homogeneous mix is obtained under 500 MPa pressure at room temperature. Then, the specimens were sintered
under 1120 C sintering temperature was selected the optimum temperature to produce the samples for tensile and
fatigue tests since it resulted in high density. All specimens were sintered for 30 minutes at 1120 C temperature,
respectively. Temperature was increased by 5 C/min until medium of furnace reached sintering temperature; and
then specimens were kept for 1 hour. After, furnace was closed and temperature was decreased by 5 C/min, until
medium of furnace was reached room temperature (RT, 22C). After this process, density of sintered and green
Distaloy AE was evaluated by the Archimedes Principle. After, the sintered samples were conducted machining
operations and polishing operations using Computerized Numerical Control (CNC) turning lathe and metal polishing
machine, in turn, to achieve optimum results for fatigue and tensile test produced. After that, fatigue and tensile test
samples and technical drawings are shown in Figure 1 and 2 separately.
Figure 1. Fatigue and tensile test specimens; a) Fatigue test sample, b) Tensile test sample
Figure 2.Technical representation of fatigue and tensile test specimens; a) Finished product for fatigue test sample, b) Finished product for tensile test sample (Dimensions are in mm)

In this study, nitriding was applied to increase fatigue life of material. To evaluate sintered and nitrited parts in
respect to mechanical properties, 11 samples were sintered and other 11 samples are nitrited at 520 C temperature and 16 hours in % 50 H2 and % 50 N2 atmosphere. After this process, tensile and fatigue test samples were
prepared [6].
160

All the experiments of fatigue tests were conducted in the axial load control which is more severe than bending
under fully reversed loading (stress or load) ratio R= min/ max=-1 which is sine (cyclic) waveforms using 11
specimens for the determination of each S-N (Whler) curve. The fatigue tests were performed at the constant
frequency of f = 10Hz. One stress ratios (R = -1) were investigated on the unnotched (Kt=1 ) specimens. Sine (cyclic) waveforms are used. The cyclic group of waveforms all start at a setpoint, proceed to a peak amplitude, either
negative or positive, before reversing direction, passing through the setpoint to the opposite peak amplitude. The
signal will then return to the initial starting position, ready to commence the next cycle. The sine waveform follows
a sinusoidal path, defined by the amplitude and frequency parameters. In the tensile test, experiment was taken v
= 0, 5 mm/min as vertical movement and this velocity was kept constant during experiments [7]. Furthermore, the
vickers hardness profile of fractured parts obtained as a result of static tests was measured at 14 different points
and intervals of 3 mm on longitudinal section using a Vickers intender with a 25 g load for time of 10 s as shown
in Figure 3.
Figure 3. Fractured sample during tensile test for vickers micro-hardness experiment
3. RESULT AND DISCUSSION
In this study, green densities of Distaloy AE powders were determined as 7.19 g/cm under 500 MPa. The average
densities of sintered and nitreded samples were found as 7.13 g/cm and 7.15. g/cm respectively. As can be seen,
green density of samples was higher than sintered densities. So, the decrease in number of pores and becoming
the internal structures more homogeneous. Hardness extremely increased after nitriding as can be easily and
clearly understood from the graph shown Figure 4. The occurrence of a layer above the nitrited sample can be
seen in Figure 5.
Figure 4. Compare hardness of sintered and nitrided specimens
Figure 5.Nitriding layer of samples
This layer provides the surface of the material gets more severe and as a result be resistant against impacts. The
hardness increases by 163 percent on the surface and by 39 percent in the inner sides.
The result of tensile test, sintered and nitreded specimens shown in Figure 6. Sintered sample ruptured 297 MPa
of maximum tensile stress while the nitrided one had 318MPa tensile stress of maximum. Diffusion of nitride atoms
through the sample plays an important role for making is stronger. Nitride atoms enter the gaps and pores of the
sample and makes its tensile stress increase by 7 percent.
161

Figure 6. Comparison sintered and nitreded specimens of tensile stress curves

In fatigue experiments, 50-140 MPa as a stress value of average are used and graphs are generated. 2*106 value
was accepted as a limit in the graph as previous ones and above this value was run-out period. After nitriding, nominal stress increased by 15-20 % and the lifetime of sample was better. 90 MPa stress, sintered sample ruptured
after 379000 cycle while the nitrited one ruptured after 1513601. The main effect on this condition is the diffusion of
nitrite atoms through the inner side of the sample and fill the gaps and pores. After that, the inner side of the sample
is becoming more stable and homogenous, and so that the lifespan gets longer shown Figure 7.
Figure 7.Comparison of S-N curves for all sintered and nitreded specimens
4. CONCLUSION
The density of Distaloy AE powder was measured in two different conditions and nitrited sample density (7, 12 at
room temperature) was more than sintered one.
After the Tensile test, the resistance of the sample increased more in nitriding, the Ultimate Tensile Strength was 8
percent more than sintering.
Fatigue resistance is 50-120 MPa for sintered samples and 70-140 MPa for nitrided samples. At 100 MPa pressure,
sintered sample ruptured 120000 rpm, nitrided sample ruptured at 150000 rpm. The increase in the density of the
nitrided sample was simply because of the decrease in pore amount.
5. REFERENCES
1.
2.
3.
4.
Angelo P.C. and Subramanian R., 2009, Powder Metallurgy Science, Technology and Applications.
ASM Handbook, 1998, Powder Metal Technologies and Applications, Vol. 7, ASM International.
German, R. M., 1997, Powder Metallurgy Science, Metal Powder Industries Federation, New Jersey, USA.
Miura, H., 2002, Fatigue Fracture Behavior of PM and PIM Steels, 3rd International Powder Metallurgy Conference, September 4-8, 2002, Turkish Powder Metallurgy Association, Gazi University, Ankara, Turkey, pp.
47-55.
5. Molinari, A., Tesi, B., Bacci, T. and Marcu, T., 2001, Plasma Nitriding and Nitrocarburising of Sintered Fe-CrMo and Fe-Cr-Mo-C Alloys, Surface and Coatings Technology 140, pp. 251-255.
6. ASTM E8M, 2004, Standard Test Methods for Tension Testing of Metallic Materials (Metric).
7. ASTM E739, 2004, Standard Practice for Statistical Analysis of Linear or Linearized Stress-Life (S-N) and
Strain-Life (-N) Fatigue Data at Room Temperature.
162

BYOMEDKAL UYGULAMALAR N Ti-Mg

KOMPOZTLERNN GELTRLMES
Ziya ESEN*, Arcan F. DERCOLU**, akir BOR***
ankaya niversitesi, Malzeme Bilimi ve Mhendislii Blm, 06530, Ankara, Trkiye,
ziyaesen@cankaya.edu.tr
**
Orta Dou Teknik niversitesi, Metalurji ve Malzeme Mhendislii Blm, 06531, Ankara, Trkiye,
arcan@metu.edu.tr
***
Orta Dou Teknik niversitesi, Metalurji ve Malzeme Mhendislii Blm, 06531, Ankara, Trkiye,
bor@metu.edu.tr
*
ZET
Biyomedikal uygulamalarda kullanlan metalik malzemeler genel olarak vcuda yerletirildikten belli bir sre sonra
vcut svlaryla tepkimeye girmekte veya herhangi bir reaksiyona girmeden btnln korumaktadrlar. Son
zamanlarda vcuda yerletirildiinde zamanla tepkimeye girerek vcutta yokolan ve herhangi bir yan etkiye neden
olmayan magnezyum ve magnezyum alamlar zerine yaplan almalar artm ve genellikle aratrmalar bu alamlarn vcutta kontroll bir ekilde znmesi zerine younlamtr. Dier yandan, vcut svlaryla tepkimeye
girmeyen titanyum ve titanyum alamlar gibi metalik malzemeler son derece yksek biyo uyumlulua ve korozyon
direncine sahip olduklarndan dolay sklkla biyo-medikal uygulamalarda kullanlmaktadrlar. Bu almada, vcutta tepkimeye giren magnezyum ile herhangi bir reaksiyona girmeden btnln koruyan titanyumun bir arada
kullanlmasyla yeni bir biyomedikal kompozit malzeme toz metalurji yntemi kullanlarak scak deformasyonla retilmitir. Hacimce % 50, 60, 70 ve 80 magnezyum tozu ieren Ti-Mg tozlar iki ucu kapatlm bakr borularn iinde
430oCde scak deforme edilen numunelerin apnda yaklak % 45 deiim gzlenmitir. Numuneler 600oCde 100
dak. sinterlendikten sonra basma ykleri altnda mekanik zellikleri karakterize edilmi ve kompozitlerin i yaplar
optik ve elektron mikroskoplar ile incelenmitir.
Anahtar Kelimeler: Kompozit, Biyo-malzeme, Toz Metalurjisi, Mekanik zellikler
DEVELOPMENT OF Ti-Mg COMPOSITES FOR BIOMEDICAL

APPLICATIONS
ABSTRACT
Metallic materials used in biomedical either interact with body fluids after a while or they preserve their integrity
without any reaction. Nowadays, the research on magnesium, which dissolves in the human body after having been
implanted without leaving harmfull remainders, has been inceased and the researches are focused on dissolving of
magnesium in vivo in a controlled fashion. On the other hand, Ti and Ti-alloys are being used as bio-inert materials
and preferred in biomedical applications as they exhibit superior biocompatibility and high corrosion resistance. In
this study, new type of biomedical composite structures made up of biodegradable magnesium and bio-inert titanium powders have been manufactured by powder metallurgy using rotary hot swaging. Around 45% reduction in
diameter has been observed in cans filled with Ti-Mg powder mixtures containing 50, 60, 70 and 80 % magnesium
by volume as a result of deformation at 430oC. The samples were compression tested under quasi-static conditions after they had been homogenized by the application of annealing heat treatment at around 600oC. In addition,
microstructure of mechanically tested samples were examined by optical and scanning electron microscopes.
Keywords: Composite, Bio-material, Powder Metallurgy, Mechanical Properties
163

1. GR
Son zamanlarda medikal alanlardaki ilerlemelerle birlikte insanlarn ortalama mr ykselmi ve dolaysyla uzun
mrl ve vucda uyumlu biyomedikal malzeme aratrmalar nceki yllara oranla byk bir art gstermitir. Biyomedikal malzemeler yapay kalp valflerinde, stentlerde ve di protezlerinde kullanlmakta, bunun yannda vcutta
deiik yklere maruz kalan omuz, diz, kala ve dirsek gibi hareketli eklem blgelerinde de protez uygulamalar sklkla grlmekte ve zellikle diz ve kala blgelerindeki protez uygulamalarnda nmzdeki 20 yl iinde % 100n
zerinde art gzlenmesi beklenmektedir [1].
Biyomedikal malzemeler vcuda yerletirildikten bir sre sonra anma, korozyon, yorulma, iltihap oluumu gibi
nedenler ile vcut kemii ile mekanik zelliklerindeki uyumsuzluklarndan dolay ilevini yitirmekte ve bundan dolay
ya yaplan operasyonlar tekrar edilmekte ya da vcut hcrelerinde geriye dnlemez hasarlar meydana gelebilmektedir. Bu nedenlerden dolay kullanlacak olan biyomedikal malzemelerin yksek derecede biyo uyumlulua, yksek
korozyon direncine sahip olmas ve vuct kemiine benzer mekanik davranlar gstermesi beklenmektedir. zellikle eklem blgelerinde kemik ile biyomedikal malzemelerin elastik modlleri arasndaki farkllk kemik ve implant
malzemenin deiik oranlarda yk tamasna neden olmakta bu da zamanla implanta temas eden blgelerdeki
kemik hcre kaybn ve implantn yerinden kmasn beraberinde getirmektedir ve bundan dolay da implant ve
kemik elastik modllerinin (katsaylarnn) benzerlik gstermesi implant malzemenin vcutta gvenli bir ekilde kullanlmas asndan nemlidir. Bunun yannda uzun bir implant mr iin biyomedikal malzemenin yksek anma
direnci ile yorulma dayanmna sahip olmas da beklenmektedir.
Gnmzde kullanlan biyomedikal malzemeler genellikle metalik, seramik ve polimerik malzemelerdir. rnein
seramik malzeme olarak aluminyum oksit ve kalsiyum fosfat, polimerik malzeme olarak poli etilen malzeme kullanmlar grlmektedir. Bunlarn yannda seramik takviyeli polimerik kompozitler ile biyouyumluluu arttrmak iin
eitli metalik malzemeler zerine seramik kaplama uygulamalarna da rastlanmaktadr [2]. Kullanlan biyomedikal
malzemeler arasnda polimerik malzemeler dk mekanik dayanmlarndan, seramik malzemeler de dk krlma tokluuna bal olarak krlgan olmalarndan dolay yke maruz kalan blgelerde kullanlamamaktadr. Bu tr
uygulamarda titanyum, titanyum alamlar, Co-Cr alamlar ve paslanmaz elik gibi metalik malzemeler tercih
edilmektedir.
Metalik malzemeler arasnda vcut kemiine benzer mekanik zellikleri, yksek biyouyumluluklar ve TiO2 pasif
yzey oksit tabakasna bal yksek korozyon direnlerinden dolay titanyum ve titanyum alamlar biyomedikal
uygulamalarda sklkla tercih edilmektedirler. Co-Cr alamlar ve paslanmaz elikler iin 240 ve 210 GPa olan elastik modl titanyum ve sklkla kullanlan Ti6Al4V alamlar iin srasyla 100 ve 112 GPa civarndadr [1]. Fakat bu
malzemelerin elastik modl kemiin elastik modlne (3-20 GPa [3]) gre farkllk gstermesinden dolay nispeten
kemiin mekanik zelliklerine daha fazla benzerlik gsteren NiTi alamlar ile Ti-Nb gibi beta tipi titanyum alamlar
gelitirilmitir. Yine de kullanlan veya gelitirilen hacimli biyomedikal malzemeler tam olarak istenilen mekanik deerlere ulaamamaktadr. Son zamanlarda istenilen mekanik zelliklere sahip ve ayn zamanda kemik hcrelerinin
bymesine olanak salayabilecek ekilde gzenekli titanyum ve titanyum alamlarnn sv veya kat faz retimi
konusunda birok almalar yaplmtr [4-6]. Bu tr gzenekli malzemelerin retilmesiyle istenilen mekanik deerlere ulalmasna ramen gzeneklerin kemik hcreleriyle dolmas iin en az 3 ay gibi bir zaman gemektedir.
Bu zaman aralnda implant malzemesinin kemie tam olarak tutanamamasndan dolay bu aamada sorunlara
neden olmaktadr.
Genel olarak hacimli veya gzenekli titanyum ve titanyum alamlar vcuda yerletirildikten sonra btnlklerini korumakta ve vcut svlaryla yok denecek kadar az reaksiyona girerek vcutta kalc implant vazifesi grmektedirler.
Dier yandan son zamanlarda titanyum ve titanyum alamlarnn aksine vcut svlaryla tepkimeye girerek bir nevi
kemik hcrelerinin bymesine yardmc olan magnezyum ve magnezyum alamlarnn kullanm artmtr. Fakat,
yeni kemik hcrelerinin bymesinde uyarc bir etki gsteren ve mekanik zellikleri kemiin mekanik zellikleri ile
kyaslanabilir olan magnezyum ve magnezyum alam implantlar kemik hcrelerinin kendini yenilemesi esnasnda
sadece 12-18 hafta arasnda mekanik btnl korumakta ve sonrasnda yksek korozyon hzndan dolay btnln yitirmektedir [3]. Magnezyumun hzla korozyona uramas mekanik btnln bozulmasna ve ilevisini
yitirmesine neden olmaktadr. Bu almada saf titanyum ve saf magnezyumun bir arada kullanlmasyla biyomedikal uygulamalarda kullanlmaya aday yeni bir kompozit malzemenin retimi ve karakterizasyonu aratrlmtr.
Bu amala, toz metalurji yntemi kullanlarak scak dvme yoluyla kompozit retimi yaplm ve kompozit retimi
esnasnda ve sonrasnda meydana gelen i yap deiikleri incelenmitir. Son olarak basma testleri ile de retilen
kompozitlerin mekanik davranlar incelenerek kompozitlerin mekanik zellikleri vcut kemii ile karlatrlmtr.
2. DENEYSEL YNTEM
Scak deformasyon yntemiyle Ti-Mg kompozit retiminde ASTM F1580-01 standartlarna uygun 55 m ortalama
tane byklne sahip ekilsiz, yaklak % 99 saflkta titanyum tozlar (Phelly Materials) ile % 99.8 safla sahip
164

ortalama tane boyutu 285 m olan kresel magnezyum tozlar (Tangshan Weihao Magnesium Powder Co. LTD)
kullanlmtr.
retimde ilk olarak homojen bir toz karm elde etmek amacyla hacimce miktar % 50-80 arasnda magnezyum
tozu ieren Ti-Mg toz karmlar yarm saat sreyle bir kartrc vastasyla kartrlmlardr. Daha sonra hazrlanan toz karmlar bir ucu kapal bakr borunun iine yerletirilmi ve birka defa vakum altna alnp bakr borulara
yksek saflkta argon doldurulmu ve bakr borular kapatlmtr. retimin bir sonraki aamasnda ise hazrlanan
numuneler scak deformasyon yntemiyle 3 basamakta toplam % 45 orannda scak deforme edilmilerdir. Tozlarn
sinterlenmesini hzlandrmak ve homojenlemeyi arttrmak amacyla numuneler hem deformasyon ncesinde hem
de deformasyon basamaklar arasnda 450oCde 20er dakika bekletilmilerdir. Ayrca scak deformasyon sonras
numunelerde olas gerilimleri azaltmak ve magnezyum tozlarnn sinterlenmesi daha da arttrmak amacyla 600oC
scaklkta 90 dakika sreyle yksek saflktaki argon altnda tavlanma ilemi yaplm ve sonrasnda numuneler oda
scaklna frnda soutulmutur. Son olarak kompozit malzemelerin yzeyindeki bakrlar ayrlm ve CNC torna
yardmyla malzemeler ilenmitir.
Numunelerde retim sonras younluk ve gzenek miktar Arimed prensibiyle younluk lm kitine sahip Sartorius marka hassas terazisi kullanlarak numunelerin ksilol zeltisine (CH3C6H4CH3) daldrlmasyla belirlenmitir.
retimde kullanlan titanyum ve magnezyum tozlar ile retilen kompozit malzemelerin X-Ray krnm erileri Rigaku
D/Max 2200/PC model X-Ray cihaz kullanlarak 40 kWta 30o-90o 2 alar arasnda belirlenmitir. Malzemelerin i
yap incelemeleri hem parlatlm, hem de dalanm yzeyde gerekletirilmitir. Kompozitlerdeki magnezyumun
i yap detaylarn ortaya karmak iin %5lik nital zeltisi, titanyum incelemesinde ise Krolls ayrac (3 ml HF+6
ml HNO3+100 ml H2O) kullanlmtr. yap incelemelerinde optik mikroskop ve Noran System 6 X-ray mikro analiz
sistemine sahip Jeol JSM 6400 elektron mikroskobu kullanlmtr. Kompozitlerde kompozisyon deiimlerini belirlemek amacyla EDS izgi analizleri de ayrca kullanlmtr. Tane bykl gibi kantatif analizler Clemex Vision
yazlm kullanlarak gerekletirilmitir.
Kompozitlerin mekanik zellikleri biyomedikal malzemelerin vcutta sklkla maruz kald basma ykleri dnlerek basma testleri ile karakterize edilmitir. Bu maksatla ykseklik/ap oran yaklak 1.5 olan numuneler hazrlanm ve numuneler 0.5 mm/min hzyla video ekstansometreye sahip 100 kN kapasiteli Instron marka niversal
ekme-basma cihazyla baslmlardr.
3. BULGULAR VE TARTIMA
Bu almada younluu %100e yakn, magnezyum miktar hacimce % 50-80 arasnda deien biyomedikal uygulamalara aday Ti-Mg kompozit numuneleri retilmitir. Magnezyum oda scaklnda sadece (0001)<11-20> kayma
sistemiyle deforme olabilmektedir ve yksek deformasyonlarda ise malzemeler kayma sistemlerinin snrl sayda
olmasndan dolay krlmaktadr. Fakat, deformasyon scaklnn yaklak 200oCnin zerine kmasyla farkl kayma sistemleri iler hale gelmekte ve magnezyumun deformasyonu ok daha kolay olabilmektedir. retilen btn
numunelerde titanyum tozlarnn arasndaki olas boluklar magnezyumun 450oC scaklkta deformasyona uramas ile doldurulmu ve younluu yksek, gzeneksiz bir yapnn eldesi salanmtr.
ekil 1de rnek olarak Ti-80Mg kompozit numunesinin retim sonras deformasyona dik ve yatay kesitlerdeki
parlatlm i yaps verilmektedir. ekilde koyu renkli blgeler magnezyumu, ak renkli blgeler ise titanyumu gstermektedir. Deformasyona dik olan kesitte magnezyum kreselliini korumasna ramen yatay kesitte magnezyum
deformasyona urayarak deformasyon ynnde uzamtr.
Biyomedikal uygulamalara aday olarak retilen Ti-Mg kompozitlerde titanyumun btnln korumas, dier yandan magnezyumun vcut svlaryla tepkimeye girerek korozyona urayp belli bir zaman sonra kaybolmas beklenmektedir. Dolaysyla retilen kompozitlerde magnezyum tozlarnn yap iinde birbiriyle balantl olup olmamas
bu tr kompozitlerin korozyon davrann deitirecek ve numunelerin biyouyumluluklar farkl olacaktr. Magnezyum tozlarnn birbiriyle temas ettii kompozitlerde korozyonun hzl, magnezyum tozlarnn birbirlerinden titanyum
tozlar ile tamamen izole edildii numunelerde ise yava bir korozyon hz beklenmektedir. Yaplan almada ise
hacimce % 50 magnezyum ieren Ti-Mg kompozit numunelerinde magnezyumun izole olarak yapda durduu,
dier numunelerde ise magnezyum tozlarnn yap iinde birbirine balantl olduu grlmtr. Dier taraftan
magnezyum tozlarnn etrafnda yapda srekli olan titanyum tozlarnda retim sonrasnda yksek derecede younlama saland saptanmtr. Yaplan i yap incelemeleri ve mekanik testlerde titanyum tozlarnn birbirine ok iyi
derecede mekanik olarak kilitlendii, fakat 600oCde uygulanan tavlama ileminin titanyum tozlarnn sinterlenmesinde etkili olamad grlmtr.
Oda scaklnda titanyum ve magnezyum birbiri iinde yok denecek kadar az znmektedirler (yaklak arlka
% 1.5) [7]. retilen kompozitlerde titanyum ve magnezyum tozlar ile arayzey boyunca yaplan EDS izgi analizlerinde ise herhangi bir kat zelti veya ikincil bir faza rastlanmam, eklenen titanyum ve magnezyum tozlarnn
retim sonras yapda olduu gibi kald gzlenmitir.
165

(a)
(b)
ekil 1. retilen Ti-%80Mg kompozitlerinin parlatlm i yaplar,

a) deformasyona dik ara kesit, b) deformasyona paralel ara kesit.
Ti-Mg kompozitlerde titanyum ve magnezyum tozlarnda retim esnasnda meydana gelecek deiiklikleri tayin
edebilmek son rndeki i yapy ve dolaysyla rn fiziksel zelliklerini kontrol etme imkan salamaktadr. Yaplan
deneylerde Ti-Mg kompozitlerde zellikle magnezyum tozlarnda mikro boyutta i yap deiimi saptanm ve bundan dolay magnezyum tozlarndaki deiimi daha iyi gzlemleyebilmek iin saf magnezyum numunelerinde retim
esnasndaki deiimler incelenmitir (ekil 2 ve ekil 3). ekil 2 (a)da grld gibi kullanlan magnezyum tozlar
retim ncesi irili ufakl dallantl bir yapya sahiptir. Tozlarn 450oCde 3 basamakta yaklak % 45 orannda deformasyona uradktan sonra bu dallantl yapnn belli ynlerde deforme olduu fakat tam olarak krlp yok olmad
grlmtr (ekil 2 (b)). Scaklk ve deformasyonun ayn zamanda uyguland numunelerde belli scaklklarn
stnde genellikle dinamik olarak yeniden ekirdeklenme ile e eksenli tane oluumu beklenmektedir. Deformasyonun scakla baskn olduu durumlarda yeni tanelerin olutuu, fakat scakln baskn olduu durumlarda ise
dinamik olarak yeniden ekirdeklenmenin mmkn olmad bilinmektedir. Bu almada scak deforme edilen numunelerde yeniden ekirdeklenme ile oluan tanelerin grlememesi her bir basamaktaki deformasyon miktarnn
(% 25) az olmasna balanm, scaklnn deformasyon miktarna baskn karak yeniden ekirdeklenmeyi engelledii dnlmtr. Numunelerin 600oCde tavlama sonras ise ok daha farkl bir i yap oluumu gzlenmi,
dallantl yapnn tamamen kaybolduu tespit edilmitir. ekil 3te saf magnezyum numunelerinin scak deformasyon ve 600oCde tavlama sonras deformasyona dik ve paralel ynlerdeki i yaplar verilmitir. ekil 3te kaln siyah
renkli izgiler magnezyum tozlarnn yzeyinden kaynakl MgO tabakalarn, ince siyah renkli blgeler ise 600oC
scaklkta tavlama sonras oluan eeksenli tane snrlarn gstermektedir. Tozlar aras MgO faznn asitle yksek
miktarda reaksiyona girmesi sonucu bu blgeler tane snrlarna gre daha kaln yapda grlmektedir. Grld
gibi deformasyon sonras yapda bulunan dallantl yap tavlama ilemi sonras dik kesitte ortalama bykl 90
m olan e eksenli tanelere dnmtr. Magnezyum tozlarnda grlen bu eeksenli yapnn yeniden ekirdeklenmeye uramadan dallantl yapdan direk olarak byd grlmtr. Uygulanan tavlama scaklnn (600oC)
magnezyumun erime scaklna (650oC) olduka yakn olmas bu direk bymenin nedeni olarak dnlmtr.
Numuneleri homojenletirmek, magnezyum tozlarnn sinterlenmesini salamak amal yaplan tavlama ileminin
scakln daha da arttrmak mmkndr. Fakat, 630oCde yaplan tavlama ilemlerinde scakln magnezyumun
erime noktasnn (650oC) altnda olmasna ramen magnezyum toz yzeylerinde buharlama olduu saptanmtr.
Erime noktasnda yaklak 3.5x10-3 atm olan magnezyumun buhar basncnn dk olmas erime noktasna ulalmadan magnezyumun ksmi olarak buharlamasna neden olmakta, bu da tavlama scakln kstlamaktadr. Dier
yandan kalsiyum ve lityum gibi yksek derecede oksitlenme potensiyeline sahip olan magnezyum ve magnezyum
ieren kompozitlerin yksek scaklklarda retimi de problem olmaktadr. Olas oksitlenme problemlerinden dolay
bu almada tavlama scakl 600oCde snrlandrlmtr.
(a)
(b)
ekil 2. a) Kullanlan magnezyum tozlarnn retim ncesi i yaps, b) scak deformasyon sonras magnezyum
numunelerinin deformasyona dik yndeki i yaps.
166

ekil 3. 600oC tavlama sonras

magnezyum numunelerinin i
yaps,
a) deformasyona dik kesit, b)
deformasyona paralel kesit.
(a)
(b)
Titanyum ve magnezyumun mekanik zellikleri oksijen gibi arayer atomlarnn znrlnden ve buna ek olarak
oluabilecek oksit fazlarndan yksek derecede etkilenmektedir. retilen kompozitlerde titanyum ve magnezyum
toz blgelerinde yaplan EDS nokta analizlerinde titanyum ve magnezyum haricinde herhangi bir elemente rastlanmam, faz oluumlarn aratrmak amacyla da balang tozlar ile retilen kompozitlerde numune yzeylerinden
tala kaldrldktan sonra deformasyona dik kesitlerde X-Ray analizleri yaplmtr (ekil 4). Grld gibi balang tozlar ile rnek olarak verilen Ti-80Mg kompozit numunesinde herhangi bir oksit ve dier ikincil faz oluumuna
rastlanmamtr. retilen dier Ti-Mg kompozit numunelerinde de Ti-80Mg kompozit numunesine benzer krnm
erileri gzlenmi fakat magnezyum ve titanyum tozlarnn miktarlarndaki farkllktan dolay magnezyum ve titanyum krnm iddetlerinde deiiklikler olduu gzlenmitir.
Saf magnezyum ve Ti-Mg kompozit numunelerinin i blgelerinde oksit veya ikincil faz oluumu gzlenmemesine
ramen numunelerin yzeye yakn blgelerinde durumun farkl olduu saptanmtr. Numunelerin yzeyinden tala
kaldrlmadan nce yzeye yakn blgelerde yaplan i yap analizlerinde zellikle magnezyum tozlarnn arasnda
kalnl 500 nmye ulaan MgO tabakasna rastlanmtr (ekil 5). Numunelerin i blgelerindeki magnezyum tozlarnn arasnda varolan birka nanometre mertebesindeki oksit tabakalar scakln etkisi ile tozlarn bakr ile temas
eden yzeye yakn blgelerde bymtr. Bu yzden mekanik test ncesinde btn numunelerin yzeyinden
yaklak 1 mm kalnlnda tala kaldrlmtr.
(a)
(b)
ekil 4. X-Ray krnm rgeleri, a) retim ncesi magnezyum ve titanyum tozlar, b) scak deformasyon ve 600oC
tavlama sonras Ti-80% Mg kompozit
(a)
(b)
ekil 5. (a) Ti-80Mg kompozitlerde yzeye yakn blgelerin i yaps ve analiz alnan blge, (b) ekil 5(a)da gsterilen blgenin EDS izgi analizi.
167

ekil 6da alma kapsamnda retilen saf magnezyum ile Ti-50Mg kompozit numunesinin basma ykleri altndaki
mekanik davranlar sergilenmekte, Tablo 1de ise retilen btn numunelerin mekanik deerleri verilmektedir.
ekil 6da grld gibi hem saf magnezyum, hem de Ti-Mg kompozit numuneleri basma ykleri altnda benzer
davran sergilemekte ve gerilim-gerinim erileri elastik blge, gerinim sertleme blgesi ve tepe noktasndan sonra
krlma blgesi olmak zere 3 blgeden olumaktadr. Grld gibi saf magnezyum numunesinde kompozitlerden farkl bir gerinim sertleme blgesi grlmtr. Bu blge kompozit numunelerde akma noktasndan maksimum
yk noktasna kadar ayn ekilde art gstermesine ramen magnezyum numunelerinde gerilim sertleme derecesinde belli bir gerinim deerinden sonra art gzlenmitir. rnein ekil 6da verilen eride magnezyum, akma
noktas ile 0.05 gerinim deeri ve maksimum yk noktas ile 0.05 gerinim deerleri arasnda farkl gerinim sertleme
davranlar gstermektedir.
ekil 6. alma kapsamnda retilen baz numunelerin basma yk altndaki gerilim-gerinim erileri
Basma testi srasnda gerilim-gerinim erilerinin tepe noktasna ulaldnda ise basma eksenine 45ode yzey
atlaklar olumu ve daha sonra malzemeler belli bir gerinimden sonra krlmlardr (ekil 7(a)). Basma srasnda
atlaklar hem titanyum toz blgelerinde, hem de titanyum magnezyum arayzeyinde meydana gelmitir. Magnezyum ve titanyum arasnda herhangi bir znrlk olmamasna ramen basma testi srasnda ilgin olarak magnezyum tozlar yapdan btnyle ayrlmam, atlak magnezyum toz taneleri boyunca ilerlemi ve magnezyum tozlar
ekil 7(b)de grld gibi gevrek olarak krlmtr. Bu etki ekil 7(a)da da aka grlmekte, ak renkli olan
magnezyum toz blgelerinde keskin, dzgn yzeyli basma ynne 45olik gevrek krlma saptanmtr. Daha nce
de belirtildii gibi magnezyumun oda scaklnda kayma sistem says az olmakla birlikte, oda scaklnda plastik
deformasyon sadece bazal yzeylerde olmaktadr.
(a)
(b)
ekil 7. Ti-80Mg kompozit numunesinde basma testi sonras krlma yzeyleri, a) basma eksenine 45ode oluan
krlma, b) Magnezyum ve titanyum toz blgelerinde oluan krlma yzeyleri
Bilindii gibi biyomedikal uygulamalarda, zellikle hareketli blgelerde bulunan kemik ve protezler arlkl olarak
basma yklerine maruz kalmaktadrlar. Bu tr uygulamalarda kemik ve protez malzemesinin mekanik zelliklerinin
birbirine benzerlik gstermesi uzun bir protez mrn garanti etmektedir ve mekanik zelliklerin farkllndan dolay
kemik dokusunun anmas ile vcutta meydana gelebilecek hasarlar azaltmas bakmndan nemlidir. zellikle kemik ve protez malzemesinin elastik modllerinin benzerlik gstermesi gerekmekte ve bundan dolay da bu konuda
yaplan almalarda implant malzemesinin elastik modlnn kemie benzerlik gstermesi zerine younlamtr.
Vcut kemikleri genel olarak sngerimsi ve kortikal kemikler olarak iki ana grupta toplanmaktadr ve kemiklerin
elastik modl 3-20 GPa arasnda, basma ykleri altnda akma dayanc ise 130-180 MPa arasnda deimektedir
[3]. Tablo 1de grld gibi retilen hem saf magnezyum numunelerinin, hem de Ti-Mg kompozit numunelerin
tmnn elastik modlleri vcut kemii elastik modl snrlar iinde kalmakta ve akma dayanlar da ayn ekilde
vcut kemiine benzerlik gstermektedir. Grld gibi Ti-Mg kompozitlerde elastik modl, dayan ve akma
dayanc magnezyum miktarnn art, dier bir deile titanyum miktarndaki azalma ile d gstermekte, te
yandan kompozitlerde krlma noktasndaki uzama ise magnezyum miktarnn art ile artmakta ve saf magnezyum
numunesinin uzama deerine (% 19.4 0.5) yaklamaktadr. retilen numunelerin mekanik zelliklerindeki ilgin
168

olan nokta ise saf magnezyum ve Ti-Mg kompozit numunelerinin elastik modl deerleri arasnadaki farkllktr.
Grld gibi saf magnezyumun elastik modl 20 GPa civarndadr. Magnezyuma titanyum eklendiinde elastik
modl deerinde bir art beklenmesine ramen iinde hacimce % 50 titanyum ieren numunede bile elastik modl
(12 GPa) saf magnezyumun altndadr. retilen kompozit numunelerde bilinen kompozitlerin aksine glendirici
fazn (titanyum) yapda rastgele deil de magnezyum tozlarnn etrafnda dalmasna bal olarak deiik bir mekanik davrann ortaya kt dnlmtr. Bu konuda yaplan almalar devam etmektedir. Dier bir nokta ise
retilen saf magnezyum numunelerinin olduka dk mekanik zelliklere sahip olmasdr. lenmi magnezyumlarda basma akma dayanc 130-180 MPa arasnda deimektedir [3]. Fakat bu almada ise retilen magnezyum
nunumelerinin akma dayancnn 38 MPa civarnda deitii gzlenmitir. Genel olarak kumda dklen magnezyum
numunelerinin akma dayancnn 20 MPa civarnda deitii ve bu deerin ekstrzyon ve scak haddeleme gibi ilemlerle arttrld bilinmektedir. Bu almada retilen saf magnezyum numunelerinin akma dayanc dkm yapsna sahip magnezyum numunelerine benzerlik gstermesine karn, krlma noktasndaki uzama miktar bakmndan
ise farkllk gstermektedir. Dkm yaplarnda % 2-6 arasnda deien uzama miktar bu almada retilen magnezyum numunelerinde yaklak % 20ye kadar ulamtr. Numunelerin 450oCde deformasyon sonras 600oC gibi
ok yksek scaklkta uygulanan tavlama ilemi taneleri bytm ve ayn zamanda malzemedeki retim kaynakl
gerilimleri de yok etmitir.
Numune
Saf Magnezyum
Ti-50%Mg
Ti-60%Mg
Ti-70%Mg
Ti-80%Mg
Tablo 1. alma kapsamnda retilen numunelerin mekanik zellikleri

Elastik Modl, E
Akma Dayanc,
Dayan, UTS
Krlma noktasndaki
(GPa)
0.2 (MPa)
(MPa)
uzama, (%)
20.8 1.4
38.2 3.3
260.0 4.1
19.4 0.5
12.0 1.1
245.0 9.6
411.7 9.4
12.9 0.3
12.5 0.6
194.0 5.3
390.0 11.6
15.1 1.0
9.6 0.5
147.3 4.9
337.8 7.4
15.4 0.6
6.0 0.7
123.0 6.4
329.5 7.6
18.0 1.0
4. SONULAR
Bu almada gzeneksiz, biyomedikal uygulamalara aday saf magnezyum ve iinde hacimce % 50-80 arasnda
deien oranlarda magnezyum ieren Ti-Mg kompozitleri scak deformasyon yntemiyle retilmitir. retim esnasnda uygulanan tavlama ilemi sonras Ti-Mg kompozitlerdeki magnezyum tozlarndaki grlen iri tanelerin dallantl yapdan direk olarak byd saptanmtr. Dier yandan 600oCde uygulanan tavlama ileminin ise titanyum
tozlarnn sinterlenmesi iin yeterli olmad ve tozlarn yapda birbirine sadece mekanik olarak ok iyi derecede
kilitlendii grlmtr. Ayrca retim sonras yaplan incelemelerde magnezyum tozlarnn arasndaki oksit tabakalarnn yzeye yaklatka kalnlat, numunelerin i blgelerinde ise sadece balang tozuna bal bir oksit
tabakasnn olduu grlmtr. Yaplan basma testlerinde ise btn numunelerin gerinim-gerinim erilerinin elastik
blge, gerinim sertlemesi ve krlma blgesi olmak zere 3 ana blgeden olutuu saptanm ve malzemelerin
snekliinin olduka yksek olduu saptanmtr. Maksimum yk sonras kompozit numunelerde krlma basma ynne 45ode meydana gelmitir. Krlma titanyum toz blgelerinde, titanyum ve magnezyum toz arayzeyinde ve de
magnezyum tozunun kendisinde meydan gelmitir. Magnezyumun oda scaklnda snrl sayda kayma sistemine
sahip olmas magnezyumun gevrek ekilde krlmasna neden olmutur. Bunun yannda retilen saf magnezyum
nunumelerinde sneklik olduka yksek olmasna ramen elastik modl ve akma dayancnn dkm yapsna
sahip magnezyuma benzerlik gsterdii grlm, bunun nedeni de uygulanan tavlama ileminin scaklnn ok
yksek olmasna balanmtr. retilen kompozitlerde elastik modl 6-12 GPa, akma dayanc da 123-245 MPa
arasnda deimektedir. Vcut kemiinin elastik modl (3-20 GPa) ve akma dayancna (130-180 MPa) benzerlik
gsteren Ti-Mg kompozitleri mekanik zellikler bakmndan biyomedikal uygulamalara olduka uygun olduu grlmtr.
KAYNAKLAR
1. M. Geetha, A.K. Singh, R. Asokamani, A.K. Gogia, Ti based biomaterials, the ultimate choice for orthopedic
implants- A review, Progress in Materials Science, 54, pp. 397- 425, 2009.
2. F. Barrre, T.A. Mahmood, K. De Groot, C.A. van Blitterswijk, Advanced biomaterials for skeletal tissue regeneration: Instructive and smart functions, Materials Science and Engineering R 59, pp. 38-71, 2008.
3. M. P. Staiger, Alexis M. Pietak, J. Huadmai, G. Dias, Magnesium and Alloys as orthopedic biomaterials: A review, Biomaterials, 27, pp. 1728-1734, 2006.
4. M. Bram, C. Stiller, H. P. Bunckremer, D. Stover, H. Baur, Titanium foams produced by solid state replication of
NaCl powders, Adv. Eng. Mater., 2, pp. 196-199, 2000.
5. C. E. Wen, M. Mabuchi, Y. Yamada, K. Shimojima, Y. Chino and T. Asahina, Processing of biocompatible porous
Ti and Mg, Scripta Mater., 45, pp. 1147-1153, 2001.
6. C. E. Wen, Y. Yamada, K. Shimojima, Y. Chino, H. Hosokawa, and M. Mabuchi, Novel titanium foam for bone
tissue engineering, J. Mater. Res., 17(10), pp. 2633-2639, 2002.
7. Nayeb-Hashemi and J.B. Clark, Phase diagrams of magnesium alloys, ASM international, pp 324, 1988.
169

Semente Bakr Matrisli- SiC Kompozitlerinin Toz Metalurjisi

Yntemi ile retimi
G. Celebi Efe, . Altnsoy, T. Yener, M. Ipek, S. Zeytin, C. Bindal
Sakarya niversitesi, Mhendislik Fakltesi, Metalurji ve Malzeme Mhendislii Blm, Esentepe Kamps,
54187 Sakarya- Trkiye, E-mail:gcelebi@sakarya.edu.tr
zet
Bu almada elektriksel uygulamalar iin 5 ve 30m boyutunda ve arlka % 0, 1, 2, 3 ve 5 miktarda SiC ieren
semente Cu matrisli SiC takviyeli kompozitlerin retimi amalanmtr. Semente bakr ve SiC tozlar mekanik olarak
kartrlm ve 280 MPa basnta tek ynde preslenmitir. Preslenen kompaktlar 700Cde 2 saat ak atmosferli
frnda sinterlenmitir. Kompozitteki Cu ve SiC bileenlerin varl XRD analiz teknii ile tespit edilmitir. Kompozitlerin nispi younluk ve elektrik iletkenlikleri, arlka artan SiC yzdesiyle azalrken artan SiC parack boyutuyla
artmtr. Sonular, 30m parack boyutlu SiC ile takviye edilen Cu-SiC kompozitlerinin 5m parack boyutlu SiC
ile takviye edilen Cu-SiC kompozitlerinden daha iyi zellikler sergilediini gstermitir. Maksimum nispi younluk
(97%) ve elektrik iletkenlik deeri (%83.0 IACS: International Annealed Copper Standard) 30m luk SiC ile takviye
edilen Cu-a.%1SiC kompoziti iin elde edilmitir.
Anahtar Kelimeler: Cu-SiC, Sementasyon, Kompozit, Sertlik, Nispi Younluk, Elektrik letkenlii
The ProductIon of Cemented Cu MatrIx-SIC ComposItes

By Powder Metallurgy Method
G. Celebi Efe, . Altnsoy, T. Yener, M. Ipek, S. Zeytin, C. Bindal
Sakarya University, Engineering Faculty, Department of Metallurgy and Materials Engineering, Esentepe Campus,
54187 Sakarya-Turkey, E-mail:gcelebi@sakarya.edu.tr
Abstract
The present paper is aimed at the production of cemented Cu matrix-SiC composites with SiC having 5 and 30m
particle size and at ratios of 0, 1, 2, 3 and 5% by weight for electrical applications. Cemented copper and SiC
powders were mixed mechanically and pressed with an axial pressure of 280MPa. Pressed compacts were sintered
at 700C in an open atmospheric furnace for 2 hours. The presence of Cu and SiC components in composites were
verified by XRD analysis technique. While relative density and electrical conductivity of composites were decreasing with increasing the weight percentage of SiC, increased with increasing particle size of SiC particles. Hardness
of the composites increased with both weight percentage and the particle size of SiC particles. The results indicate
that Cu-SiC composite with 30m particle sized SiC has superior properties than the Cu-SiC composite with 5m
particle sized SiC. The maximum relative density of 97% and electrical conductivity of 83.0%IACS (International
Annealed Copper Standard) were obtained for Cu-1wt.%SiC with SiC particle size of 30m.
Keywords: Cu-SiC, Cementation, Composite, Hardness, Relative density, Electrical conductivity.
1. GR
Bakr, tm metaller arasnda gmten (6,21x107/.m) sonra elektrik iletkenlii en yksek metal (5,88x107/.m )
olup elektrik iletkenliinin ana talep olduu uygulama alanlarnda yaygn olarak kullanlmaktadr. Gm, yksek
170

fiyat ve tedarikindeki glkler nedeni ile bu tr uygulama alanlarnda az kullanlmaktadr. Bakra bir rakip yine
elektrik iletkenlii yksek olan alminyumdur, ancak onun hem iletkenlii (3,65x107/.m) hem de mukavemeti bakrnki kadar yksek deildir. Bakrn dier btn metaller ierisinde gmten sonra elektrii en iyi ileten metal
olmas, elektrik iletkenliinin ana talep olduu uygulama alanlarnda yaygn olarak kullanmn salamaktadr [1,
2]. Bakrn yksek elektriksel iletkenlii (5,88x107/.m ), yksek sl iletkenlii (400 W/m.K), korozyon direnci, dekoratif rengi, orta derecedeki mukavemet ve kolay ekillendirilebilirlii onu tarih boyunca nemli klmtr ve [1, 3]
eitli mhendislik uygulamalarnda en ok kullanlan yapsal ve ilevsel metallerden biri yapmtr [4- 6]. letkenler,
elektrotlar, ama kapama kontaklar gibi elektrik iletkenliinin birinci derecede nemli olduu uygulama alanlarnda
kullanlacak olan bakrlarda u temel zellikler aranr: Yksek elektrik iletkenlii, yksek oda scakl mukavemeti,
mukavemetini yksek scaklklarda koruyabilme zellii (yksek scaklk mukavemeti). Saf bakr, ilk zellik asndan neredeyse rakipsiz bir malzemedir. Bu noktada oksijensiz yksek iletken bakr ok uygundur. Ancak, saf bakrn
snrl bir mukavemeti vardr [3, 6- 8]. Bakrn dk mukavemeti ve zellikle yksek scaklklarda yumuamas
yaygn kullanm alann kstlamaktadr [5, 9].
Bakr elektrik iletkenliinde nemli bir kayp olmakszn, sadece souk deformasyon ile sertletirilebilir. Bu ekilde
mukavemetlendirilse bile, saf bakr 100oCye yaklaan scaklklarda, hzl bir ekilde yeniden kristalleir, sertlik ve
mukavemetini kaybeder. Bakrn mukavemetini artrmann bir dier yolu alamlamadr. Alamlama sonucunda, bakr alamnn mukavemeti ya kat eriyik sertletirmesi veya kelti sertletirmesi ile artrlabilir. Ancak, elektrik iletkenliindeki kaybn yksek olmamas iin alam elementi ilavesinin snrl tutulmas gerekir. nk alam elementi
ilavesi ile, mukavemetin artmasna karlk elektrik iletkenlii azalr. Bu bakmdan, iletken olarak kullanlacak bakr
alamlarnda az miktarda alam elementi bulunur (genellikle a. %2 mertebesinde). Bilindii gibi, yalandrlm
alamlar yalandrma scaklnn zerinde kullanlmamaldr, aksi halde hzla yumuarlar. Dolaysyla, az alaml
bakrlarn mukavemet performanslar ykselen scaklklarda deimektedir [10].
Bakrn yksek scaklklarda azalan zelliklerini kazanmann bir yoluda, bakr matris ierisinde seramik paracklarinin dispersiyonu ile kompozit oluturmaktr. Bu amala bakr matrise ilave edilen seramiklere rnek olarak Al2O3,
SiC, TiC, WC, B4C ve TiB2 saylabilir [5]. Bunlardan, SiC yksek elastik modl ve aluminadan ok daha yksek sl
iletkenlii ile dikkat ekmektedir. Cu- SiC kompozitleri, bakrn iyi sneklii ve tokluu ile SiC paracklar takviyelerinin yksek mukavemeti ve elastik modllerinin her ikisini birletirir [11]. Bu kompozitler diren kaynak elektrotlar,
klavuz ereveleri, elektrik klemensleri, rleler, iletkenler, kondaktrler, elektrik anahtarlar, akm devresi kesicileri,
elektronik paketleme uygulamalarnda elektrik temas malzemeleri olarak kullanlabilirler [11- 13].
Bu almada sementasyon yntemiyle retilen bakr tozunun farkl parack boyut ve bileimdeki seramik karakterli SiC tozu ile takviye edilerek yksek iletken Cu-SiC kompozit retimi hedeflenmitir. Sonular mekanik, mikroskobik ve elektriksel olarak karakterize edilmitir.
almalarda balang malzemeleri olarak semente bakr (%99.5 safiyette, 0.1-0.5 m) ve SiC (% 99.5 safiyette,
5 ve 30 m, Struers) tozlar kullanlmtr. Balang tozlar bilyeli deirmende 2 saat sre ile kartrlarak, semente
Cu-SiC (5 m) ve semente Cu-SiC (30 m) eklinde, srasyla a. % 1, 2, 3 ve 5 SiC takviyeli toz karmlar hazrlanm ve sz konusu karmlar tek eksenli kalp ierisinde pres yardmyla 280 MPa basnla kompaklanmtr.
Kompaktlanan numuneler grafite gml halde ak atmosferli elektrikli frnda, 700oCde 2 saat sinterlenmitir. Sinterlenen numunelerin nispi younluklar Arimed Prensibi ne gre hesaplanm, sertlik ve elektriksel iletkenlikleri
srasyla Vickers indentasyon teknii ve DC elektrik iletkenlik lm cihaz kullanlarak llmtr. Numunelerin
mikroyaplar SEM mikroskobu ile incelenmi ve kompozitlerin ierisindeki fazlar XRD analizi ile belirlenmi, SEM
incelemelerindeki baz bulgular ve XRD analizi SEM-EDS yardmyla teyit edilmitir.
Sinterlenmi semente Cu-SiC (5 ve 30 m) kompozit numunelerine ait SEM mikroyaplar ekil 1ve 2de gsterilmitir. Mikroyaplar incelendiinde, gri, geni alanlarn Cu, siyah ve keli paracklarn ise SiC olduu grlmektedir. Takviye miktar artka SiC paracklerinin matriks ierisindeki miktar artmakta ve paracklar aras mesafe
ksalmaktadr. Her iki SiC parack boyutuna sahip numunelerde de, takviye faz matriks ierisinde Cu taneleri
etrafnda homojen olarak dalmaktadr (ekil 1-2). Sz konusu homojen dalm daha kk (5 m) SiC patiklleriyle takviye edilmi numunelerde daha belirgin gzkmektedir. SiC parack boyutu arttka SiC dalm daha
uzun mesafeli hale gelmektedir (ekil 2). Mikroyaplarda grlen kk beyaz kresel paracklar ise parlatma
malzemesi olan Al2O3 n matriks yzeyine gmlmesinden kaynaklanmaktadr.
171

ekil 1. Sinterlenmi semente Cu-SiC (5 m) kompozit numunelerine ait SEM mikroyaplar.
ekil 2. Sinterlenmi semente Cu-SiC (30 m) kompozit numunelerine ait SEM mikroyaplar.
Kompozit numuneler ierisinde balang bileenleri dnda, proses srelerine bal olarak hangi fazlarn bulunduu XRD analizleriyle incelenmi ve analiz sonular grafiksel olarak ekil 3 ve 4 te verilmitir. (XRD patternlerinde
C1Ss eklindeki ksaltmalarda C: bakr, rakam: takviye miktarn ve S: SiC, s: semente matriks tozu kullanldn
sembolize etmektedir.) XRD analizlerinde SiC ve Cu dnda bir faza rastlanlmamtr (ekil 3-4). SiC piklerinin
SiC miktarndaki arta bal olarak belirginlememesi ise takviye miktarlarnn XRD cihaznn deteksiyon limitlerine
yakn olmasndan kaynaklanabilmektedir.
ekil 3. 700 Cde sinterlenen 5m tane boyutunda SiC ieren Cu (semente)-SiC kompozitlerinin XRD paternleri.
172

ekil 4. 700 Cde sinterlenen 30m tane boyutunda SiC ieren Cu (semente)-SiC kompozitlerinin
XRD paternleri.
XRD ile tespit edilen hakim fazlar ve yapdaki bilenler SEM- EDS nokta analizleri desteklenmitir. 700Cde sinterlenmi 5 ve 30mluk SiC ile takviye edilmi Cu-SiC kompozitlerine ait SEM-EDS analizleri ekil 5, 6 da verilmitir.
Analizlerde koyu gri ve keskin keli fazlar SiC ak gri alanlar Cu matriksi, serbest beyaz alanlar muhtemelen
parlatmadan kaynaklanan alminay gstermektedir. ekil 6 da matriste serbest gri renkte adacklarn bulunduu
grlmtr. Bu blgelerden biri olan 3 noktasndan alnan SEM-EDS analizlerinde Fe ve O2 tespit edilmitir. Fe
sementasyon prosesinden kaynaklanmaktadr ve muhtemelen sinterleme scaklnda oksitlenmitir.
ekil 5. 700Cde sinterlenmi 5 mluk SiC ile takviye edilmi C5Ss numunesinin EDS analizi.
ekil 6. 700Cde sinterlenmi 30 mluk SiC ile takviye edilmi C2Ss numunesinin EDS analizi.
173

700Cde sinterlenmi numunelerin Archimedes prensibi ile llen nispi younluklarnn SiC ieriine ve boyutuna bal olarak deiimi ekil 7 de stun grafii olarak verilmitir. Semente bakr tozuna SiC takviyesi ile nispi
younluklar azalmaktadr. SiC parack takviyeli numunelerde younluk, SiC parack boyutu art ile artmaktadr.
Kompozit numunelerde dk SiC hacim oranlarnda Cu-SiC arayzeyi daha azdr ve bakr atomlar iin daha az
difzyon bariyeri sz konusudur. Bakr atomlarnn kolaylkla difze olmas ve SiC paracklar arasndaki boluklar
doldurabilmesi kompozitte younluk artna neden olur [14]. SiC parack boyutu arttka yzey alan ve Cu-SiC
arayzeyleri azalmakta, buna bal olarak ta daha youn bir yap ortaya kmaktadr. Kompozitlerin nispi younluklar SiC parack boyutunun artyla art sergilemitir ve en iyi younluk deerleri 30 mluk SiC parack takviyeleri ile elde edilmitir. SiCn artan parack boyutu ile birlikte, daha fazla bakr-bakr taneleri birbirleri ile temas
etmekte ve sinterleme sonrasnda daha youn bir yap ortaya kmaktadr.
ekil 7. 700C de Sinterlenmi kompozitlerin % nispi younluklarnn SiC ieriine ve boyutuna bal olarak
deiimi.
Kompozit numunelerde sertlik lm Cu ve SiC tanelerini homojen olarak kapsayacak ekilde iz oluturulmasna dikkat edilerek yaplmtr. Cu ve 5mluk SiC takviyeli Cu-SiC kompozitlerinin sertlik lmlerinde 50gr yk,
30mluk SiC takviyeli Cu-SiC kompozitlerinin sertlik lmlerinde ise, sertlik izinin Cu ve SiCn her ikisinide kapsamas iin 100gr yk kullanlmtr. Kompozitlerin sertliinin SiC ieriine ve parack boyutuna bal olarak deiimi ekil 8de stun grafiinde verilmitir.
ekil 8. 700C de Sinterlenmi kompozitlerin sertliklerinin SiC ieriine ve boyutuna bal olarak deiimi.
SiC ierii arttka kompozitlerin sertlik deerleri artmtr. Snek bakr matrisin sertlii sert disperse faz ilavesiyle
artmaktadr [15, 16]. Kompozit numunelerin mikrosertlik deerlerinin SiC parack boyutunun artmasyla daha da
artmasnn nedeni, indenterin sert takviye bileenine temas alannn artmas olabilir.
Cu ve Cu-SiC kompozitlerinin elektrik iletkenliklerinin SiC boyut ve ieine gre deiimi ekil 9 da verilmitir. Nispi
younluk sonularna benzer ekilde kompozititn elektrik iletkenlii artan SiC miktar ile artmaktadr. Matris ierisinde dalan SiC paracklar elektron hareketine engel olarak elektrik iletkenliini drmektedir. SiC tane boyutu
arttka birim alana den SiC parack says azaldndan elektrik iletkenlii artmtr.
174

ekil 9. 700C de Sinterlenmi kompozitlerin sertliklerinin SiC ieriine ve boyutuna bal olarak deiimi.
4. SONULAR
Gerekletirilen amada aadaki sonular elde edilmitir:
1. Cu-SiC kompozitleri, sementasyon yntemiyle retilen bakr tozuna farkl ierik ve boyutta SiC paracklar
takviye edilerek, Toz Metalurjisi yntemiyle baaryla retilmitir.
2. Kompozillerdeki hakim fazlar Cu ve SiC, XRD ve SEM- EDS nokta analizleri ile tespit edilmi ve yapda herhangi bir oksit pikine rastlanlmamtr.
3. Takviye bileeni olan SiC paracklar matriks ierisinde homojen olarak dalmtr.
4. 700C de 2 saat sinterlenmi kompozilerin nispi younluklar ve elektrik iletkenlikleri, artan SiC miktar ile
birlikte azalrken, artan SiC parack boyutuyla art gstermitir.
5. Kompozitlerin mikrosertlikleri artan SiC miktar ve parack boyutu ile artmtr.
TEEKKR
Yazarlar Sakarya niversitesi, Mhendislik Fakltesi, Metalurji ve Malzeme Mhendislii Blm teknikeri Ersan
DEMIRe, SEM, XRD incelemelerini gerekletiren uzman Fuat KAYIa, Federal Elektrik A..ye, TBTAKa teekkkr ederler.
KAYNAKLAR
1. www.bpc.edu/mathscience/chemistry/electrical_conductivity.html
2. http://en.wikipedia.org /wiki/Copper
3. www.cda.org.uk
4. Zhu, J., Liu, L., Zhao, H., Shen, B., Hu, W., Microstructure And Performance of Electroformed Cu/Nano-Sic Composite, Materials & Design, Vol. 28, pp. 1958-1962, 2007.
5. Xu, Q., Zhang, X., Han, J., He, X., Kvanin, V.L., Combustion Synthesis and Densification of Titanium Diboride-Copper
Matrix Composite, Materials Letters, Vol. 57, pp. 4439-4444, 2003.
6. Dobrzanski, L.A., Significance of Materials Science for The Future Development of Societies, Journal of Materials
Processing Technology, Vol. 175, pp.133-148, 2006.
7. Zhan, Y., Zhang, G., The Effect of Interfacial Modifying on The Mechanical and Wear Properties of Sicp/Cu Composites, Materials Letters, Vol. 57, pp.4583-4591, 2003.
8. http://www.matweb.com/reference/copper-alloys.aspx
9. Ahmed, R. N., Ramesh, C.S., Tribological Properties of Cast Copper-Sic-Graphite Hybrid Composites, International
Symposium of Research on Materials Science and Engineering, Chennai India, December 20-22, 2004.
10. Salam, ., Cu-Cr-Zr Alamnda Yalandrma Isl leminin, Elektrik letkenlii ve Anma Davranlar zerine Etkisinin ncelenmesi, Bilim Uzmanl Tezi, Karabk niversitesi, Fen Bilimleri Enstits, Makine Eitimi Anabilim
Dal, Ocak, 2008.
11. Zhang, R., Gao, L., Guo, J., Effect Of Cu2O on The Fabrication of Sicp/Cu Nanocomposites Using Coated Particles
and Conventional Sintering, Composites, Vol. 35, pp. 1301-1305, 2004.
12. Motta, M.S., Jena, P.K., Brocch, E.A., Solorzano, I.G., Characterization of Cu-Al2O3 Nano-Scale Composites Synthesized By In Situ Reduction, Materials Science and Engineering C, Vol. 15, pp. 175-177, 2001.
13. Zhang, R., Gao, L., Guo, J., Temperature-Sensitivity of Coating Copper on Sub-Micron Silicon Carbide Particles by
Electroless Deposition in A Rotation Flask, Surface and Coatings Technology, Vol. 166, pp. 67-71, 2003.
14. Efe, C.G., Altinsoy, I., Ipek, M., Zeytin, S., Bindal, C., Some Properties of Cu-Sic Composites Produced by Powder
Metallurgy Method, Kovove Metallic, Vol. 49, No.2, pp. 131- 136, 2011.
15. Efe, C.G., Altnsoy, ., Ipek, M., Zeytin, S., Bindal, C., Investigation of Some Properties of Sic Particle Reinforced
Copper Composites, 5. Uluslararas Toz Metalurjisi Konferans, Ankara, 8-12 Ekim 2008.
16. Celebi Efe, G., Altinsoy, I., Yener, T., Ipek, M., Zeytin, S., Bindal, C., Characterization of Cemented Cu-SiC Composites, Vacuum, Vol. 85, pp. 643-647, 2010.
175

FERROUS POWDER
METALURGY
www.turkishpm.org
176

THE MICROSTRUCTURE AND PROPERTIES OF LOW CARBON

PM Mn STEELS SINTERED UNDER DIFFERENT CONDITIONS
Maciej SULOWSKI*, Andrzej CIAS*, Tadeusz PIECZONKA*
*AGH University of Science and Technology, Faculty of Metals Engineering and
Industrial Computer Science, Physical and Powder Metallurgy Research Unit,
PL 30-059 Krakw, Poland, Al. Mickiewicza 30, sulek@agh.edu.pl
ABSTRACT
The paper presents the effect of sintering conditions on the microstructure and properties of low-carbon Mn-Cr-Mo
PM steels. It was proved there is no effect of tempering temperature on the mechanical properties of Astaloy CrLbase steels, sintered at 1250C in 5H2-95N2 mixture as compared with the properties of those sintered at 1120C.
The properties of Astaloy CrM-base steels, sintered at 1250C in air were comparable or higher on the contrary to
Astaloy CrL-base steels. The addition of lump ferromanganese was not sufficient for metal oxides reduction. The
structure investigation confirmed the Mn-Cr-Mo PM steels have predominantly bainitic microstructure.
Keywords: Structural PM Materials, PM Mn Steels, Sintering Process, Sintering Atmosphere, Microstructure, Mechanical Properties.
1. INTRODUCTION
Manganese and chromium are two important elements in steels, which show effective strengthening. The issue of
sintering low alloy steels containing these metals having high affinity for oxygen is one of the most important topics
in powder metallurgy (PM), as testified by the number papers on this subject that have taken place over the last
few years [1-6]. The question of the role of micro-atmosphere in the development of microstructure is fundamental
to our understanding of sintering process, especially the relationship of microstructure evolution to mechanical
properties evolution. The thermodynamics bonds concerning carbon equilibrium during sintering were discussed
and possible interactions between steel and various controlled atmosphere were examined [7-10]. Therefore it is
anticipated that this topic would generate a great deal of interest among powder metallurgy specialists.
The PM industry needs economical ways of producing components with higher densities in order to effect the
stepwise improvement in dynamic mechanical properties necessary to compete with highly loaded wrought and
machined components. This paper aims to determine the processing conditions necessary for standard and high
temperature sintering in nitrogen rich, non-flammable atmospheres of PM ferrous structural parts, which contain
the easily oxidisable chromium and manganese in addition to carbon and molybdenum. These components are to
possess high fatigue strength, good dimensional accuracy, be fully recyclable and of lower cost than equivalent
wrought and machined parts. Recyclability is achieved by substitution of the normal (for PM) alloying elements of
copper and phosphorus by chromium and manganese. Recyclable components are of paramount importance to
automotive manufacturers due to increasingly stringent legislation that now sees the manufacturers responsible for
the whole life cycle of vehicles, i.e. birth to grave. Another element often used in PM is the expensive and potentially
carcinogenic nickel. Its exclusion as an alloying element can only make for a safer workplace. Also the issue has a
high profile in public awareness because of a series of magazine articles.
To research a potentially economical route for production of components made of Fe- Mn-Cr-Mo-C structural steels,
ways of maximising mechanical properties were investigated. The slow cooling of large masses in semi-closed containers in the sintering furnace favours bainite formation. Correct sinter-hardening of these steels should lead to a
tough, potentially bainitic, core with a hard wear resistant surface. The new processing conditions aim to make use
of carbothermic reduction of metal oxides by promotion of a local micro-climate or micro-atmosphere around the
sintered components, with
177

low oxygen potential and high CO/CO ratio. It is well known, from iron and steel-making processes, that at tem2
peratures >900C carbon monoxide is a more efficient reducing gas than pure dry hydrogen. Also CO is efficiently
2
reduced to CO by solid carbon by means of the Boudouard reaction at temperatures >927C. It was proposed to
model theoretically the metal-metal oxide-carbon reactions to predict the generation of CO and CO versus tem2
perature and the projected efficiency for gaseous-metal oxide reduction. These analyses were used to corroborate
the theoretical modelling and also to help with design improvements of semi-closed container systems.
The use of semi-closed containers is envisaged in order to produce and maintain an efficient reducing atmosphere
around the components being sintered. Various semi- closed container designs have been used previously in [1116] during authors work on the understanding and development of sintering parameters for manganese and chromium containing PM alloys. The relatively small volume of reducing gas (CO/CO ) in these containers ensures that
2
the process is more eco-friendly than when either flowing endogas (unacceptable due to its wetness) or cracked
ammonia (or other nitrogen-hydrogen, minimum 10%, mixture) plus methane addition is employed, as currently in
industry. The use of carbon and/or manganese vapour producing getter systems will be investigated for the purposes of increased CO/CO2 generation and drying of the micro-climate, thus ensuring low oxygen potential and
best possible reducing conditions. Avoidance of formation of deleterious manganese and chromium oxides and
chromium nitrides has already been demonstrated.
The pre-alloyed Hgans Astaloy CrL and Astaloy CrM powders were used as the base materials. 3% of manganese,
in the form of low-carbon (1.3% C) ferromanganese (77% Mn), and 0.15% ultra fine graphite powder were added to
the base powders in order to prepare two mixtures Fe-3%Mn-1.5%Cr-0.2%Mo-0.15%C and Fe-3%Mn-3%Cr0.5%Mo-0.15%C, based on Astaloy CrL and Astaloy CrM, respectively (Fig. 1).
Figure 1. Micrographs of base powders: a) pre-alloyed Astaloy CrL powder, b) pre-alloyed Astaloy CrM powder, c)
ferromanganese Elkem powder, d) graphite powder grade C-UF.
The powders were mixed in a Turbula mixer for 30 min, and compacted in steel dies with zinc stearate lubricated
walls. Two types of compacts were prepared: 55x10x5 mm TRS specimens and ISO 2740 dog-bone tensile test
bars. The green and as-sintered densities of compacts, d0 and d1, respectively, are summarised in Table 1. Before
sintering process, green compacts of each mixture were numbered from 1 to 40. The scheme of sintering is presented in Table 2. Isothermal sintering was carried out:
in dry (10 ppm moisture) 5% H2-95% N2 (the flow rate of atmosphere was approximately 1 ml/min) atmosphere
in the laboratory horizontal tube furnace,
in presence of Mn vapours (a lump of the ferromanganese was placed in the boat), at 1120C and 1250C for 60
minutes, employing convective (65Cmin-1) cooling. To improve the local dew point of microatmosphere and to minimise the loss of manganese due to volatilisation, sintering was carried out in a semi-closed stainless steel container.
178

The mass of lump of FeMn was 52 g and it was added per 489,5 g of compacts, both rectangular and ISO 2740. The
total number of compacts during single sintering process was 20 - 10 rectangular and ISO 2740. Samples based both
on Astaloy CrL and Astaloy CrM pre-alloyed powders, numbered 6-10, 16-20, 26-30 and 36-40 were subsequently
tempered at 200C for 60 minutes in air.
Table 1. Green densities, d0, and as-sintered densities, d1, of Fe-Mn-Cr-Mo-C PM steels - mean values for 40
(green compacts) and 20 (as-sintered materials) measurements.
Table 2. The scheme of sintering compacts.
3. RESULTS
The mechanical properties of investigated PM steels are summarised in Table 3 and in Figures 2-9. LECO instruments were employed to check the chemical composition of Fe-Mn-Cr-Mo-C PM steels. After mechanical tests, the
structure of sintered Mn-Cr-Mo steels was examined using light optical microscopy (LOM) technique.
Table 3. Mechanical properties of Fe-3Mn-Cr-Mo-C steels based on Astaloy CrL
prealloyed powder- mean values and standard deviation.
179

Figure 2. Representative tensile curves for Astaloy CrL-based 3%Mn + 0.15%C PM steels sintered at 1120C in 5%
H2 / 95% N2 mixture; not tempered (right) and after tempering (left).
Figure 3. Representative tensile curves for Astaloy CrL-based 3%Mn + 0.15%C PM steels sintered at 1120C in air
+ 52g FeMn (added in the form of a lump); not tempered (right) and after tempering (left).
Figure 4. Representative tensile curves for Astaloy CrL-based 3%Mn + 0.15%C PM steels sintered at 1250C in 5%
H2 / 95% N2 mixture; not tempered (right) and after tempering (left).
Figure 5. Representative tensile curves for Astaloy CrL-based 3%Mn + 0.15%C PM steels sintered at 1250C in air
180

Figure 6. Representative tensile curves for Astaloy CrM-based 3%Mn + 0.15%C PM steels sintered at 1120C in
5% H2 / 95% N2 mixture; not tempered (right) and after tempering (left).
Figure 7. Representative tensile curves for Astaloy CrM-based 3%Mn + 0.15%C PM steels sintered at 1120C in air
Figure 8. Representative tensile curves for Astaloy CrM-based 3%Mn + 0.15%C PM steels sintered at 1250C in
5% H2 / 95% N2 mixture; not tempered (right) and after tempering (left).
Figure 9. Representative tensile curves for Astaloy CrM-based 3%Mn + 0.15%C PM steels sintered at 1250C in air
181

Following the results of chemical analysis presented in Table 4, higher sintering temperature contributes the
decarburization effect in investigated steels. This effect is connected with carbothermic reaction between C and
O2 which can be possible during the whole heating and sintering steps. This phenomenon was widely reported
by Cias et al [11]. Also the lower oxygen content in PM steel after sintering at 1250C suggests the carbon oxygen reactions. It has to be also pointed out that sintering in air with additions of FeMn, irrespective to sintering
temperature, contributes to decreasing decarburization effect due to the shortage of hydrogen. Higher nitrogen
level in investigated steels can be explained by nitrogen-rich atmosphere; also porosity which is seen in Figs. 10-11
play important role in nitriding Mn-Cr-Mo PM steels.
Table 4. Chemical composition of investigated not tempered 3Mn-Cr-Mo-0.15C PM
Figure 10. The microstructure of Astaloy CrL-based not tempered steel sintered at 1120C
(left) and 1250C (right).
Figure 11. The microstructure of Astaloy CrM-based not tempered steel sintered at 1120C
(left) and 1250C (right).
The heterogeneous microstructure of investigated PM steels observed in bright field (Figs. 10 and 11) mainly
consists of martensite or martensite+bainite (lower and upper); also a lot of upper bainitic islands, homogeneous
arranged, were observed.
4. DISCUSSION
The strength properties of PM Mn-Cr-Mo-C steels obtained during investigations indicate that these steels can be
classified as medium-to-high strength wrought steels. As was shown in Tables 1, compacts based on Astaloy CrL
pre-alloyed powder are characterised by a little bit higher densities than those based on Astaloy CrM powder. It can
be connected with better compressibility of powder mixture containing less chromium and molybdenum.
Mechanical properties of investigated PM steels were summarised in Tables 3 and in Figures 2-9. High temperature
sintering of steels based on Astaloy CrL powder in 5%H2-95% N2 mixture and their tempering doesnt influence
on strength properties of investigated steels. UTS and TRS strengths and R0,2 yield offset are comparable
182

for tempered and not tempered samples; toughness and hardness values recorded for not tempered samples
increased by 4.8% and 25% than those obtained for as-tempered steels.
There are some materials e.g. gray cast iron or porous steels for which the initial elastic portion of the stress-strain
curve is not linear; hence, it is not possible to determine a modulus of elasticity as for wrought steel. For this
nonlinear behaviour, either tangent or secant modulus is used. Tangent modulus is taken as the slope of the stressstrain curve at some specified level of stress, while secant modulus represents the slope of a secant drawn from
the origin to some given point of the stress-strain curve. For the investigated specimens the proportional limit stress
was ~160MPa and Young modulus at this limit (measured either as secant or tangent modulus) was 150GPa (146160GPa measured using ultrasonic technique).
The mechanical properties of both group of steels (Astaloy CrL and Astaloy CrM-based materials) are comparable,
irrespective of sintering atmosphere. Not tempered steels, sintered in air with addition of 52g of FeMn obtained
higher mechanical properties.
After sintering at 1120C in 5%H2-95% N2 mixture, irrespective of heat treatment, the comparable mechanical
properties of investigated PM steels were obtained. Mechanical properties of steels based on Astaloy CrM prealloyed powder, sintered at 1250C in air with addition of 52g of FeMn were higher or comparable to properties of
low- chromium, low-molybdenum steels sintered at the same temperature in 5%H2-95% N2 atmosphere.
A specific characteristic of manganese in relation to sintering mechanisms is its vapour pressure, the highest of all
the alloying elements in PM structural steels. Its significance was first recognised by Salak [17, 18], who reported
that manganese sublimation and evaporation plays a significant part in such phenomena as homogenisation and
self-gettering action of Mn vapour. The observed rapid alloying of iron particles in Mn steels can only be accounted
for by transport of manganese via gaseous phase.
High manganese vapour pressure make possible manganizing of the sintered alloy, a process the diffusion
of manganese into the surface of a metal, particularly the steel compacted powder particles, and improve its
mechanical properties. This may be achieved by sintering the compacts (open-porous material) at 1100-1250C
in a sealed boat packed with compacts and ferromanganese lumps and with an inert gas/manganese vapour
atmosphere. Additionally manganese and carbon loss is lowered.
The effect low temperature sintering (at 1120C) and the use tempering on increasing the strength properties,
irrespective of chemical composition of sintering atmosphere, in Astaloy CrL based steel was observed. When
tempering wasnt carried out, the higher properties were recorded for steel sintered in air with addition of 52 g of
FeMn.
Chemical analysis has showed (Table 4), that reduction of oxides is more advanced in 5%H2-95% N2 atmosphere.
It can be pointed out that the addition of 52 grams of ferromanganese is not sufficient to oxide reduction presented
in sintered steels. Higher amount of nitrogen in compacts can be explained by nitriding in nitrogen-rich atmosphere.
The highest decarburization was observed for Astaloy CrL-based steels sintered at 1250C in the presence of
hydrogen. This phenomenon was also recorded in Astaloy CrM-based steels sintered in air with addition of 52g
FeMn.
5. CONCLUSIONS
Assuming present work, the following conclusions can be drawn:
1. The effect of heat treatment on the mechanical properties of Astaloy CrL-based steels sintered at 1250C in 5%
H2 / 95% N2 mixture was not observed.
2. Mechanical properties of Astaloy CrM-based steels sintered at 1250C in air + FeMn were comparable or higher
than those recorded for low-chromium, low- molybdenum PM steels.
3. Low temperature sintering (1120C) and the use of tempering, irrespective of sintering atmosphere, allow
increasing strength properties of low-chromium, low- molybdenum PM steels.
4. Not tempered, low-chromium, low-molybdenum PM steels sintered in air + 52 g FeMn obtained higher mechanical
properties than those sintered in nitrogen/hydrogen mixture.
5. The addition of lump of ferromanganese in amount of 52 g is not sufficient for oxides reduction.
6. Both higher sintering temperature and the presence of hydrogen in sintering atmosphere are favourable for
decarburization effect in sintered steels.
7. The heterogeneous microstructure of investigated PM steels mainly consists of martensite or martensite+bainite
(lower and upper).
183

ACKNOWLEDGEMENTS
The financial support of the Ministry of Science and Higher Education under the contract no N N507 477237 (AGH
no 18.18.110.961) is gratefully acknowledged.
REFERENCES
1. Cias, A., Development and Properties of Fe-Mn-(Mo)-(Cr)-C Sintered Steels, Ed. AGH-UST, Krakow, Poland,
2004.
2. Youseffi, M., Mitchell, S.C., Wronski, A.S., Cias, A., Sintering, Microstructure, and Mechanical Properties of PM
Manganese-Molybdenum Steels, Powder Metallurgy, Vol. 43, No. 4, pp. 353-358, 2000.
3. Cias, A., Mitchell, S.C., Wronski, A.S., Microstructure and Properties of PM 0.6%C Manganese Steels, Proc.
of the 1998 Powder Metallurgy World Congress, EPMA, Granada, Spain, Vol. 3, pp. 179-184, 1998.
4. Cias, A., Mitchell, S.C., Watts, A., Wronski, A.S., Microstructure and Mechanical Properties of Sintered (2-4)Mn(0.6-0.8)C Steels, Powder Metallurgy, Vol. 42, No. 3, pp. 227-233, 1999.
5. Mitchell, S.C, Wronski, A.S., Cias, A., Stoytchev, M., Microstructure and Mechanical Properties of Mn-Cr-Mo-C
Steels Sintered at >1140C, Advances in Powder Metallurgy and Particulate Materials, Vol .2, part 7, MPIF,
pp. 129 to 144, 1999.
6. Mitchell, S.C., Becker, B.S., Wronski, A.S., Further Alloying Additions to PM Fe- Mn-C Steels, Proc. of the 2000
PM World Congress, Kyoto, Japan, The Japan Soc. Of Powder and Powder Metallurgy, Vol. II, pp. 923-926,
2001.
7. Slesar, M., Danninger, H., Sulleiova, K., Microstructure Formation and Fracture Processes in Fe-C Systems
Sintered in Nitrogen, Powder Metallurgy Progress, Vol. 2, No 4, pp. 199-210, 2002.
8. Kremel, S., Danninger, H., Yu, Y., Effect of Sintering Conditions on Particle Contacts and Mechanical Properties
of PM Steels Prepared from 3%Cr Prealloyed Powder, Powder Metallurgy Progress, 2, pp. 211-221, 2002.
9. Mitchell, S. C., Cias, A., Carbothermic Reduction of Oxides During Nitrogen Sintering of Manganese and Chromium Steels, Powder Metallurgy Progress, Vol. 4, No 3, pp. 132-142, 2004.
10. Bocchini G. F., Influence of Controlled Atmospheres on the Proper Sintering of Carbon Steels, Powder Metallurgy Progress, Vol. 4, No 1, pp. 1-34, 2004.
11. Cias, A., Mitchell, S. C., Pilch, K., Cias, H., Sulowski, M., Wronski A.S., Tensile Properties of Fe-3Mn-0.6/0.7C
Steels Sintered in Semi-closed Containers in Dry Hydrogen, Nitrogen and Mixtures Thereof, Powder Metallurgy, Vol. 46, No 2, pp. 165-170, 2003.
12. Cias, A., Mitchell, S. C., Sulowski, M., Wronski, A. S., Sinter-hardening of Fe- Mn-C Steels, Proc. of Euro
PM2001, EPMA, Nice, France, Vol. 4, pp. 246-251, 2001.
13. Cias, A., Mitchell, S.C., Wronski, A. S., Mechanical Properties of Chromium PM Steel Sintered in Technical Nitrogen, Proc. of PM 2004 World Congress & Exhibition, EPMA, Vienna, Austria, Vol. 2, pp. 7-12, 2004.
14. Cias, A., Wronski, A.S., Mechanical Properties Distributions of PM Manganese Steels Analysed by Gaussian
and Weibull Statistics, Powder Metallurgy, Vol. 53, No 4, pp. 328-335, 2010.
15. Salak, A., Seleck, M., Bures, R., Manganese in Ferrous Powder Metallurgy, Powder Metallurgy Progress,
Vol. 1, No 1, pp. 41-58, 2001.
16. Hryha E., ajkova E., Dudrov E., Study of Reduction/Oxidation Processes in Cr- Mo Prealloyed Steels During
Sintering by Continuous Atmosphere Monitoring, Powder Metallurgy Progress, Vol. 7, No 4, pp. 181-197,
2007.
17. Salak, A., Effect of Extreme Sintering Condition upon Properties of Sintered Manganese Steels, Powder
Metallurgy International, Vol. 16, No. 6, pp. 260- 263, 1984.
18. Salak, A., Selecka M., Bures, R., Manganese in Ferrous Powder Metallurgy, Powder Metallurgy Progress,
Vol. 1, no 1, pp. 41-58, 2001.
184

HGANAS NEW LEAN ALLOYS FOR PM PARTS

Philippe SZABO*, Eda YILMAZTRK YKSEKDA**
*Hganas AB, France Office, 1117 Avenue Edouard Herriot, B.P. 117, F 69654, Villefranche sur Saone Cedex,
France, philippe.szabo@hoganas.com
**Hganas AB, Turkey Agency Office, Eksper Endustriyel Hammadde ve Dis Ticaret Ltd Sti, Sipahioglu Caddesi,
Salkim Apartmani, No:11 D:13, 34149, Yesilyurt, Istanbul, Turkey, eda@eksperdisticaret.com
ABSTRACT
In order to cut costs and to be less sensitive to price versatility of raw materials, Hgans AB recently developed
and put in mass production 2 new promising materials. Presented paper will cherry pick among examples of typical
results which can be achieved with these 2 products:
The so called Distaloy AQ, is part of the famous Hgans ABs family line of Distaloy (pre-diffusion
-
alloyed powders). Distaloy AQ is specifically designed to get very interesting mechanical properties after
standard heat treatments & tempering. It could also allow high compressibility and very easy machinability
after standard sintering.
The so called Astaloy CrA, is part of the Hgans ABs family line of pre-alloyed Cr content powders.
-
Due to Cr content process routine shall use N2 + H2 for furnace atmosphere. Astaloy CrA is designed to get
very nice global properties with standard sintering conditions. These properties will be emphasized a lot within
sinterhardening conditions and small addition of Copper or Ni.
Key Words: Distaloy AQ, Astaloy CrA, Alloyed Iron Powders, Mechanical Properties of PM Parts.
1. BACKGROUND FOR STRUCTURAL PARTS IN PM
It is well known that traditional materials for PM parts often include copper, nickel, or molybdenum in quantities of
totally 2-6%.

Due to recent cost increases & cost versatility for these alloying elements, these materials are becoming less competitive compared to solid steel process routes. (Figure 1.)
With a low alloy route, the sensitivity to price fluctuations can be reduced, and a robust product from an economical
point of view can be ensured.
Figure 1. Price changes for metals in max. and min. levels during 5 years and 1 year periods.
1.1. Hgans Routes To Be Less Sensitive To Versatile Material Costs
In order to reduce the amount of alloying elements and/or change the nature of alloying elements, Hgans decided
to work on LEAN ALLOYS way. Constraints being to use standard PM process routines and obviously to get good
level of properties for the PM parts.
This presentation is done in order to present 2 new alloys designed by Hgans, called DISTALOY AQ and
ASTALOY CrA .
1.2 eminder Of Hgans Standard Grades
Hgans is working for PM structural parts for a very long time. Its portfolio is very large and it is covering Sponge
Powders, Atomized powders and famous brand names as Distaloys and Astaloys.
All these root materials able to be mixed in Premix, Starmix and Densmix ways. (Figure 2.)
185

Figure 2. Key elements of powders portfolio and Lean Alloys in green.

2. DISTALOY AQ
CHEMICAL COMPOSITION : Fe base + 0.5% Mo + 0.5% Ni.
The Iron Base powder is the high purity atomized ASC100.29. Mo and Ni elements are diffusion- alloyed elements
(Figure 3.)
Figure 3. Sketch of a pre-diffusion alloyed particle.

The diffusion-alloying process allows for high compressibility together with good consistency of properties on the
PM components.
The key process routine is defined as: COMPACTION + STANDARD SINTERING + CONVENTIONAL HEAT
TREATMENT
186

2.1 Properties
2.1.1 Green and Sintered Density
Figure 4. Green density levels, in different compaction levels and in different lubricants additions.
Figure 5. Sintered density levels, in different compaction levels, in different lubricant additions and in different
sintering temperatures.

Compaction and sintering conditions are within, 600 and 700 MPa/70C compaction, 0.6% Lube E used as lubricant, sintering done at 1120C for 30 minutes and at 1250C for 1h, with 90/10 N2/H2atmosphere, no forced cooling
was applied.
2.1.2 Sintered Properties and Typical Microstructures
Figure 6. Dimensional Change after sintering at the

same sintering conditions, due to added graphite
content before sintering.(Green Line: 700 MPa compaction to 7,25 g/cm3 density, Blue Line: 600 MPa
compaction to 7,10 g/cm3 density)
Figure 7. Hardness variation after sintering

at the same sintering conditions, due to the
added graphite content before sintering.
187

Figure 8. Tensile strength variation after sintering at the same sintering conditions, due to the added graphite
content before sintering.
Figure 9. Microstructure of Distaloy AQ + 0.46%C
Figure 10. Microstructure of Distaloy AQ + 0.78%C
2.1.3 Heat Treated Properties

Compaction + Sintering + Heat Treatment conditions are within 20 min, 920C, C-neutral, oil quench, tempering
200C 1h in air.
Figure 11. Tensile Strength variation after Q&T heat

treatment at the same heat treatment conditions due
to the graphite content in the part.
Figure 12. Hardness variation after Q&T heat

188

Figure 13. Elongation variation after Q&T heat treatment at the same heat treatment conditions due to
the graphite content in the part.
Figure 14. Impact Energy variation after Q&T heat

2.1.4 Typical Performances
Figure 15. Tensile Strength comparison of different

grades, after the same sintering conditions.
Figure 16. Yield Strength comparison of different

grades, after the same compaction and sintering
conditions
Figure 17. Hardness comparison of different grades,

after the same sintering conditions.
Figure 18. Elongation comparison of different grades,

after the same compaction and sintering conditions.
3. ASTALOY CrA
CHEMICAL COMPOSITION: Fe base + 1.8% Cr, Fully Pre-Alloyed
189

Figure 19. Sketch of a pre-alloyed particle. The key process routine

is defined as: COMPACTION + STANDARD SINTERING or SINTERHARDENING in N2+H2 Atmosphere.
3.1 Properties
3.1.1 Green Density
Figure 20. Green Density variation of Astaloy CrA depending on different compaction pressures and different
lubrication systems.
3.1.2 Sintered and Sinterhardened Properties
Figure 21. Sintered and Sinter Hardened Properties of Astaloy CrA according to different process parameters.
3.1.3 Typical Microstructures
In this section, different examples of microstructures depending on Carbon content, sinter-hardening conditions
and different Copper or Nickel additions are displayed.
190

Standard Sintering
Figure 22. Microstructure of Astaloy CrA with %0,4

sintered carbon content shows Pearlitic structure with
around %5 ferrite inside.

sintered carbon content shows totally Pearlitic structure.
Figure 24. Microstructure of Astaloy CrA with %0,8 sintered carbon content shows totally Pearlitic structure.
Astaloy CrA is basically a pearlitic material regardless of treatment under normal un-alloyed conditions.
Sinter-Hardening at Cooling Rate 3 4 C/sec

sintered carbon content shows Pearlitic structure with
around %5 ferrite inside.

sintered carbon content shows totally Pearlitic structure.
Figure 27. Microstructure of Astaloy CrA

with %0,8 sintered carbon content shows
totally Pearlitic structure.
191

In sinterhardened conditions, the pearlite will be finer and some islands of martensite will form. Astaloy CrA is basically a perlitic material regardless of treatment under normal un-alloyed conditions.
Ni or Cu Admixing (Sinterhardened Microstructures, cooling rate 3-4C/s)
Figure 28. Microstructure of Astaloy CrA + %2 Ni with

%0,6 sintered carbon, shows Martensitic structure
with %20 pearlit as well.
Figure 29. Microstructure of Astaloy CrA + %1 Cu

with %0,6 sintered carbon, shows Martensitic
structure with around %10 pearlite and some Bainite.
4. CONCLUSIONS
Distaloy AQ, is a newly developed diffusion-alloyed low Mo & Ni containing powder, suitable for manufacturing of
high performance PM components after sintering at 1120C + conventional heat treatment .
The optimum carbon content for this lean alloyed steel is between 0.5% and 0.6%.
Tensile strengths of 800 ~1300 MPa can be achieved with the density level from 6.8 to 7.25 g/cm3
Astaloy CrA , is a newly developed pre-alloyed Cr containing powder, suitable for manufacturing of high performance PM components, after sintering at 1120C .
Depending on carbon content, tensile strength levels from 500 MPa to 700 MPa can be obtained after conventional
sintering at 1120 C.
By adding Cu or Ni to Astaloy CrA; materials that possess good hardenability and thereby give excellent response
to sinter hardening operations can be obtained. Martensitic structures can be achieved already at cooling rates of
2.0 C/s at a density of 7.0 g/cm3 .
At a sintered carbon content of 0.5-0.6% Tensile Strength around1000 MPa is obtained with 1% Cu addition and
around 1100 MPa can be obtained by a Ni addition of 2%.
Hardness levels in the range of 300-400HV10 and elongation in the range 0.5 to 0.8 % can be obtained for both
alloyed materials after sinter hardening.
All results and figures thank to Ulf Engstrm and team from Hgans AB
192

AN EXAMINATION OF COBALT EFFECT ON HEAT TREATED POWDER

METALLURGICAL TOOL STEELS
. Hakan ATAPEK*, eyda POLAT*, Serap GM*,
Ersoy ERR* and Gzde S. ALTU*
*
Kocaeli University, Faculty of Engineering,
Department of Metallurgical and Materials Engineering, 41380, Kocaeli, hatapek@kocaeli.edu.tr, seyda@kocaeli.
edu.tr, sgumus@kocaeli.edu.tr, eerisir@kocaeli.edu.tr, gsultan.altug@gmail.com
ABSTRACT
In this study, two commercial grades of powder metallurgical tool steels (DIN 1.3394 and 1.3395) are investigated to
determine cobalt effect on the matrix, carbide distribution and hardness in soft annealed and hardened conditions.
The steels have a similar composition of 1.30C, 4.20Cr, 6.40W, 5.00Mo and 3.10V, with the exception that DIN
1.3394 steel has 8.50Co as well. In order to investigate the primary carbides, soft annealing and solution annealing
heat treatments were carried out. The specimens were heated stepwise (650 C, 850 C and solution annealing
temperature) and hardened at 1000 C, 1100 C and 1200 C for 15 min followed by water quenching. In the first
step, all samples are prepared by grinding and then ground surfaces are polished. Nital and Beraha solutions
are used as etchants. Electrolytic etching is then carried out with AC2-I solution to characterize the matrix phase
(martensite) after hardening. In the second step, all samples are examined using scanning electron microscope
and energy dispersive x-ray spectrometer to investigate the carbide type in the matrix. In the third step, hardness
values of the steels are determined in Vickers scale. The microstructural characterization reveals that DIN 1.3395
steel exhibits dispersed M6C and MC type carbides and carbides have poor interfaces with the matrix. On the other
hand, DIN 1.3394 steel has M6C and MC carbides in the matrix, with skeleton morphology, due to cobalt wetting.
Vickers hardness measurements show that DIN 1.3394 steel has a higher hardness value than DIN 1.3395 steel
due to strengthening effect of cobalt in ferrite.
Keywords: Tool steels, Powder Metallurgy, Microstructure, Carbides, Cobalt Wetting.
1. INTRODUCTION
Proper heat treatment of tool steels is essential for their properties. Powder metallurgical (PM) tool steels have
similar heat treatment routes as conventional tool steels, but they respond more rapidly to heat treatments due to
their more uniform microstructure and finer carbides [1, 2]. PM tool steels may include cobalt as alloying element.
Costly addition of cobalt increases solidus temperatures, thus permitting the use of higher solution temperatures.
Furthermore, cobalt enhances hot hardness and temper resistance by promoting a finer carbide size, without entering the carbide lattice [1, 3]. The properties of tool steels are determined by the type, distribution and morphology
of the primary carbides. The secondary carbides, precipitated during tempering, determine the hot hardness of the
material [4]. Depending on the chemical composition of PM tool steels and on the cooling rate, following types of
primary carbides appear in the alloyed steels after solidification: MC, M2C and M6C. Other carbides are of a minor
importance [5]. During high temperature annealing, unstable M2C carbides decompose into M6C and MC carbides
[5-7].
In tool steels, the improvement in the cutting performance with the addition of cobalt is indisputable. The more difficult the material is to machine, the more effective the addition of cobalt to the tool steel. Cobalt dissolves in iron
(ferrite and austenite) and strengthens it at the same time imparting high temperature strength. During solution heat
treatment to dissolve the carbides, cobalt helps the resist grain growth so that higher solution temperatures can
be used to ensure the dissolution of higher percentage of carbides. Steels are quenched after solution annealing
and a microstructure consisting of hard martensite with fine alloy carbides is obtained. Tempering will cause the
precipitation of ultrafine carbides still in solution and maximum hardness will be attained. Here, cobalt plays another
193

important role, in that it delays their coalescence. This is important as it means that during cutting, the structure
is stable up to higher temperatures. Thus, cobalt-containing tool steels are capable of retaining strength at higher
temperatures [8-10].
In the present study, cobalt effect on the matrix of a soft annealed powder metallurgical tool steel was investigated.
DIN 1.3394 and DIN 1.3395 powder metallurgical steels in soft annealed and hardened conditions were examined
using light microscope (LM), scanning electron microscope (SEM) and energy dispersive x-ray spectrometer (EDS).
M6C and MC type carbides were found. Cobalt alloying resulted in a skeleton morphology of carbides due to wetting.
2.1. Materials
Two commercial grades of powder metallurgical tool steels, DIN 1.3394 and DIN 1.3395, were used in the experimental studies. The chemical compositions of the experimental steels are listed in Table 1. The soft annealing and
solution annealing heat treatments were carried out in order to investigate the primary carbides. The specimen size
of 10mm x 10mm x 15mm was used. The specimens were heated stepwise (650 C, 850 C and solution annealing
temperature) and hardened at 1000 C, 1100 C and 1200 C for 15 min followed by water quenching. Hardness
values of the steels for soft annealed condition were measured in Vickers scale. After three measurements, a mean
value of hardness was determined as 204.7 HV10 for DIN 1.3395 and 285.2 HV10 for DIN 1.3394. As can be seen
from the hardness measurements, Co-free steel has a lower hardness value than the one having 8.50Co (wt. %).
Table 1. Chemical compositions of the experimental steels (wt.%).
Materials
DIN 1.3395
DIN 1.3394
C
1.30
1.30
Cr
4.20
4.20
Mo
5.00
5.00
V
3.10
3.10
W
6.40
6.40
Co
8.50
Fe
balance
balance
2.2. Metallographical preparations and microscopic examinations

The specimens were metallographically prepared. After grinding, they were polished using diamond pastes with
particle sizes of 3 m. Beraha II (100 ml H2O +20 ml HCl + 0.30.6 g of potassium metabisulfite) and % 3 nital
solutions were used as etching agents. Electrolytic etching was then carried out with AC2-I solution to characterize
the matrix phase (martensite) after hardening. Zeis Axitotech 100 model light microscope, Jeol JSM 6060 model
scanning electron microscope and energy dispersive x-ray spectrometer were used to observe the morphology of
carbides and to analyze their chemical compositions.
3.1. Microstructural characterization in soft annealed condition
The microstructures of DIN 1.3395 and DIN 1.3394 grade tool steels in soft annealed condition are given in Figure1. Cobalt free DIN 1.3395 tool steel has random distributed carbides in matrix phase (Figure 1a). As shown in
Figure 1b, cobalt affects the distribution of carbides. A skeleton structure of carbides is seen after soft annealing.
Figure 1. SEM micrographs of tool steels in soft annealed condition, electrolytic etching; (a) DIN 1.3395 and (b)
DIN 1.3394.
194

3.2. Microstructural characterization in solution annealing condition

In order to reveal the primary carbides in martensitic matrix, electrolytic etching was carried out using AC2-I solution. Figure 2 shows a SEM micrograph of DIN 1.3395 steel after solution annealing at 1000C for 15 min. Micrometer sized MC (grey) and sub-micrometer sized M6C (white) primary carbides exist in the microstructure. It should
also be mentioned that deep etching reveals also martensitic plates of the matrix phase.
Figure 2. SEM micrograph of DIN 1.3395 after solution annealing at 1000 C for 15 min., electrolytic etching.
The carbides (MC and M6C) and the matrix could be differentiated in this sample by using secondary electron (SE)
imaging and backscattered electron (BSE) imaging (Figure 3). Since the carbides vary strongly in composition, W/
Mo (higher atomic number than Fe in the matrix) rich M6C carbides appear in white contrast. On the other hand,
MC carbides rich in V (atomic number close to Fe in the matrix) appear in gray and cannot be distinguished from
the matrix in Figure 3b.
Figure 3. SEM micrographs of DIN 1.3395 after solution annealing at 1000 C for 15 min., etched by Beraha; (a)
SE mode and (b) BSE mode.
In order to determine the chemical compositions of the primary carbides, microanalysis was carried out using EDS
(Figure 4 and 5). The spot analyses (Figure 4b and 5b) revealed two types of primary carbides, tungsten and molybdenum being present in both. According to the EDS peaks, M6C carbides include mainly W and Mo (Figure 4b),
whereas in primary MC carbides V exists as well and is dominant (Figure 5b). As it is seen, there is no cobalt content
in both carbides. Cobalt takes place in iron lattice to strengthen the matrix phase.
Figure 4. (a) SEM micrograph and (b) EDS analysis of M6C carbides.
195

Figure 5. (a) SEM micrograph and (b) EDS analysis of MC carbides.

The microstructure of primary carbides in 8.5% cobalt alloyed PM steel (DIN 1.3394), after solution annealing at
1000 C for 15 min. is given in Figure 6. Similar primary carbides appear in DIN 1.3394 steel as well, however their
distribution in matrix phase is markedly different than DIN 1.3395 case. The wetting effect of cobalt results in orientation of carbides rather than random distribution.
Figure 6. SEM micrograph of DIN 1.3394 after solution annealing at 1000 C for 15 min., electrolytic etching.
The microstructures observed in solution annealed samples, etched by nital and Beraha solutions, are presented in
Figures 7-12. The steel (DIN 1.3395), heated up to 1000C and then quenched, has random distributed carbides in
the matrix (Figure 7). However, as the hardening temperature increases the amount of the carbides in the matrix decreases (Figures 8 and 9). This indicates that temperature promotes the dissolubility of the alloying element in iron
lattice. In Figure 9, the mobility of grain boundaries is clearly seen in DIN 1.3395 tool steel heated up to 1200C.
Effect of cobalt on wetting is seen in the matrix as given in Figures 10-12. The matrix of DIN 1.3394 tool steel
heated up to 1000C exhibits fine and homogeneous carbides and it is obvious that there is no significant effect
on the dissolubility of the carbides due to heating (Figure 10). As the heating temperature increases, the tendency
of austenite grain size to be coarsened increases (Figures 11 and 12). Both steels showed grain coarsening with
increasing annealing temperature.
Figure 7. Micrograph of DIN 1.3395 tool steel. Solution annealing temperature : 1000C, etched by nital +
Beraha II solution.
196

Beraha II solution.
eraha II solution.
Beraha II solution.
Beraha II solution.
Beraha II solution.
4. CONCLUSION
Powder metallurgical high-speed steels were soft annealed and hardened. Primary carbides observed in the matrix
were analyzed using scanning electron microscope and energy dispersive spectrometer. The following preliminary
results were obtained:
(i) Soft annealing revealed that cobalt had a significant effect on the carbide distribution in matrix phase. A skeleton
structure of carbides was seen in DIN 1.3394 steel.
197

(ii) After solution annealing, SEM investigations and EDS analyses indicated that the primary carbides were of M6C
and MC type.
(iii) Comparison of hardened steel with soft annealed condition revealed that the secondary carbides remained
undissolved after solution annealing at 1000C. When the micrographs are considered, as temperature of solution
annealing increases the amount of carbides within the matrix decreases due to dissolutions.
(iv) In solution annealed samples, grain coarsening was observed for both steels as annealing temperature increased.
References
1. Davis, J. R., ASM Specialty Handbook: Tool Materials, ASM International, Materials Park, OH-USA, 1995.
2. Roberts, G., Krauss, G., Kennedy, R., Tool Steels, ASM International, Materials Park, OH-USA, 1998.
3. Fischmeister, H. F., Karagz, ., Andrn, H. O., An Atom Probe Study of Secondary Hardening in High Speed
Steels, Acta Metall, Vol. 36, pp. 817-825, 1988.
4. Riedl, R., Karagz, ., Fischmeister, H. F., Jeglitsch, F., Developments in High Speed Tool Steels, Steel
Research, Vol. 58, pp. 339-352, 1987.
5. Pippel, E., Woltersdorf, J., Pckl, G., Lichtenegger, G., Microstructure and Nanochemistry of Carbide Precipitates in High-Speed Steel S 6-5-2-5, Materials Characterization, Vol. 43, pp. 41-44, 1999.
6. Lee, E. S., Park, W. J., Baik, K. H., Ahn, S., Different Carbide Types and Their Effect on Bend Properties of a
Spray-Formed High Speed Steel, Scripta Materialia, Vol. 39(8), pp. 1133-1138, 1998.
7. Zhou, X., Fang, F., Li, G., Jiang, J., Morphology and Properties of M2C Eutectic Carbides in AISI M2 Steel, ISIJ
International, Vol. 50(8), pp. 1151-1157, 2010.
8. ASM Handbook, Machining, Vol. 16, pp. 51-59, ASM International, Ohio-USA, 1989.
9. Moiseev, V. F., Geller, Y. A., Effect of Cobalt on Structure and Properties of Fast-Cutting Steel, Metal Science
and Heat Treatment, Vol. 7(4), pp. 245-249, 1965.
10. Gulyaev, A. P., Kupalova, I. K., Effect of Cobalt on the Structure and Properties of High-Speed Steels, Metal
Science and Heat Treatment, Vol. 12(8), pp. 666-671, 1970.
198

FORMING
PROCESSES
www.turkishpm.org
199

NI 625 Speralamlarnn Toz Enjeksiyon

Kalplama Yntemiyle retilmesi
zgr ZGN*, H. zkan GLSOY**, Fehim FINDIK***, Ramazan YILMAZ****
Bingl niversitesi, Teknik Bilimler Meslek Yksekokulu, Bingl, Trkiye, oozgun@bingol.edu.tr
**
Marmara niversitesi, Teknoloji Fakltesi, Gztepe, stanbul, 34722, Trkiye
**
TBTAK MAM, Malzeme Enstits, Gebze - Kocaeli, 41470, Trkiye, ogulsoy@marmara.edu.tr
***
International University of Sarajevo, Faculty of Engineering and Natural Sciences
Department of Mechanical Engineering, 71000 Sarajevo, Bosnia-Herzegovina, ffindik@ius.edu.ba
****
Sakarya niversitesi, Teknoloji Fakltesi, Esentepe Kamps, 54187, Sakarya, Trkiye, ryilmaz@sakarya.edu.tr
*
ZET
Toz Enjeksiyon Kalplama (TEK) metalik ve metalik olmayan eitli boyutlardaki karmak ekilli paralarn retiminde yksek katma deere sahip ve gelimekte olan bir teknolojidir. Speralamlarn otomotiv, havaclk, medikal ve
endstriyel uygulamalardaki stn zellikleri nedeniyle demir, krom ve/veya kobalt ieren nikel esasl speralamlarn gelitirilmesi zerine aratrmalar younlatrlmtr. Bu almada nikel esasl speralamlarn TEK yntemi
ile retilmesi ve optimum retim parametrelerinin incelenmesi gerekletirilmitir. Deneysel almalar iin nikel
esasl speralam gruplar ierisinde nemli bir yere sahip olan NI 625 tipi speralam tozlar, parafin mum (PM),
polipropilen (PP), brezilya mumu (BM) ve stearik asit (SA) ieren ok bileenli bir balayc sistemi ile kartrlmtr.
Elde edilen karm granl haline getirildikten sonra enjeksiyonla kalplanarak standart ekme ubuu formu kazandrlmtr. Kalplama sonrasnda NI 625 numunelerinin polimerik malzemelerden arndrlmas amacyla solvent ve
termal balayc giderme ilemleri uygulanmtr. Balaycs giderilen numuneler DSC ve dilatometre analizlerine
tabi tutularak, farkl scaklklarda ve yksek vakum altnda sinterlenmitir. retilen numunelerin younluk lmleri
ve optik mikroskop incelemeleri yaplmtr. Sinterleme scakl artna bal olarak younluk deerleri art gstermi ve en yksek younluk deerine 1300oCde sinterlenen numunelerin sahip olduu gzlenmitir.
Anahtar Kelimeler: Toz Enjeksiyon Kalplama, Speralam, NI 625, Sinterleme.
ProductIon of NI 625 Superalloys BY Powder

InjectIon MouldIng Method
ABSTRACT
Powder injection molding (PIM) is a maturing technology which is highly useful for the production of complex metallic and non-metallic parts of various sizes. Considering the advantageous properties of superalloys in automotive, aerospace, medical, and industrial applications, the development of nickel based superalloys containing iron,
chromium and/or cobalt have become of great interest in recent years. In this work we present our effort made on
developing nickel based superalloys by PIM process. A multiple component binder system consisting of paraffin
wax (PA), polypropylene (PP), carnauba wax (CW), and stearic acid (SA) were mixed with metal powder (62.5
vol.%). NI 625 was prepared and injection molded as standard tensile bars. Solvent and thermal debinding process
was employed to remove the polymeric materials. An optimized sintering cycle derived from differential scanning
calorimetry (DSC) was used to sinter the specimens at different temperatures and in a high vacuum furnace. After
production, a number of density measurements and light microscopes examinations were conducted. Density values of the materials increases depending on increasing of the sintering temperature and the highest density value
was obtained for the sample sintered at 1300oC.
Key words: Powder Injection Moulding, superalloy, NI 625, sintering
200

1. Giri
Enjeksiyon kalplama yksek boyutsal hassasiyete sahip rnleri kusursuz, ince taneli yapda ve mekanik zellikleri
anizotropik olmayacak bir ekilde retmeyi mmkn klmakla birlikte; %95in zerinde verim salayan, para retimindeki iilii 3 kat veya daha da aa dren ve ilk yatrm maliyeti dk olan bir retim yntemidir. Enjeksiyon
kalplamayla tek aamada kalplanan ve sinterlenen paralarn younluu geleneksel yntemlerle preslenerek sinterlenen paralardan daha yksek olup mukavemetleri dkm ve haddeleme ile retilenlere yakndr [1].
Nikel esasl speralamlar gaz trbinleri, uak motoru bileenleri, jet motorlar iin kritik paralar, roket motorlar,
nkleer paralar takm malzemeleri ve metaller iin scak ilem kalplarnda en sk kullanlan malzemelerdir [2]. NI
625 ve NI 718 mhendislik uygulamalarnda en baarl uygulanm speralamlar arasnda yer almaktadrlar [3].
Nikel esasl bir speralam olan NI 625 alam mukavemet ve korozyon dayanmnn mkemmel bir kombinasyonunu sergilemektedir. Cr, Mo ve Nb gibi temel alam elementlerini ieren bu malzeme kat zelti ile mukavemetlenen bir alam olarak snflandrlmtr [4,5]. Mikroyapsal kararllndan dolay servis scakl kriyojenik scaklklar
ile 1000oC arasnda olabilmektedir [6]. Gnmzde bu alamdan dvme yntemiyle retilen paralar endstride
byk kabul grmesine ramen, karmak ekle sahip ou parann talal ilem gerektirmesi retim maliyetinin
ok yksek olmasna yol amaktadr [7]. Geleneksel dkm yntemiyle retimde kimyasal segregasyonun neden
olduu malzeme zelliklerindeki ktleme homojen iyap ve ince tane yaps salayan toz metalurjisi ile retime
ynelmeye neden olmutur. Son gnlerde speralamlardan gaz trbin motorlar iin eitli paralarn retiminde
metal enjeksiyon kalplama byk ilgi grmektedir [812].
Bu almada yksek ekme mukavemeti, srnme dayanm, kopma mukavemeti ve korozyon direnci gibi zellikleri beraber sergilediinden dolay olduka geni kullanm alan bulan NI 625 alamnn [4,5] toz enjeksiyon kalplama yntemiyle ekillendirilerek farkl scaklklarda sinterlenmesi sonucu mikroyapsal zelliklerinin karakterize edilerek belirlenmesi ve bu sayede genellikle dkm ve dvme yntemleriyle retilmekte olan bu denli geni kullanm
alanna sahip bir malzeme iin alternatif bir retim yntemi olan TEK metodu iin optimum retim parametrelerinin
tespit edilmesi amalanmaktadr.
2. Deneysel almalar
Bu almada Osprey Co. (UK) firmasndan temin edilen NI 625 speralam tozlar kullanlmtr. Deneylerde kullanlan NI 625 speralam tozunun kimyasal bileimi Tablo 1de verilmitir. Kullanlan tozun parack ekli hakknda
bilgi edinmek amacyla SEM grnts alnm, boyut dalm hakknda bilgi edinmek zere Malvern Mastersizer
cihaz ile boyut dalm analizi gerekletirilmitir. Tablo 2de tane boyutu dalm analizine ait sonular da ieren
balang tozuna ait baz zellikler verilmitir.
Tablo 1. NI 625 speralam tozlarnn kimyasal bileimleri
Ni
Cr
Fe
Nb
Mo
% arlk
Al
Ti
Co
Si
Mn
NI 625
64,043
20,9
2,600
3,2
8,4
0,01
0,01
0,01
0,029
0,31
0,39
Tablo 2. NI 625 speralam tozlarnn zellikleri

zellik
retici
retim yntemi
Toz ekli
Vurgu younluu (g.cm3)
NI 625
Osprey
Gaz atomizasyonu
Kresel
5,3
Teorik younluk (g. cm3)
8,58
Partikl boyutu (m)
D10
3,7
D50
11,1
D90
26,7
Polipropilen, parafin mum, brezilya mumu ve stearik asidin farkl oranlarda kartrlmas ile elde edilen ok bileenli
bir sistem halindeki balayc ile NI 625 tozu hacimce %60 ana toz%40 balayc olacak ekilde vakum altnda ve
170oC scaklkta 30 dk kartrlarak besleme stou hazrlanmtr. Besleme stou souduktan sonra el ile granle
edilerek enjeksiyon cihaznda 12,5 MPa basn ve 20 saniye tutma sresi uygulanarak MPIF 50 standardna uygun
olarak hazrlanm kalp kullanlarak ekme numuneleri kalplanmtr.
201

ekillendirilen numunelerin balayc giderme ilemi iki aamada gerekletirilmitir. lk aama solvent balayc
giderme ilemi olup, 70oCye stlan heptan ierisinde numunelerin 6 saat bekletilmesi eklinde gerekletirilmitir.
Bu ilem sonucunda stearik asit, brezilya mumu ve parafin mumun numuneleri terk edip heptana gemesiyle yap
ierisindeki balayclarn byk bir ksm uzaklatrlmtr. Balayc gidermenin ikinci aamas sl balayc giderme aamas olup, numunelerin almina altlk zerinde ve vakum ortamnda ekil 1de verilen sl evrime maruz
braklmasyla gerekletirilmitir.
ekil 1. Isl balayc giderme ilemi evrimi

TEK ile ekillendirilmi ve balaycs giderilmi numunelerin sinterleme davranlarnn belirlenmesi iin DSC ve
dilatometrik testler uygulanmtr. DSC analizi Setaram marka DSC131 model cihazla (Fransa) 108,6 mg arlndaki numunenin 10oC/dk stma hzyla 1350oCye kadar 100 ml/dk debili yksek saflktaki Ar gaz atmosferi altnda
stlmas ile gerekletirilmitir. Referans malzeme olarak Al2O3 kullanlmtr. Scaklk deiimine bal olarak malzemede meydana gelen genleme veya bzlmenin tespit edilebilmesini salayan dilatometre analizi iin ilk l
boyu 3,47 mm olan numune kullanlmtr. Analiz, Unitherm Model 1161H cihaz (USA) kullanlarak numunenin H2
atmosferi altnda 10oC/dk stma hz ile 1313oCye kadar stldktan sonra 10oC /dk ile oda scaklna soutulmas
eklinde gerekletirilmitir.
NI 625 numuneleri 12601320oC arasnda farkl scaklklarda sinterlenmilerdir. Tm sinterleme ilemleri vakum
ortamnda 10oC/dk stma ve soutma hzlaryla sinterleme scaklnda 1 saat tutma sresiyle gerekletirilmi olup
frnn soumas srasnda 150oCye kadar vakum ak braklmtr. ekil 2de NI 625 tozundan retilmi ekme numunelerinin kalplama sonras ve sinterleme sonras grntleri verilmitir. ekme numunelerinin balayc giderme
ilemine de bal olarak sinterleme sonras boyutsal olarak %1618 orannda ekme gsterdii grlmektedir.
Sinterleme ileminin yksek vakum deerlerine klarak yaplmasna bal olarak numune yzeyinde herhangi bir
oksitlenme olmad grlmtr.
ekil 2. NI 625 tozundan TEK ile retilen ekme numunelerinin kalplama sonras ve sinterleme
sonras grntleri
Sinterleme sonras Arimet prensibine gre numunelerin younluklar llmtr. Zmparalama ve parlatma gibi
metalografik hazrlklardan sonra ve uygun dalayclarla dalandktan sonra numunelerin mikroyapsal geliimi
incelenmitir.
3. Sonular ve Tartma
Balang tozunun tane ekli hakknda bilgi edinmek amacyla alnm ekil 3teki SEM grntsnden de grlecei gibi tozlar kresel ekle sahiptirler. Toz enjeksiyon kalplamada kullanlan tozlarn partikl boyutu 20 mnin
202

altndadr [8]. ekil 4teki tane boyutu analizine ait eriden tane boyut dalmnn toz enjeksiyon kalplamada kullanlmaya uygun aralkta olduu grlmektedir.
ekil 3. NI 625 tozunun SEM grnts
ekil 4. Ni625 tozuna ait tane boyut dalm erisi

TEK ile ekillendirilen numuneler iin uygun sinterleme scakl aralnn belirlenebilmesi amacyla gerekletirilen
DSC ve dilatometre analizlerine ait eriler srasyla ekil 5 ve ekil 6da verilmitir. DSC erisine gre 1170oCde
faz dnm olabilecei dnlen bir endotermik pik olumutur. NI 625 numuneleri iin ergimenin yaklak
1298oCde balad ve 1331oCye kadar devam ettii grlmektedir. ekil 6da grlen dilatometre erisine gre
bzlmenin 1190oCde balayp 1305oCye kadar devam ettii, en yksek bzlmenin 1300oC civarndaki scaklkta
meydana geldii grlmektedir. Kimyasal bileimi bu almada kullanlan NI 625 tozuna ok yakn olan tozlarn
kullanlmasyla gerekletirilmi olan bir baka almada yaplm olan dilatometre analizi sonucunda maksimum
bzlmenin 1294oCde meydan geldii bildirilmitir [7].
ekil 5. NI 625 numunelerine ait DSC erisi
203

ekil 6. NI 625 numunelerine ait dilatometre erisi

DSC ve dilatometrik analiz sonular esas alnarak, farkl scaklklarda ve birer saatlik sreyle gerekletirilen sinterleme ilemleri sonras numunelerde ulalabilen grnr younluk deerleri ekil 7.ada, bal younluk deerleri ekil 7.bde verilmitir. En yksek younluk deerine 1300oCde yaplm olan sinterleme ilemiyle ulald
grlmektedir. 1300oCnin zerindeki scaklklarda gerekletirilen sinterleme ilemlerinin younluun daha ok
artmasna herhangi bir katk salamad, aksine de yol at grlmtr. 1320oC ve zerindeki sinterleme
scaklklarnda numunelerde ksmi ergimelerin olduu ve buna bal olarak numune ekillerinin bozulduu gzlemlenmi; sinterleme ileminin 1320oCden yksek scaklklarda yaplamayaca tespit edilmitir.
ekil 7. Sinterleme scaklna bal olarak a) elde edilen grnr younluk deerleri, b) ulalabilen
bal younluk deerleri
204

Sinterlenen numunelerin gzenek miktar hakknda bilgi edinmek amacyla numunelerden parlatma ilemi sonrasnda alnm olan optik grntler ekil 8de verilmitir. Toz enjeksiyon kalplama yntemiyle retilen paralar
geleneksel toz metalurjisi ile retilenlerden daha youndurlar. Para iinde kalan az miktardaki gzenekler de kk
ve kresel ekilli olup birbirleriyle balantl deillerdir [13]. Grntler incelendiinde yukardaki aklamaya uygun
olarak gzenek yapsnn kresel olduu ve gzeneklerin birbirleriyle balantl olmadklar grlmektedir.
ekil 8. a) 1260oCde, b) 1280oCde, c) 1300oCde, d) 1320oCde bir saat sreyle sinterlenen numunelerin
parlatma sonras, dalama ncesi optik grntleri
Farkl scaklklarda sinterlenmi numunelerin tane yaplarnn anlalabilmesi amacyla dalama ilemi sonrasnda
alnm olan optik grntleri ekil 9da verilmitir. Gzeneklerin ounlukla tane ilerinde hapsolmu durumda
bulunduu fakat ksmen tane snrlarnda da gzeneklere rastland ve bu gzeneklerin tane ierisindeki gzeneklerden daha iri olduu sylenebilir. 1260oCde sinterlenen numunenin optik grntsnden sadece toz partiklleri
arasnda boyun oluumunun gerekletii, dolaysyla bu scakln sinterleme iin yetersiz olduu anlalmaktadr.
Elde edilen younluk deerlerine uygun olarak en az gzenek miktarnn 1300oCde sinterlenen numunenin grntsnde olduu ve bu numunedeki gzeneklerin dierlerine kyasla daha kk boyutlu olduu gzlenmitir. Tane
boyutunun artan sinterleme scakl ve sresi ile birlikte artt bilinen bir gerektir [14,15]. Grntler incelendiinde artan sinterleme scaklyla beraber tane boyutunun da iriletii grlmektedir. En yksek younluu salayan
1300oCde sinterlenmi numunenin ortalama tane boyutunun 100 m civarnda olduu grlmektedir. 1320oCde
yaplan sinterleme sonucu malzemede gzeneklerin iriletii ve buna bal olarak dk younluk deeri elde edildii grlmtr. Bu durumun yksek miktarda sv faz oluumundan kaynaklanm olabilecei dnlmektedir.
205

ekil 9. a) 1260oCde, b) 1280oCde, c) 1300oCde, d) 1320oCde bir saat sreyle sinterlenen numunelerin
dalama sonras optik grntleri
Yaplm olan bir almada 8,5 m boyutunda NI 625 tozu kullanlarak hidrojen atmosferi altnda, 1288-1298oC
scaklk aralnda ve 2460 dakika tutma sreleriyle gerekletirilen sinterleme sonucu % 99un zerinde bal younlua ulalabildii rapor edilmitir [12]. Bir baka almada ortalama tane boyutu 9,7 m olan NI 625 tozundan
retilen ham paralarn hidrojen atmosferi kullanlarak 1290oCde 0,5 saat sinterlenmesi sonucu 8,4 g.cm-3 younluk
deeri (%99,5 bal younluk) elde edildii bildirilmektedir.
Yine bu almada daha yksek younluk deerleri elde edilebilmesi iin sinterleme artlar zerinde yaplacak
almalarn gerekliliine de vurgu yaplmaktadr [16]. Bu almada biraz daha dk younluk deerleri elde edilmi olmasnn, kullanlan balang tozunun ortalama tane boyutunun daha byk olmasndan ve balang tozlar
arasndaki kimyasal bileim farkllklarndan kaynaklanm olabilecei dnlmektedir.
Sinterleme ileminde itici g yzey enerjisindeki azalmadr. Daha kk boyutlu toz partiklleri daha yksek yzey
enerjisi salar ve bu sayede daha ksa srede daha yksek younluk deerleri elde edilebilir [14]. Bu almada
zellikle 1260oCde 1 saat sre ile sinterlenen numunenin optik grnts incelendiinde kk boyutlu tozlarn
olduu ksmlarda younlamann daha ok olduu, iri partikllerin evresinde ise balanmann daha az ve gzeneklerin daha iri olduu grlmektedir.
Bu durum bu tr malzemeler iin daha kk boyutlu tozlar kullanlarak daha yksek younluk deerlerine klabileceini dndrmektedir.
4. Sonular
Bu almada Toz Enjeksiyon Kalplama yntemiyle NI 625 tipi nikel esasl speralam tozlarndan para retimi
yaplm; yaplan deneysel almalardan aadaki sonular karlmtr.
1.
ok bileenli bir balayc sistemi kullanlarak NI 625 speralam tozundan baarl bir ekilde para
retimi gerekletirilmitir.
2.
Yaplan boyut dalm analizi sonularna gre toz partikl boyutunun 3,7 ila 26,7m arasnda olduu,
bu toz partikllerinin %50sinin 11,1 m boyutunda olduu tespit edilmitir.
3.
Balayclar sisteme baarl bir ekilde dhil edilmi ve uygulanan bir dizi ilem sonrasnda sistemden
baarl bir ekilde uzaklatrlmtr.
4.
Balaycs giderilen malzemeler DSC, TGA ve Dilatometre analizlerine tabi tutulmulardr. DSC analizine gre malzemenin 1298oC civarnda ergimeye balad grlmtr. Dilatometre testinden elde edilen eriye
gre 1190oC civarnda malzemede bzlmenin balad ve bu durumun 1300oCnin biraz zerine kadar devam
ettii tespit edilmitir.
5.
Farkl scaklklarda gerekletirilen sinterleme ilemlerinde 1300oCye kadar scaklk artna paralel olarak younluk deerleri artm ve en yksek younluk deeri 8,415 g.cm-3 olarak bu scaklkta elde edilmitir. Bu scakln zerindeki sinterlemelerle younlukta d olduu grlmtr. Artan sinterleme scaklnn malzemenin
tane yapsnn irilemesine yol at gzlenmitir.
TEEKKR
NI 625 tozlarnn temini konusundaki desteklerinden dolay Osprey Co. (UK) Firmasna teekkr ederiz.
206

KAYNAKLAR
1. V. M. Kryachek, Injection Moulding (Review), Powder Metallurgy and Metal Ceramics, cilt: 43, sayfa: 78,
2004.
2. Z. Zhong, K. Ramesh, S. H. Yeo, Grinding of nickel-based super-alloys and advanced ceramics, Mater Manuf Process 16 (2), sayfa:195207, 2001.
3. M. J. Cieslak, The solidification behavior of an alloy 625/718 variant, Proceedings of the International
Symposium on the Metallurgy and Applications of Superalloys 718, 625 and Various Derivatives, Pittsburgh, Pennsylvania sayfa: 7180, 1991.
4. H. K. Kohl, Thermal stability of the superalloys Inconel 625 and Nimonic 86, Journal of Nuclear Materials,
cilt: 101, sayfa: 243250, 1981.
5. V. L. Tellkamp, M. L. Lau, A. Fabel, and E. J. Lavernia, Thermal spraying of nanocrystalline inconel 718,
Nanostructured Materials, cilt: 9, sayfa: 489492, 1997.
6. Kyung H. Chung, Jongsang Lee, Rodolfo Rodriguez, and Enrique J. Lavernia, Grain Growth Behavior of Cryomilled Inconel 625 Powder During Isothermal Heat Treatment, Metallurgical and Materials Transactions
A, cilt: 33A, sayfa: 125134, 2002.
7. A. SIMCHI, Densification and Microstructural Evolution during Co-sintering of Ni-Base Superalloy Powders,
Metallurgical and Materials Transactions A, cilt: 37A, sayfa: 2549, 2006.
8. J.J. Valencia, J. Spirko, and R. Schmees, Sintering Effect on the Microstructure and Mechanical Properties of
Alloy 718 Processed by Powder Injection Molding, Superalloys 718, 625, 706 and Various Derivates, E.A.
Loria, ed., TMS, Warrendale, PA, sayfa: 753762, 1997.
9. J.J. Conway, M.S. Sperber, and F.J. Rizzo: Advances in Powder Metallurgy and Particular Materials, MPIF,
Princeton, NJ, blm 8, sayfa: 123137, 2002.
10. H. Wohlfromm, A. Ribbens, J. Maat, and M. Blomacher, Proc. Eur. PM2003 Congr. Exhib., Powder Injection
Moulding, European Powder Metallurgy Association (EPMA), Shrewsbury, U.K., sayfa: 20715, 2003.
11. A. Bose, J. J. Valencia, J. Spirko, and R. Schmees Powder Injection Molding of Inconel 718, Advances in
Powder Metallurgy and Particulate Materials, (MPIF, Princeton, NJ, sayfa: 1809918112, 1997).
12. K.F. Hens, J.A. Grohowski, R.M. German, J.J. Valencia, and T. McCabe, Processing of Superalloys via
Powder Injection Molding, Advances in Powder Metallurgy and Particular Materials, (MPIF, Princeton,
NJ, sayfa: 137148, 1994).
13. P. J. VERVOORT, R. VETTER and J. DUSZCZYK, Overview of Powder Injection Molding, Advanced Performance Materials 3, sayfa: 121151, 1996.
14. R. M, GERMAN, Sintering Theory and Practice, Wiley-Interscience, 1996, Newyork, USA.
15. R. M. GERMAN, Powder Metallurgy and Particulate Materials Processing, 2005, USA.
16. John L. Johnson, Lye King Tan, Pavan Suri and Randall M. German, Mechanical Properties and Corrosion
Resistance of MIM Ni-Based Superalloys. presented at PM2Tec2004, Chicago, IL (June 1417, 2004).
207

BLYEL TME YARDIMIYLA LE KARBON NANOTP RETM

mer GLER, Ertan EVN, Mustafa AKSOY
Frat niversitesi Metalurji ve Malzeme Mhendislii Blm, Elaz
zet
Bu almada tme ilemi yardm ile karbon nanotp (KNT) retilmitir. Bu amala ncelikle katalizr olarak
kullanmak zere nano boyutlu demir tozu retilmitir. kincil adm olarak ise saf grafit tozlar 5 saat yksek enerjili
tme ilemine tabi tutularak nano karbon tozu elde edilmitir. Bu ilemlerden elde edilen tozlar belirli oranlarda
kartrldktan sonra 1400 oC de argon atmosferi altnda tavlanmtr. Elde edilen numuneler zerinde XRD ve
HR-TEM incelemeleri yaplmtr. ncelemeler sonucunda aplar 15-30 nm arasnda deien karbon nanotpler
tespit edilmitir.
Anahtar Kelimeler: Karbon nanotp, Bilyeli tme
CARBON NANOTUBE PRODUCTION ASSISTED BY BALL MILLING

mer GLER, Ertan EVN, Mustafa AKSOY
Frat University, Metallurgy and Materials Engineering Department, Elaz
Abstract
In this study, carbon nanotubes were produced assisted by ball milling process. For this aim, firstly nano-sized iron
powder was produced as a catalyst. Secondly, pure graphite powders were ball milled in a high energy ball mill for 5
h to attain nano carbon powders. These powders obtained from the process were mixed at the different proportions
then annealed at 1400 oC in Ar gas. Then, samples were investigated by X-Ray diffraction (XRD) and High Resolution Transmission Electron Microscopy (HR-TEM). As a result of the investigations, carbon nanotubes with diameter
varying from 15 to 30 nm were determined.
Keyword: Carbon nanotube, Ball Milling
1.GR
Karbon nanotpler (KNT) ilk kez Iijima tarafndan kefedilmitir ve o tarihten itibaren pek ok aratrmac KNT in
zelliklerini anlamak ve yksek kalitede nanotpler retebilmek iin saysz aratrmalar yapmtr [1]. Elektrik ark
boalm, kimyasal buhar ktrme (CVD), sol-jel gibi pek ok yntem kullanlarak KNT in retimi baar ile gerekletirilmitir [2]. Y.Chen ve arkadalar ise yaptklar almalarda KNT in tlm grafit tozlarnn tavlanmas
ile retilebileceini ortaya koymulardr [3]. KNT in bymesini kontrol etmek ve yksek kalitede KNT retebilmek
iin artlarn optimize edilmesi gerekir ve bu durum oluum mekanizmasnn anlalabilmesi iin gayet nemli bir
husustur. CVD veya elektrik ark boalm gibi KNT retiminde ok kullanlan metotlardaki temel oluum mekanizmas; karbon atomlarnn uygun artlar altnda tek tek dizilmesi ile nanotp oluturmas esasna dayanr. Y. Chen
208

ve arkadalar mekano-termal yntem ile KNT retiminde oluum mekanizmasn; 150 saat tme ilemine tabi
tutulmu ve tme ilemi sonunda eilmi-kvrlm grafit tabakalarnn 1000-1500 oC gibi bir scaklkta tavlanmas
sonucunda KNT e dnt eklinde belirtmektedirler. Ayn aratrmaclar 1000 oC in altnda ise kristallemenin
ok az olmas sebebiyle hi nanotp olumadn belirtmektedirler [3-4]. X.H. Chen ve arkadalar ise yaptklar
almada grafitin 150 saat tlmesi ve 1400 oC scaklkta tavlanmas sonucu eitli alarda eilmi, kvrlm
grafit tabakalar gibi eitli nano yaplarn ortaya ktn rapor etmilerdir [5].
Daha nceki almalarmzdan, 5. ulusal nanobilim ve nanoteknoloji kongresinde sunulan almamzda mekanotermal yntem ile karbon nanotp retimi aratrlm ve 5 saat tme ilemi sonunda karbon naotpler sentezlenmitir [6]. Belirtilen almada sentezlenen tplerin aplar 50-200 nm arasnda deimektedir. Bu almada ise
elde edilen karbon nanotplerin aplar 15-30 nm ye kadar drlmtr.
2.DENEY ALIMALARI
Daha nceki almamzda deneyler sonucu kaln nanotpler elde edildii giri ksmnda belirtilmiti. Bu almada
ise elde edilen nanotplerin aplarn kltmek amacyla nano boyutlu katalizr kullanlmasna karar verilmitir. Bu
sebeple yaplan deneyler iki admda gerekletirilmitir. lk adm; nano boyutlu demir tozu retimi, ikinci adm ise
karbon nanotp retimidir.
Katalizr retimi iin, % 99,9 saflkta ve 30 m boyutundaki demir tozlar Fritsch Pulverisette 7 cihazda 3 saat tlmtr. Nano boyuta inen demir tozu 200 oC de 30 dakika tavlama ilemine tabi tutulmutur. Elde edilen tozdaki
yapsal deiimleri tespit etmek iin CuK mas yapan Bruker Advanced D8 marka X-n difraktometresi kullanlmtr. Ayrca demir tozu Jeol Jem 2100F marka yksek znrlkl geirmeli elektron mikroskobu (HR-TEM)
ile incelenmitir.
Deneyin ikinci aamasn karbon nanotp retimi kapsamaktadr. Bu amala; grafit tozlar (Merck kGAA, 99.5%,
<50 m) yksek enerjili bir deirmende tlmtr. Deneylerde kullanlan deirmen Fritsch Pulverisette 7 olup,
kullanlan kap ve bilyeler sertletirilmi sade karbonlu elikten imal edilmitir. tme deneylerinde bilye/toz oran
32/1 olarak seilmi ve deneyler 850 devirde gerekletirilmitir. Grafit tozlar 1/4, 2, 3, 4, 5 saat tme ilemine
tabi tutulmulardr. Ardndan, tlen numunelerdeki yapsal deiimleri tespit etmek iin X-n analizi alnmtr.
Bylece grafitin tamamen amorf hale geldii tme sresi tespit edilmitir. Tamamen amorflamann 5 saat tme ilemi sonunda gerekletii tespit edilmitir. deal tme sresinin tespit edilmesinin ardndan, homojen bir
karm salayabilmek iin 5 saatlik tme ileminin bitmesine 30 dakika kala almann ilk admnda retilen
nano boyutlu demir tozu kaba ilave edilmi ve tme ilemi 5 saate tamamlanmtr. tme ileminin ardndan, tozlar bir tp frn ierisinde 5.10-2 l/min lk argon gaz ak altnda 1400 oC de 4 saat tavlama ilemine tabi
tutulmulardr. Elde edilen numuneler Jeol Jem 2100F marka yksek znrlkl geirmeli elektron mikroskobu
(HR-TEM) ile incelenmitir.
3.SONULAR
Daha nceki almalarmz nda [6], nanotp retiminde katalizr olarak nano boyutlu saf demire ihtiya olduuna karar verilmitir, bu sebeple bu almann ilk admnda nano boyutlu demir tozu retilmitir. 3 saat sreyle
demir tozu tme ilemine tabi tutulmutur. Nano boyutlu demirin yeniden kristalleme scaklnda bir sre tavlandktan sonra aktif karbona katlmasna karar verilmitir. Bu sebeple elde edilen nano demir tozlar 200 oC de 30
dakika tavlama ilemine tabi tutulmutur. Bu ilemden sonra elde edilen tozun XRD analizi ekil.1 de verilmitir.
Debye-Scherrer (1) forml kullanlarak elde edilen demirin ortalama parack boyutunun 17 nm civarnda olduu
hesaplanmtr.
(1)
Ps parack boyutu, dalga boyu, FWHM full width at half-maximum, 1 ise krnm asdr.
XRD analizinde verilen demirin karakteristik pikleri incelendiinde bu piklerin ilem grmemi demir piklerine gre
geniliklerinin artt sylenebilir. Bu durum ise toz parack boyutunun azaldn ve kristal rgdeki i gerilmelerin
arttn tarif etmektedir.
209

ekil 1.tme ilemiyle retilen nano boyutlu demirin XRD analizi

ekil.2 de, retilen nano boyutlu demirden alnan HR-TEM grnts verilmitir. ekilde de grld gibi farkl
boyutlarda pek ok partikl bulunmaktadr. HR-TEM incelemelerinden tespit edildii kadaryla yapda ortalama
aplar birka nm den 20 nm kadar demir partiklleri bulunmaktadr.
ekil 2. tme ilemiyle retilen nano boyutlu demirden alnan HR-TEM grnts
Nano boyutlu demir retiminin ardndan grafit tozlarnn tlmesi ilemlerine geilmitir. tme ilemi uygulanm tozlar XRD incelemelerine tabi tutulmulardr. ekil 3. de 1/4, 2, 3, 4, 5 saat tme ilemlerine tabi tutulmu
grafit tozlarndaki deiim verilmitir. 1/4 saat tme sonunda grafitin (002) pikinde ciddi bir azalma meydana gelmitir. Ayrca, tmenin ilk 4 saatine kadar kristal rgye sahip grafit tozlarnn miktar artan sre ile azalmakta bu
sreden sonra ise kristal rgye sahip grafit tozlarnn miktar ihmal edilecek kadar kk miktarlara dmektedir.
Tozlarda meydana gelen deformasyonlarn artmas zaman ierisinde, nce grafit levhalar arasndaki zayf balarn
kopmasna, sonra her bir grafit levhasnda karbon atomlar arasndaki balarn krlmasna sebep olmakta ve sonu
yap amorf bir hal almaktadr.
ekil 3. tme sresinin artmasyla grafit tozunda meydana gelen XRD deiimi.
210

ekil 3 de grlecei zere 5 saat tme sonunda yapda demir karbr olumutur. tme ilemi sresince bilye
ve kaplardan kopan demir paracklar tme sresinin artmas ile beraber demir karbre dnmlerdir.
Bilyeler vastas ile tozlara yklenen enerji, tozlarn krlm ba saysn ve dolaysyla i enerjisini arttrmtr. Bu
tozlar i enerjilerini minimuma indirerek kararl hale gemek iin fazladan enerjiye ihtiya duymaktadrlar. Bu enerji
sl ilem sayesinde tozlara kazandrlmaktadr. 5 saat tme yaplm ve 1400 oC de 4 saat sl ilem grm
tozlar incelendiinde yapda aplar 15-30 nm arasnda olan nanotplerin olutuu grlmektedir (ekil.4.a ve b).
Oluan bu tplerin ok cidarl nanotpler olduu kolaylkla sylenebilir. Karbon nanotplerde boy/ap oran nemli
bir parametredir. ap kk boyu uzun nanotpler daha ok tercih sebebidir. ekil 4.a. incelendiinde boylar 0,5-1
m arasnda deien tpler grlmektedir. Oluan nanotplerin bir ksm karbon ktlenin alt ksmnda kalmtr.
ekil 4a,b: 5 saat tme yaplm ve 1400 oC de 4 saat sl ilem grm tozlarn HR-TEM grnts.
ekilde 4.b de grlen sa taraftaki koyu renkli blge karbon ktle olup, sol taraftaki ak renkli ubuk eklindeki
yap ise ok duvarl karbon nanotptr. Grlen nanotpn ap yaklak olarak 20 nm dir. Tpn dier ucu karbon
ktlenin altnda kaldndan dolay boyu konusunda kesin bir ey sylemek mmkn deildir. Karbon nanotpn grlen ksmnn uzunluu ise yaklak 300 nm dir. Nanotpn u ksmnda ise demir katalizr grlmektedir. Oluan
nanotpn bu katalizr zerinde gelitii aktr. Katalizr amal kullanlmak zere retilen nano demir tozlarnn
katlmad daha nceki deneylerden, aplar 50-200 nm arasnda olan karbon nanotpler elde edilmitir [6]. retilen katalizrn tlen toza katlmas sayesinde karbon nanotplerin aplar 20 nm civarna indirilebilmitir.
Nanotpler genellikle katalizr etkisi gsteren gei elementleri zerinde olumaktadrlar. ekil 4a ve b de grlen
nanotplerin oluumunda da bu katalizr etkinin sz konusu olduu dnlmektedir. zellikle mekano-termal
(tme ve sonrasnda sl ilem) yntemde demirin katalizr etkisi meydana getirdii hususunda literatrde rapor
edilmi almalar bulunmaktadr [8]. Bu dnceyi irdelemek amacyla bu ekirdek yaplar zerinden TEM teknikleri kullanlarak EDS analizi alnm ve bu sonular ekil 5 de verilmitir.
ekil 5: Karbon nanotpn zerinde gelitii ekirdekten alnan EDS analizi.

Elde edilen sonuca gre karbon nano tpn ucunda bulunan metal paracnn Fe olduunu sylemek mmkndr. Analizde tespit edilen dier elementlerden Cu nun TEM incelemesi iin kullanlan karbon elekten dolay, C
nin metal paracn yzeyi karbonla kapl olduundan dolay pikler verdikleri eklinde dnlmektedir. Si nin ise
sl ilem frnnda kullanlan almina tpn kapan izole etmekte kullandmz silikon contadan dolay ortaya
ktklar dnlmektedir.
211

Literatrde tme yoluyla karbon nanotplerin nasl olutuu konusunda kesin bir fikir olmamakla birlikte, bu
yntemle retim konusunda Avustralya Ulusal niversitesinden (ANU) Y.Chen, SLS ksaltmasyla tanmlad bir
oluum mekanizmasndan bahsetmektedir [4].
ekil 6. Kat halde karbon nanotp

oluumunun ematik gsterimi [4].
Bu mekanizmaya gre uygulanan sl ilem scaklnn karbonun bilinen yaplarnn dnm scaklnn altnda
olmasndan dolay bu scaklkta karbonun kat halde demirin ise sv fazda bulunmas sz konusudur. Bu yzden,
bu model Solid-Liquid-Solid (SLS) oluumu zerine oturtulmutur. Yksek miktarda kusurlar ihtiva eden eilmi
bklm grafenler ve amorf haldeki karbon tme ilemi ile ortaya kar ve bu yaplar kararsz yaplardr. Bu
yaplar sl ilem esnasnda yksek hareketlilik sebebiyle nanotpler gibi daha kararl olan ekle ve geometriye
dnmek isteyeceklerdir. Nano boyutta hatalar ihtiva eden ve dzensiz yapda olan zincirler ve halkalar nanotplerin
geliimi iin bir kaynak grevi grmektedir. Bu esnada sv fazda bulunan demir ise ideal bir ekirdek grevi grerek
nanotplerin geliimini salamaktr. Bu modelle ilgili olarak yazarn sunduu ematik resim ekil 6. da verilmitir.
ekilde M, metal nano parac temsil etmekte olup, nano hatalar ihtiva eden nano karbon tozlar tpn geliimi
iin bir kaynak oluturmaktadr. Bu modele gre amorf karbonla temas halinde bulunan Fe, sv evreye geerek
ierisinde znm halde bulunan karbonu yzey ksmna doru itmekte ve Fe paracnn yzeyinde oluan
karbon filmi ise amorf karbondan beslenerek nanotp oluturmaktadr.
4.GENEL SONULAR
Nano boyutlu demir tozu retebilmek iin demir yksek enerjili deirmende 3 sat tlmtr. Sonuta
-
ortalama boyutu 17 nm olan demir tozu elde edilmitir.
Grafitin 1/4, 2, 3, 4, 5 saat tme ilemine tabi tutulmutur. 5 saat tmenin ardndan yapnn tama-
men amorflat grlm, (002) piki tamamen kaybolmutur.
5 saatlik tme ileminin son yarm saatinde, daha nce retilen nano boyutlu demir tozlar kaba ek-
lenmitir.
Elde edilen tozun 1400 oC de 4 saat tavlama ilemine tabi tutulmasyla yapda karbon nanotpler olu-
mutur. Oluan tplerin aplar 15-30 nm civarndadr. Tplerin ularnda ise 10-15 nm civarnda demir partiklleri
mevcuttur.
5.KAYNAKLAR
Iijima S. Helical microtubules of graphitic carbon. Nature 1991; 354:56-8.
1.
2.
Terrones M, Hsu WK, Kroto HW, Walton DRM. Nanotubes: A revolution in materials science and electronics. Top Curr Chem, 199:189-34, 1999
Chen Y, Conway MJ, Fitz Gerald JD, Williams JS, Chadderton LT. The nucleation and growth of carbon
3.
nanotubes in a mechano-thermal Process. Carbon; 42:1543-48, 2004
Chen Y. Solid-state formation of carbon nanotubes. In: L. Dai, editor. Carbon Nanotechnology,
4.
UK;Elsevier; 53-58, 2006
Chen XH, Yang HS, Wu GT. Generation of curved or closed-shell Carbon nanostructures by ball-milling
5.
of graphite. J Cryst Growth 2000; 218:57-61.
Evin,E., Gler,.,Aksoy,M.Carbon Nano Tube Formation by Mechano-Thermal Process, 5th Nanosci6.
ence and Nanothecnology Conference, p.19, June 8-12, Eskiehir, 2009
Geng Y., Wang S.J., Kim K.J., Preparation of graphite nanoplatelets and graphene sheets, Journal of
7.
Colloid and nterface Science, vol.336, pp. 592-598, 2009
Chen Y, Conway M.J., Fitz Gerald J.D., Carbon nanotubes formed in graphite after mechanical grin8.
ding and thermal annealing, Applied Physics A, vol. 76, pp. 633-636, 2003
Surov D.V., Lomovsk O.I., Boldyrev V.V., Low- Temperature Crystallization of Mechanically Amorphi9.
zed Graphite Inorganic Material, vol. 42, pp.116-120, 2006
212

SNTERLEME PARAMETRELERNN MONEL 400 ALAIMI TOZUNDAN

RETLM PARALARIN MEKANK ZELLKLERNE ETKS
Sultan ZTRK*, Blent ZTRK*, Fatih ERDEMR* ve Yksel PALACI**
Trabzon, suozturk@ktu.edu.tr
**
Nide niversitesi, Mhendislik Fakltesi, Makine Mhendislii Blm, 51240, Nide, ypalaci@nigde.edu.tr
*
zet
Bu almada, sinterleme scaklnn ve sresinin 69 m ortalama boyuta sahip Monel 400 alam tozlardan retilmi paralarn mekanik zelliklerine etkisi incelenmitir. Yksek saflkta hidrojen gaz atmosferinde gerekletirilen
sinterleme ileminde, sinterleme scaklnn etkisini incelemek amacyla 1100, 1140, 1180 ve 1200 oC scaklklar
ve sinterleme sresinin etkisi iin 60, 75, 90 ve 105 dak. sreler kullanlmtr. Sinterleme ncesi Monel 400 alam
tozlarn yzey oksitleri hidrojen gaz atmosferinde indirgenmi ve sonrasnda tek eksenli ift etkili preste 600 MPa
sabit basnta preslenerek ham para haline getirilmitir. Deneysel sonular en optimum mekanik zelliklerin 1200
o
C scaklkta ve 90 dak. sinterleme sresinde elde edildiini ortaya koymutur.
Anahtar Kelimeler: Monel 400 Alam, Sinterleme Scakl, Sinterleme Sresi, Mekanik zellikler.
EFFECT OF SINTERING PARAMETERS ON THE MECHANICAL PROPERTIES OF SINTERED PARTS PRODUCED BY MONEL 400 ALLOY POWDERS
ABSTRACT
In this study, the effects of sintering parameters such as temperature and time on the mechanical properties of compacts produced by Monel 400 alloy powders which have mean particle size of 69 m have been investigated. The
sintering process was carried out in high purity hydrogen atmosphere by using temperatures of 1100, 1140, 1180
and 1200 oC and times of 60, 75, 90 and 105 minutes. The surface oxides of Monel 400 alloy powders were reduced
in hydrogen atmosphere before sintering and then the powders were pressed as green compacts with pressure of
600 MPa by using a uniaxial and double action pres. The experimental results showed that the optimal mechanical
properties were obtained with sintering temperature of 1200 oC and sintering time of 90 minutes.
Key words: Monel 400 Alloy, Sintering Temperature, Sintering Time, Mechanical Properties.
1.GR
Sinterleme, preslenmi ham haldeki paralarda birbirine temas eden tozlarn aralarnda ba oluturmas amacyla
yksek scaklkta uygulanan stma ilemidir. Sinterleme ile gzenekli yapdaki ham paradan gzeneksiz veya ok
dk oranda gzenekli para elde edilir. Sinterleme ilemi sonrasnda paralarn mukavemet deerlerinde nemli
artlar meydana gelir. Sinterleme ileminde tozlar arasnda balanma kat halde, ergime scaklnn altnda atomik
difzyon mekanizmasyla gerekleir. Kat hal sinterlemesi metal veya alamn ergime noktas altnda bir scaklkta
yaplan sinterleme ilemidir. Bu ilem, birbirine temas eden paracklarn yksek scaklklarda birbirine balanmasn salar. Bu balanma, ergime scaklnn altnda kat halde atom hareketleriyle oluabilir. Baz durumlarda sv
faz oluumu ile de gerekleebilir. Mikroyap leinde balanma, temas eden paracklar arasnda boyun oluumu
ile gerekleir [1-4].
Sinterleme ilemi difzyonla gerekleen bir ktle transferi olaydr. Uygun scaklk ve srede atomlarn yaynm
ile ktle transferi geekleir ve tozlar arasnda ba oluur. Bu adan sinterleme scakl ve sresi en nemli ilem
213

deikenleridir. Kullanlan tozun bileimine ve ortalama boyutuna bal olarak bu deikenler belirlenir. Kk paracklar yksek yzey enerjisine sahip olduklarndan, yksek scaklkta atomlarn yaynm ve kk paracklarn
yzey enerjilerinin azalmasyla sinterleme gerekleir. Tozlarda yzey enerjisi toz boyutuyla ters orantldr. Kk
boyutlu tozlar, byk boyutlu olanlara nazaran daha yksek yzey enerjisine sahiptirler ve daha hzl sinterlenirler.
Byk boyutlu tozlarn sinterlenmesinde difzyon mesafesinin uzamasndan dolay tam younlua ulamak iin
daha uzun sre sinterlemek gerekir [5,6].
Sinterleme balangcnda tozlar birbirleriyle noktasal temas halindedirler. Sinterleme ilemi ilerledike birbirine
temas eden paracklar arasndaki ba byr ve birleir. ki paracn tamamen birlemesiyle, ap balang
apnn 1,26 kat olan tek parack oluur. Kresel tozlarn temas noktalarna boyun ad verilir. Boyun blgelerinin
bymesi ile morfolojik deiimler balar. Boyun bymesi, birbiriyle temas eden tozlardan boyun blgesine doru
atomlarn difzyonu ile gerekleir. Tane snrlar ktle transferinin saland yerlerdir [1,3,7].
Sinterlemede ba oluumu, yzey difzyonu, tane snr difzyonu ve tane ii hacim difzyonu mekanizmalaryla
gerekleir. Yksek scaklklarda atomlar komularyla balarn koparp yeni yerlerine gidecek dzeyde enerjiye
sahip olurlar. Atomlarn hareket edebilmesi iin gerekli olan en dk enerjiye aktivasyon enerjisi denir. Kat hal
sinterlemesinin ilk aamasnda birbirinden bamsz olarak boyun bymesi grlr. Sktrlmam tozlarda temas
kk noktalar ile balar. Balangta gzenekler dzensiz ve keli ekillidir. Optimum sinterlemede gzenekler
kk ve yuvarlak biimde olmaldr. Tane snr difzyonu mekanizmas geliirken gzenekler tane snrlarnda
younlar. Tane snrlarna yerleen gzenekler tane bymesini engeller. Sinterlemenin ara aamasnda boyunlar
birbiri ile etkileerek byrler. Gzenekler yuvarlak ve dzgn hale gelmeye balarlar. Sinterlemenin ilerleyen aamalarnda taneler byr, gzenekler klr. Tane snr alanlarn azaltan gzenekler nedeniyle sistem enerjisinde
bir azalma olur. Tane snrlarndan daha yava hareket eden gzenekler tane bymesi esnasnda tane snrlar
tarafndan ya srklenir ya da yok edilirler [8,9].
Bu almada, sinterleme scaklnn ve sresinin Monel 400 alam tozlardan retilmi paralarn mekanik zelliklerine etkisi incelenmitir. Sinterleme ilemi yksek saflkta hidrojen gaz atmosferinde gerekletirilmitir. Frn
atmosferi bileimindeki hidrojen gaz oran %100 olarak alnmtr. Sinterleme scaklnn etkisini incelemek amacyla 1100, 1140, 1180 ve 1200 oC scaklklarda sinterleme gerekletirilmi olup, sinterleme sresi olarak 60, 75, 90
ve 105 dak. sreler kullanlmtr. Sinterleme ileminde Monel 400 alamndan su jeti soutmal dner disk atomizasyonu yntemiyle retilmi ortalama boyutu 69 m olan 125 m elek alt tozlar kullanlmtr. Bu tozlar sinterleme
ncesi tek eksenli ift etkili preste 600 MPa sabit basnta preslenerek ham para haline getirilmitir.
Bu almada, bileimi izelge 1de verilen Ni-Cu alam (Monel 400) kullanlm olup, bu alamdan su jeti soutmal dner disk atomizasyonu yntemiyle toz retimi yaplm, retilen tozlar tek eksenli ift tesirli preste preslenerek; ortalama toz boyutu, boyut dalm ve presleme basncnn ham younlua etkileri incelenmitir.
izelge 1. Monel 400 alam kimyasal bileimi (% A.)
Element
Ni
Cu
Mn
Fe
Si
66.8
31.45
1.33
0.97
0.38
0.1
0.013
0.002
Monel 400 alamndan toz retimi KT Metalurji ve Malzeme Mhendislii Blmnde mevcut bulunan su jeti soutmal dner disk atomizasyon nitesinde gerekletirilmitir. retilen 125 m elek alt Monel 400 alam tozlarnn ortalama boyutunun (d10), (d50 ) ve (d90) belirlenmesinde Malvern Mastersizer 2000 model parack boyut analiz
cihaz kullanlmtr. retilen paralarda younluk gradyannn olumamas iin presleme ncesi toz numuneler
Trbila tr bir kartrcda 30 dak. sre ile 55 d/d devir saysnda kartrlarak homojen bir dalm salanmtr.
Tozlarn presleme ncesi yzey oksitlerinin indirgenmesi ve preslenen paralarn sinterlenmesi amacyla 1300
C maksimum alma scaklna sahip atmosfer kontroll sinterleme frn kullanlmtr. Oksit indirgeme ve sinterleme ileminde %100 orannda yksek saflkta (%99,999 saflkta) hidrojen gaz kullanlmtr. Ortama hidrojen
gaz gndermeden nce azot gazyla sprme ilemi gerekletirilmitir. Yaplan ilemlerin tamam frn zerinde
bulunan PLC kontrol nitesi zerinde gerekletirilmitir. Tozlardaki yzey oksitleri 550 oC scaklkta 10 dak. sre ile
indirgeme ile temizlenmitir. ndirgeme ileminin tam olarak gerekleip gereklemedii XRD cihazyla yaplan faz
214

analizi ile kontrol edilmitir. Sinterleme scaklnn etkisini incelemek amacyla 1100, 1140, 1180 ve 1200 oC scaklklarda sinterleme gerekletirilmi olup, sinterleme sresi olarak 60, 75, 90 ve 105 dak. sreler kullanlmtr.
Hidrojen atmosferinde indirgenmi tozlardan ham younlukta para retmek amacyla PLC kontroll, tek eksenli ve
ift etkili 50 ton kapasiteli hidrolik toz kalplama presi kullanlmtr (ekil 1). Monel 400 tozlar ASTM 8M04 standardnda tel erozyon yntemiyle hazrlanm olan ekme numunesi kalbnda preslenmilerdir. Presleme basnc
600 MPa olarak sabit tutulmutur. Tozlarla kalp yzeyi srtnmesini en aza indirmek amacyla presleme ncesi
kalp ve zmba yzeyleri inko stearat ile yalanmtr.
retilen Monel 400 alam tozlarn morfoloji ve mikroyaplar ile tozlardan presleme ve sinterleme ile retilmi
paralarn mikroyap incelemeleri Zeiss EVO LS10 marka taramal elektron mikroskobunda (SEM) yaplmtr. Monel 400 tozlarnn morfoloji incelemeleri ift tarafl yapkan karbon band kullanlarak gerekletirilmitir. Yine ayn
tozlarn mikroyap incelemeleri iin tozlar, bir kalp ierisinde souk sertleen epoksi reine ile yataklandrlmtr.
Dalama ilemi, taze hazrlanan 8 g FeCl3, 25 mL HCl , 100 ml H2Odan oluan dalama ayrac kullanlarak 20
s srede gerekletirilmitir. SEM incelemeleri ncesinde, reine kalba yataklanm tozlar iletkenlik salanmas
amacyla altn kaplanmtr.
Preslenmi ve sinterlenmi numunelerin sertlik, akma dayanm, ekme dayanm ve yzde uzama gibi mekanik
zellikler incelenmitir. ekme zellikleri Instron marka ekme cihaznda 0,01 mm/s hzda ekme deneyleri yaplarak belirlenmitir. Mikro sertlik lmleri Struers Duramin marka cihazda en az 10 farkl noktadan 98,12 mN yk 10
s sreyle uygulanarak gerekletirilmitir. Makro sertlik lmleri Rockwell sertlik lm cihaznda 1/16 in bilya ile
10 kg n yk ve 60 kg esas yk artlarnda sertlik lmleri gereklemitir.
ekil 1. ift tesirli tek eksenli presin ematik resmi.

1-Kauuk ayak, 2- kolonlar, 3- klavuz silindir, 4- st silindir piston, 5- alt silindir, 6- pres tablas,
7- alt zmba ve kalp boluu, 8- st zmba, 9- PLC kontrol nitesi,
10- hidrolik devre elemanlar, 11- motor,
12- pompa, 13- hidrolik ya tank.
Bu almada sinterleme scaklnn ve sresinin etkisini incelemek amacyla, su jeti soutmal dner disk atomizasyonu yntemiyle retilen, 69 m ortalama boyuta sahip 125 m elek alt Ni-Cu alam (Monel 400) tozlar
kullanlmtr. retilen numunelerin tamam 600 MPa sabit basnta preslenmitir. Kullanlan Monel 400 tozlardan
215

deiik elek aralklarna ait SEM fotoraflar ekil 2de verilmitir. ekilden de grlebilecei gibi, tozlarn tamam
kresel ekilli olup, toz boyutuna bal olarak toz ekli deimemitir. Genellikle 90 mdan byk boyutlu olan
tozlarda yzeylerde ekilme boluu olumutur. Toz boyutu bydke ekilme boluu miktarnn artt tespit
edilmitir. ekilme boluklarnn nispeten byk apl tozlarda daha fazla olmas, toz boyutunun bymesiyle souma hznn azalmasna iaret etmektedir.

(a)
(b)
ekil 2. Monel 400 tozlar morfolojisi. a) -36/25 m elek aral, b) -125/90 m elek aral.
Sinterleme sresinin sinter younluuna etkisi, 1180 ve 1200 C scaklklar iin ekil 3te verilmitir. Artan sinterleme sresi ve scaklk artlarnda sinter younluunun artt gzlenmitir. Ham younluu %80 olan para iin 1180
Cde 60, 75, 90 ve 105 dak. sinterleme sreleri sonunda elde edilen younluk deerleri srasyla %84, %87, %91
ve %91 olarak elde edilmitir. Ayn srelerde 1200 C de sinterlenen %80 ham younluktaki numunelerin sinterleme younluklar srasyla %88, %91, %94 ve %93 olarak bulunmutur. Artan sinterleme sresiyle atomik difzyona
daha fazla zaman tannmakta ve younluk art meydana gelmektedir. Ancak, sinterleme sresi snrsz deildir.
Belli bir aamadan sonra ok uzatlan sinterleme sresinin younluk artrc etkisi grlmemektedir. Son aamada
gerekleen bu olayda tane snr enerjisinin azalmasndan dolay sinterleme ilemi yavalar. Baz durumlarda tane
bymesi gibi gzenek bymesi de oluabilir. Bu durumda gzenek says azalrken ortalama gzenek boyutu
artar. Bu yzden gereinden uzun tutulan sinterleme srelerinde kayda deer bir younluk art meydana gelmez.
1180 Cde 90 ve 105 dak srelerde yaplan sinterlemede elde edilen younluklar srasyla %91 ve %91 olarak
elde edilirken, 1200 C sinterleme scaklnda 90 ve 105 dak. sinterleme srelerinde elde edilen younluklar ise
srasyla %94 ve %93tr. Yukarda belirtilen sebeplerden dolay artan sre ile birlikte younlukta bir miktar azalma
meydana gelmitir.
ekil 3. Sinterleme sresinin sinter younluuna etkisi (presleme basnc 600 MPa).
Sinterleme sresinin sertlie etkisi, 1180 ve 1200 C scaklklar iin ekil 4de gsterilmitir. 1180 oC scaklkta 60,
75, 90 ve 105 dak. sinterlenen numuneler iin makro sertlik deerleri srasyla 61, 67, 72 ve 74 HRF olarak elde
edilmitir. 1200 Cde ayn srelerde yaplan sinterlemede elde edilen sertlikler srasyla 73, 75, 79 ve 76 HRFdir.
Artan sinterleme sresiyle sertliin artt aka grlmektedir.
216

ekil 5de sinterleme sresi ile ekme mukavemetinin deiimi grlmektedir. Buna gre; 1180 C scaklkta 60,
75, 90 ve 105 dak. sinterleme sreleri iin ekme mukavemeti deerleri srasyla 167, 202, 234 ve 258 MPa olarak
elde edilmitir. Ayn sinterleme srelerinde 1200 Cde sinterlenen numunelerin ekme mukavemeti deerleri ise
srasyla 211, 248, 259 ve 244 MPa olarak bulunmutur. Artan sinterleme sresiyle difzyona daha fazla zaman
salandndan tozlar arasnda daha gl ba oluumu salanm, gzenek saylar ve boyutlar azalmtr. Dier
taraftan, gereinden fazla sinterleme sresinin gzenek bymesine yol ap mekanik zellikleri olumsuz etkilemesi burada da ortaya kmtr. 1200 Cde 90 dakikalk sinterlemede 259 MPa ekme mukavemeti elde edilirken, 105
dak. sinterlemede ise bu deer 244 MPa olmutur. Sinterleme sresine bal olarak elde edilen mekanik zelliklerin
tamam izelge 2de verilmitir. Sinterleme sresiyle ekme mukavemeti ve kopma uzamasndaki deiim, 1180 C
ve 1200 C sinterleme scaklklar iin ekil 6 ve ekil 7de verilmitir.
ekil 4. Sinterleme sresi ile sertliin deiimi

(presleme basnc 600 MPa).
ekil 5. Sinterleme sresi ile ekme mukavemeti

deiimi.
ekil 7. Sinterleme sresiyle ekme mukavemeti ve

kopma uzamasnn deiimi
(sinterleme scakl 1200 C).
ekil 6. Sinterleme sresiyle ekme mukavemeti ve

kopma uzamasnn deiimi
(sinterleme scakl 1180 C).
izelge 2. Sinterleme sresine bal olarak mekanik zelliklerin deiimi.

Sinter.
sresi (dk.)
Sinterleme
younluu(%)
Akma mukavameti
(MPa)
ekme mukavameti
(MPa)
Uzama (%)
1180 C
1200 C
1180 C
1200 C
1180 C
1200 C
1180 C
1200 C
84
88
74
102
167
211
5,7
6,0
75
87
91
89
90
202
248
7,2
11,3
90
91
94
92
92
234
259
9,3
11,7
105
91
93
108
71
258
244
9,4
13,2
60
Sinterleme scaklyla sinter younluunun deiimi, 60 dakikalk sinterleme sresi iin ekil 8de verilmitir. 1100,
1140, 1180 ve 1200 C scaklklarda 60 dak. sinterlenen numuneler iin sinter younluklar srasyla %82, %83, %84
ve %88 olmutur. ekil 9da sinterleme scaklyla sertliin deiimi, 60 dakikalk sinterleme sresi iin verilmitir.
1100, 1140, 1180 ve 1200 C scaklklarda 60 dak. sreyle yaplan sinterlemede sertlikler srasyla 55, 58, 61 ve 73
217

HRF olarak gereklemitir. Artan sinterleme sresiyle sinter younluunda olan artla birlikte sertliin de artt
aka grlmektedir.
ekil 8. Sinterleme scaklyla younluunun

deiimi (sinterleme sresi 60 dakika).
ekil 9. Sinterleme scaklyla sertliin deiimi

(sinterleme sresi 60 dakika).
Sinterleme scaklyla ekme mukavemetinin deiimi, 60 dakikalk sinterleme sresi iin ekil 10da verilmitir.
1100, 1140, 1180 ve 1200 C scaklklarda yaplan sinterlemelerde ekme mukavemeti deerleri srasyla 126, 138,
167 ve 211 MPa olarak bulunmutur.
ekil 10. Sinterleme scaklyla ekme mukavemetinin deiimi.

Sinterlenmi numunelerde, sinterleme sresine bal olarak i yap deiimi, 1200 C sabit sinterleme scaklnda,
60, 75, 90 ve 105 dak. sreler iin, ekil 11-14de sunulmutur. ekillerden de grlebilecei gibi, 60 dakikalk
sinterlemede i yapda gzenek says yksek olup, sinterleme sresinin yetersizliinden dolay toz paracklar
arasndaki snr belirgin durumdadr. Srenin 75 dak. kartlmasyla gzenek miktarnda grlr bir azalma ve
toz tanecikleri arasndaki snr, tam olarak yok olmasa da, ok byk oranda azalm durumdadr. 90 ve 105 dak.
sinterleme srelerinde elde edilen i yaplarda ise tane snrlarnn tamamen ortadan kalkt, gzeneklerin ise
kreselletii grlmektedir. 90 dak. sinterlenen paradaki gzenek miktar 105 dak. sinterlenen paraya gre
daha fazla iken, 105 dak. sinterlenen numunedeki gzeneklerin, nispeten uzun olan sinterleme sresinden dolay
birleerek byd anlalmaktadr.
ekil 11. 1200 oC scaklkta sinterlenen numunede

sinterleme sresi ile i yapnn

218



4. SONULAR
Yaplan deneysel almalardan ve elde edilen bulgularn deerlendirilmesinden elde edilen sonular aada
verilmitir:
1. retilen Ni-Cu alam (Monel 400) alam tozlarn tamam kresel ekilli olup toz boyutuna bal olarak toz ekli
deimemitir. 90 mdan byk boyutlu tozlarda yzeylerde ekilme boluu olutuu gzlenmitir. Toz boyutu
bydke ekilme boluu miktarnn artt tespit edilmitir.
2. Monel 400 alamndan retilen tozlarnn yzeylerindeki ince oksit film tabakasnn yksek saflkta (%99,999
saflkta) hidrojen atmosferinde 550 0C scaklkta 10 dak. sre ierisinde indirgendii anlalmtr.
3. Artan sinterleme sresi ve scaklk artlarnda sinter younluunun artt gzlenmitir. 1180 C sinterleme scaklnda optimum sinterleme sresi 105 dakika olurken, 1200 C iin bu sre 90 dakika olarak tespit edilmitir.
4. Artan sinterleme sresiyle sertlik ve ekme mukavemeti deerlerinde artlar gzlenmitir. Sertlik ve ekme
mukavemetinin sinter younluuyla doru orantl olarak deitii tespit edilmitir.
5. 90 ve 105 dakika sinterlenen numunelerden elde edilen i yaplarda tane snrlar tamamen ortadan kalkt,
gzeneklerin ise kreselletii tespit edilmitir. Gzeneklerin, 105 dakikalk sinterlemede nispeten uzun olan
sinterleme sresinden dolay birleerek byd gzlenmitir.
KAYNAKLAR
1. German, R.M., Toz Metalurjisi ve Parackl Malzeme lemleri eviri Editrleri: S. Sarta, M. Trker, N. Durlu,
Trk Toz Metalurjisi Dernei Yaynlar:05, 2007,Ankara.
2. Yamaguchi, K., Takakura, N., Imatani, S., Compaction and Sintering Characteristics of Composite Metal
Powders, Journal of Materials Processing Technology, 63, 364-369, 1997.
3. German, R.M. Sintering Theory and Practice, Wiley-Interscience Publications, New York, 1996.
4. Narasimhan, K.S., Sintering of Powder Mixtures and The Growth of Ferrous Powder Metallurgy, Materials
Chemistry and Physics, 67, 56-65, 2001.
5. Missiaen, J.M., Solid-State Spreading and Sintering of Multiphase Materials, Materials Science and Engineering A, 475, 2-11, 2008.
6. Liu, S., Zhang, H., Hu, J., Effect of Carbusintering on Densification Behavior and Mechanical Properties of Fe2%Ni-x%Cu Alloys, Materials Design, 32, 3686-3691, 2011.
7. Okuyama, K., Sintering, Hiroshima University, Higashi-Hiroshima, Japan,2007.
8. Wang ,Y.,U., Computer Modeling and Simulation of Solid-State Sintering: A Phase Field Approach, Acta Materialia, 54, 953961, 2006.
9. Ji, C.H., Loh, N.H., Khor, K.A., Tor, S.,B., Sintering Study of 316L Stainless Steel Metal Injection Molding Parts
Using Taguchi Method: Final Density, Materials Science and Engineering A, 311, 7482, 2001.
219

RENE TR VE ELYAF UZUNLUUNUN FREN BALATALARININ

MEKANK VE TRBOLOJK ZELLKLERNE ETKS
Blent ZTRK* ve Sultan ZTRK*
*
Karadeniz Teknik niversitesi, Mhendislik Fakltesi, Metalurji ve Malzeme Mhendislii Blm,

61080, Trabzon, bozturk@ktu.edu.tr
zet
Bu almada, reine tr ve elyaf uzunluunun otomotiv fren balatalarnn mekanik ve tribolojik zelliklerine etkileri incelenmitir. Srtnme deneyleri, Chase tipi srtnme-anma deney dzeneinde yaplmtr. Elde edilen sonulardan hem reine trnn hem de elyaf uzunluunun balata malzemelerinin
mekanik ve tribolojik zellikler zerinde etkisi olduu grlmtr. Reine tr dikkate alndnda MR
ve SR kodlu numuneler srasyla en dk ve en yksek srtnme katsays gsterirken CR ve MR
kodlu numuneler en dk ve en yksek anma direnci gstermitir. Ayrca artan elyaf uzunluuyla da
numunelerin srtnme katsaylar derken anma dayanmlar artmtr. almada balata malzemelerinin anma yzeyleri ve anma paracklar da incelenmitir.
Anahtar Kelimeler: Balata, Srtnme, Anma, Reine Tr, Elyaf Uzunluu.
EFFECTS OF RESIN TYPE AND FIBER LENGTH ON THE

MECHANICAL AND TRIBOLOGICAL PROPERTIES OF BRAKE
FRICTION MATERIALS
ABSTRACT
In this study, the effects of resin type and fiber length on mechanical properties and friction characteristics of automotive brake materials were studied. The friction tests were performed using a Chase type
friction tester. The results showed that both resin type and fiber length played an important role on the
mechanical and tribological properties of the friction materials. The highest and the lowest friction coefficient for resin types were recorded for series SR and series MR composites, respectively, while the
series MR and CR composites showed the highest and the lowest wear resistance, respectively. For the
fiber length considered, increasing the fiber length increased the wear resistance of the composites. The
morphological features of worn surfaces and wear debris of the composites were analyzed.
Keywords: Brake Pad, Friction, Wear, Resin Type, Fiber Length.
1. GR
Srtnme malzemelerinin (balata) balca uygulama alanlar debriyaj ve fren balatalardr. Bu malzemeler ok bileenli kompozit malzemeler olup deien scaklk, hz, basn ve evre artlarnda kararl bir
srtnme katsaysna, dk anma, yeterli dzeyde mukavemete ve alma esnasnda grlt ve titreim oluturmama gibi zelliklere sahip olmas istenir [1-5]. Bu nedenle balatalarn performanslar kendilerini oluturan bileenlerin zelliklerine baldr. Gnmzde balatalarda kullanlan bileen says 700
220

n zerinde olmasna ramen bu bileenler 4 ana grupta toplanr. Bunlar balayclar, elyaflar, dolgu
malzemeleri ve srtnme dzenleyicilerdir [6-8]. Balayc malzemeler veya balayclar, balata bileenlerini bir arada tutan malzemelerdir [7]. Elyaflar, balataya mukavemet, tokluk ve sl kararllk salarlar.
Dolgu malzemeleri, balatann maliyeti drmek amacyla katlr ve balatann hacmini arttrmak zere
kullanlrlar. Srtnme dzenleyici malzemeler ise balatann srtnme-anma davrann deitirmek
zere kullanlrlar. Balatay oluturan bileenlerin birletirilmesi ve bu bileenlerin ortaya koyduklar sinerjik etki, balatann performansn nasl etkileyeceini tam olarak bilmek olduka zordur [9].
Modifiye edilmi ve edilmemi fenolik reineler, balatay oluturan bileenleri iyi slatmas ve maliyetinin
de dk olmas nedeniyle genellikle fren malzemelerinde balayc olarak kullanlrlar. Ancak fenolik
reine neme ve scakla kar duyarldr. Yksek sl kararlla ve oksitlenme direncine sahip reine
seimi balatann feyd (artan scaklkla birlikte srtnme katsaysnda dme) dayanmn etkiler [7, 10].
Fenolik reine dndaki reineler maliyetlerinin nispeten yksek olmas nedeniyle balata retiminde
genellikle tercih edilmemektedirler [7].
Fren balata malzemelerin retiminde farkl elyaflar kullanlmaktadr. Bu elyaflarn tr ve oranlar balatann srtnme performans ve anma miktar zerine olduka etkilidir. zellikle volkanik kayalardan
elde edilen Lapinus elyaf, dier balata bileenleriyle birlikte kullanldklarnda balatann feyd dayanm
arttrmtr. Aramid elyaf, ta yn ve cam elyafla birlikte balatalarda kullanldnda balatann yksek scaklklardaki srtnme performansn gelitirmi ve daha karal srtnme katsays ortaya koymutur [1].
Son yllarda yaplan almalarda, balatann performansna elyaf hacim orannn, elyaf ynlenmesinin
ve elyaf trnn etkileri incelenmi ancak elyaf uzunluunun etkisi tam olarak ortaya konmamtr [11].
Bu nedenle bu almann amac hem reine trnn hem de elyaf uzunluunun balatann performansna etkisini incelemektir. Srtnme performans deneyleri Chase tipi srtnme test dzeneinde SAE
J661 standardna uygun olarak yaplmtr.
2.1. Numune retimi
almada incelen numuneler asbest iermeyen organik trde (NAO) olup reine, elyaf, yalayc, andrc, dolgu malzemesi ve srtnme dzenleyici iermektedir. Her bir numune grubunda matris malzemesi olarak farkl tr reine (dz fenolik reine, kaju fst kabuu svs (CNSL) ile modifiye edilmi
fenolik reine ve melamin reine) kullanlmtr. Takviye edici malzeme olarak kullanlan elyaflarn kodlar ve uzunluklar ise srasyla RB215, RB260, RB280 ve 15025 m, 30050 m, 650150 m dir. Elyaf
ap yaklak 9 m dir. Balata retiminde kullanlan bileenler ve bu bileenlerin arlk oranlar izelge
1 de verilmitir. Balata numuneleri seri (SR, CR ve MR) halinde retilmitir. Numune retiminde hem
reine tr hem de elyaf uzunluu deiken olarak alnm, balata bileenleri ise btn numunelerde
ayn oranda sabit tutulmutur. Balatay oluturan bileenler 0,1 mg hassasiyetle tartldktan sonra bir
kartrc ierisinde 3-4 dakika sreyle kartrld. Karm daha sonra 150 oC scaklk, 15 MPa basnca
sahip bir kalpta 15 dakika sreyle tutularak sertletirildi. Sertlemenin tamamlanmas iin numuneler
180 oC scakla sahip frnda 4 saat sreyle tutuldu. retilen numuneler daha sonra talal ileme tabi
tutularak deneylere hazr hale getirildi.
izelge 1. Numune bileenleri ve oranlar.
221

almada kullanlan reinelerin sl analizleri Seiko II Exstar 6000 termal analiz cihaznda azot atmosferinde ve 20 oC/dak stma orannda yaplmtr. ekil 1(a-c), reinelerin TG ve DTG erilerini gstermektedir. ekilden grld zere dz fenolik reine (SR), CNSL modifiyeli reine (CR) ve melamin
reinenin (MR) ekzotermik reaksiyonlar srasyla 154, 159 ve 152 oC dir. Ayrca bu reinelerin ayrma
scaklklar da srasyla yaklak olarak 550, 431 ve 408 oC de meydana gelmitir.
(a)
(b)
(c)
ekil 1. Reinelerin TG ve DTG erileri: (a) dz fenolik reine;
(b) CNSL modifiyeli fenolik reine; ve (c) melamin reine.
2.2. Fiziksel ve Mekanik zelliklerin llmesi
Numunelerin fiziksel (younluk) ve mekanik zellikleri (sertlik, eilme, kesme ve darbe mukavemetleri) ilgili standartlara gre tespit edildi. Numune sertlikleri ASTM D785-03 standardna uygun olarak
Rockwell sertlik test makinesinde ve M skalasnda tespit edildi. Eilme, kesme ve darbe mukavemet
deerleri srasyla ASTM D790, ASTM D732 ve ASTM D256 standartlarna gre gerekletirildi. Btn
deneyler oda scaklnda yapld. Eilme ve kesme mukavemet deerleri Instron marka niversal test
makinesinde yapld. Darbe deneylerinde kullanlan ekicin arl ise 15 J dr.
2.3. Test Cihaz ve Test artlar
Srtnme performans deneyleri SAE J661 standardna uygun olarak Chase tipi test cihaznda gerekletirildi. Test cihaz ekil 2 de verilmitir. Cihaz numune tutucu, tambur ve kontrol nitesi olmak zere
3 ana ksmdan olumaktadr. Srtnme deneylerinde kullanlan numune boyutu 25x25x7 mm dir. Srtnme performans deneyleri izelge 2 de verilen test artlarnda yaplmtr.
ekil 2. Srtnme test

dzenei (Chase tipi).
222

izelge 2. Test artlar.
Srtnme deneyleri yanma, dzenleme, birinci altrma, birinci yorma, birinci toparlama, anma, ikinci
yorma, ikinci toparlama ve ikinci altrma ksmlarndan olumaktadr. zgl anma miktar, birim srtnme ii bana anan balata hacmi olup aadaki formlle bulunmutur [11].

(1)
Burada; m numune arlk kayb (anma deneyinden nce ve sonra numunedeki arlk kayb), L kat
edilen toplam yol, numune younluu, Fn ise uygulanan yktr.
Numune anma yzeyleri ve anma paracklar ZEISS marka taramal elektron mikroskobunda, anma parack boyutu ise Malvern Mastersizer 2000 cihaz kullanarak tespit edildi.
3.1. Fiziksel ve Mekanik zellikler
Balata numunelerinin younluk, sertlik, eilme, kesme ve darbe mukavemet deerleri izelge 3 de
verilmitir.
izelge 3. Numunelerin fiziksel ve mekanik zellikleri.
izelge 3 den grld zere numunelerin sertlik deerleri artan elyaf uzunluuyla birlikte dmtr.
Maksimum sertlik deerleri hem reine tr hem de elyaf uzunluu gz nne alndnda CR kodlu
numunelerde elde edilmitir. Eilme mukavemeti genellikle artan elyaf uzunluuyla artmtr. Literatrde
yaplan almalar incelendiinde ksa elyaf takviyeli kompozitlerin eilme mukavemet deerleri artan
elyaf uzunluuyla artt grlr [11, 12]. En yksek ve en dk eilme mukavemet deerleri srasyla
CR ve MR kodlu numunelerde elde edilmitir. Bununla birlikte CR kodlu numuneler maksimum kesme
mukavemet deeri gsterir. Numunelerin kesme mukavemetleri genellikle hem SR kodlu hem de CR
kodlu numunelerde artan elyaf uzunluuyla artarken, bu iliki MR kodlu numunelerde grlmemitir.
Ayn elyaf uzunluklar dikkate alndnda en yksek darbe mukavemet deeri SR kodlu numunelerde
elde edilirken, CR ve MR kodlu numunelerde bu deerler yaklak olarak ayndr.
3.2. Srtnme Performans
Numunelerin srtnme katsaylarnn artan scaklkla (II-yorma) deiimi ekil 3 (a-c) de verilmitir.
SR1, SR2, SR3 kodlu numunelerin deney balangcndaki srtnme katsaylar 0,45, 0,44, 0,45, CR1,
CR2, CR3 kodlu numunelerin 0,44, 0,45, 0,43 ve MR1, MR2, MR3 kodlu numunelerin 0,43, 0,42 ve 0,39
dur. Deney sonucunda bu deerler srasyla SR1, SR2, SR3 kodlu numuneler iin 0,49, 0,47, 0,47, CR1,
CR2, CR3 kodlu numuneler iin 0,48, 0,47, 0,45 ve MR1, MR2, MR3 kodlu numuneler iin 0,41, 0,41 ve
0,40 olarak elde edilmitir.
223

(a)
(b)
c
ekil 3. Numunelerin srtnme katsaylarnn scaklkla deiimi: (a) SR; (b) CR; ve (c) CR.
ekil 3 (a-c) de grld gibi, numunelerin srtnme katsaylar deneyin balamasyla birlikte artan
scaklkla kayma ara yzeyindeki gerek temas alanndaki deiimler nedeniyle artmtr. Numunelerin
srtnme katsaylar, deneyin balamasyla birlikte artmasnn nedeni birincil temas platolarnn oluumu ve buna bal olarak da gerek temas alanlarnn artmasdr. Platolar, disk ile temas alanlar olup
birincil ve ikincil platolar olmak zere iki ksmdan oluur. Birincil platolar balatann daha yksek anma
dayanmna sahip, mekanik olarak kararl ve anmaya direnli bileenlerinden oluur. kinci safhada
ise bu bileenler ikincil platolarn olumas ve bymesi iin ekirdeklenme yeri olutururlar. Anma
paracklar yer yer birincil platolarn arkasna skarak birikir ve ikincil platolar olutururlar [13, 14].
Deney balangcndaki srtnme, matris-disk eklinde olurken artan deney sresi ve scaklkla birlikte
matrisin giderek anmasyla elyaf paracklar yzeye kmakta, srtnme arlkl olarak elyaf-disk
ekline dnmektedir.
SR ve CR kodlu numunelerin srtnme katsaylarnda deney sresinin art ile birlikte yaklak 345
C disk scaklna kadar nemli bir dme olmad iin bu numunelerin yksek scaklk feyd dayanmlar olduka iyidir. Ancak MR kodlu numunelerin srtnme katsaylar, artan deney sresi ile birlikte
275 oC disk scaklna kadar artmakta ancak bu scakln zerinde keskin bir ekilde dmektedir.
Bu numunelerin feyd dayanmlar ktdr. Bu melamin reinenin bozunma scaklnn dk olmas
nedeniyledir.
o
SR, CR ve MR kodlu numunelerin ortalama srtnme katsaylar ekil 4 (a-c) de verilmitir. Ortalama
srtnme katsays, farkl ilem basamaklarndan alnan 10 srtnme katsays deerinin ortalamasdr.
Bu deerler srasyla birinci toparlama esnasnda 204 ve 149 oC, ikinci yorma esnasnda 232, 260, 288,
316 ve 343 oC ve ikinci toparlama esnasnda 260, 204 ve 149 oC dir.
224

(a)
(b)
c
ekil 4. Numunelerin ortalama srtnme katsaylarndaki deiim: (a) SR; (b) CR; ve (c) MR.
SR ve CR kodlu numunelerin ortalama srtnme katsays deerleri artan elyaf uzunluuyla dmtr.
Ancak MR kodlu numunelerde ise belirli bir deiim elde edilmemitir. Ayn elyaf uzunluklar dikkate alndnda maksimum ve minimum ortalama srtnme katsays srasyla SR ve MR kodlu numunelerde
elde edilmitir. 150 m elyaf uzunluunda ortalama srtnme katsaylar SR1 ve MR1 kodlu numunelerde srasyla 0,494 ve 0,468 olarak bulunmutur.
Bu deerler 300 m elyaf uzunluklarnda SR2 ve MR2 kodlu numunelerde 0,481 ve 0,441 ve 650 m
elyaf uzunluklarnda ise SR3 ve MR3 kodlu numunelerde 0,472 ve 0,444 olarak elde edilmitir.
Elyaf takviyeli kompozitlerde eer elyaf kompozit malzemeyi yeteri kadar desteklemez ve mukavemet
kazandrmazsa, matris malzemesi kar yzey zerinde mevcut przler tarafndan mikro kazma ve
mikro kesme ilemine tabi tutulur. Bunun sonucunda matris malzemesinde daha fazla anma olur.
Matris grevini yapamazsa kayma esnasnda oluan srtnme kuvveti numunedeki elyaflar krmadan
direkt olarak onlar yapdan kopartr.
Kopan bu elyaflar ara yzeyde andrc ve kazyc olarak hareket eder bu ise muhtemelen hem srtnme katsaysn hem de zgl anma miktarn arttrr. (ekil 5a). Nispeten daha uzun elyaflarda
anma daha zor meydana gelir. Balangta elyaflar yapdan kopmadan yava yava anmaya balar
ve elyaflarda incelmeyle birlikte kopmalar meydana gelir. Kopan elyaflarn bir ksm anma yzeyinden
ayrlrken geri kalan ksm ise belirli bir sre ikincil platolar oluturarak kompozit malzemeyi desteklemeye devam eder. Belirli bir zaman sonra mevcut elyaf btnyle kopar ve andrc olarak ilevini
yapar. Ancak bu andrclk, ksa elyafla karlatrldnda nispeten daha dk oranda meydana
gelir. (ekil 5b) [11, 15].
225

(a)
(b)
ekil 5. Numunelerin anma yzeylerin SEM grntleri: (a) CR1; ve (b) CR3.
Numunelerin srtnme katsaylarnn frenleme saysyla deiimi ekil 6 (a-c) de verilmitir. ekil 6a
da grld gibi, SR kodlu numunelerin srtnme katsaylar beinci frenlemeye kadar artmtr. Srtnme katsays otuzuncu frenlemeye kadar dm ve bu deerin zerinde yaklak olarak sabit kalmtr. ekil 6b de ise CR kodlu numunelerin srtnme katsaylar onuncu frenlemeye kadar artmtr.
Bu deerden sonra yaklak otuzuncu frenlemeye kadar benzer ekilde dm ve bu deerden sonra
yaklak olarak sabit kalmtr. MR kodlu numunelerde ise MR1 kodlu numune hari hem MR2 hem de
MR3 kodlu numunelerde artan frenleme ile birlikte srtnme katsaylar yaklak olarak sabit kalmtr.
MR1 kodlu numune ise deneyin balangcndan yirminci frenlemeye kadar srtnme katsays dmekte, bunun zerindeki frenleme saysnda srtnme katsays sabit olmaktadr (ekil 6c).
(a)
(b)
c
ekil 6. Srtnme katsaysnn frenleme says ile deiimi: (a) SR; (b) CR; ve (c) MR.
226

3.3. Anma Oran

Anma genellikle scaklk, hz, basn, evre artlar ve numune-kar yzey arasndaki etkileim gibi
faktrlere baldr. Balatalarn anmasna, balatada oluturan reine, elyaf ve srtnme dzenleyiciler
gibi bileenler etki ederler [6, 16]. Numune gruplarnn zgl anma oranlar ekil 7 (a-c) da verilmitir.
ekilde grld zere, reine tr dikkate alndnda CR kodlu numune grubu en yksek zgl anma oranna sahiptir. SR kodlu numune grubu ise zgl anmas CR kodlu numunelere gre nispeten
daha dk, MR kodlu numuneler ise en dk zgl anma oranna sahiptir.
(a)
(b)
ekil 7. Numunelerin
zgl anma miktarlar:
(a) SR; (b) CR; ve (c) MR.
c
Elyaf uzunluklar gz nne alndnda artan elyaf uzunluu ile birlikte numunelerin genellikle zgl
anma miktarlar azalmtr. Bunun nedeni ise ksa elyaflarn kayma esnasnda matristen daha kolay
ayrlmasdr.
3.4. Anma Yzeylerin ve Anma Paracklarnn SEM Analizi
SR1, CR1 ve MR1 kodlu numunelerin anma yzeylerinin grntleri ekil 8-10 da verilmitir. ekil
8 (a-b) de grld gibi, SR1 numunesi birincil ve ikincil platolara ilaveten anma yzeyinde toz
anma paracklar mevcuttur. Ayrca numune anma yzeyinde anm fakat kopmam elyaflar da
bulunmaktadr.

(a)
(b)
ekil 8. SR1 kodlu numunenin anma yzeyinin SEM grnts: (a) X500; ve (b) X2000.
227

ekil 9 (a-b), CR1 kodlu numunenin anma yzeyini gstermektedir. SR1 kodlu numuneyle kyaslandnda CR1 kodlu numunenin anma yzeyinde daha fazla oranda krlm ve kopmu elyaflar, daha
fazla elyaf-matris ayrlmas mevcuttur. Krlm ve yzeyden ayrlm olan elyaflar kar yzey przlln artrmakta bunun sonucunda artan kar yzey przll ise kazma etkisiyle zgl anma
miktarn artrmaktadr [17].

(a)
(b)
ekil 9. CR1 kodlu numunenin anma yzeyinin SEM grnts: (a) X500; ve (b) X1000.
MR kodlu numunelerin mekanik zellikleri, dier numunelere gre daha dk olmasna ramen en
dk zgl anma deeri gstermitir. ekil 10 (a-b) de grld gibi numune anma yzeyi, daha
byk boyutta ikincil temas platosuna sahiptir. Ayrca, SR1 ve CR1 kodlu numunelerle kyaslandnda
MR1 kodlu numunenin anma yzeyinde az oranda krlm ve yzeyden ayrlm elyaflar mevcuttur.

(a)
(b)
ekil 10. MR1 kodlu numunenin anma yzeyinin SEM grnts: (a) X500; ve (b) X500.
Anma deneyi srasnda olumu anma paracklar ve bu paracklarn boyut dalm ekil 11-13
de verilmitir. Bu paracklarn incelenmesi de anma mekanizmalarnn ortaya konmas ve yzey etkileimi asndan nemlidir [18].

(a)
(b)
ekil 11. SR1 kodlu numunenin (a) anma paracklarnn SEM grnts; (b)Parack boyut dalm.
228


(a)
(b)
ekil 12. CR1 kodlu numunenin (a) anma paracklarnn SEM grnts; (b)Parack boyut dalm.

(a)
(b)
ekil 13. MR1 kodlu numunenin (a) anma paracklarnn SEM grnts; (b)Parack boyut dalm.
Anma paracklar genellikle krlm ve daha sonra yzeyden kopmu elyaf paracklarndan, numune yzeyindeki tabakalardan ve kar yzeyden kopan anma paracklarndan oluur. Bu paracklar,
kar yzeyin numune yzeyine temas etmesiyle hemen yzeyden ayrlabilir veya tabaka eklinde bir
sre yzeyde kalabilir. Dk anma direnci gsteren SR1 ve CR1 kodlu numunelerin anma parack
ekilleri, MR1 kodlu numuneye gre olduka kresel ve birka plaka eklindedir. Yksek anma direnci
gsteren MR1 kodlu numunenin anma paracklarnn ekli ise genellikle plaka ve az da olsa kreseldir. SR1, CR1 ve MR1 kodlu numunelerin ortalama anma parack boyutlar srasyla 2,609 m, 2,521
m ve 4.822 m dir.
4. SONULAR
almada reine tr ve elyaf uzunluunun fren balatalarnn mekanik ve tribolojik zelliklerine etkisi
incelenmitir. Srtnme performans deneyleri Chase tipi srtnme test dzeneinde gerekletirilmitir.
Yaplan mekanik ve tribolojik deneylerden aadaki sonular elde edilmitir.
1. Numunelerin mekanik ve tribolojik zellikleri arasnda direkt bir iliki yoktur. Numunelerin anma
oranlar srtnme katsaylaryla ilikilidir.
2. En dk ve en yksek srtnme katsays MR ve SR kodlu numunelerde elde edilirken, MR ve CR
kodlu numuneler en yksek ve en dk anma direnci sergilemitir.
3. Numunelerin srtnme katsaylar ve zgl anma oranlar genellikle artan elyaf boyuyla azalmtr.
4. Uzun elyaf takviyeli numunelerin mekanik zellikleri genellikle ksa elyaf takviyeli numunelerden daha
fazladr.
TEEKKR
Bu alma, Karadeniz Teknik niversitesi BAP Birimi 2007.112.010.1 kodlu proje kapsamnda yaplmtr. Proje desteklerinden dolay Karadeniz Teknik niversitesine teekkr ederiz.
229

KAYNAKLAR
1. Satapathy, B.K., Bijwe, J., Fade and Recovery of Non-Asbestos Organic (NAO) Composite Friction Materials Based on Combinations of Rock Fibers and Organic Fibers, Journal of Reinforced
Plastics and Composites, Vol. 24, pp. 563-576, 2005.
2. Kim, S.J., Cho, M.H., Lim, D.S., Jang, H., Synergistic Effects of Aramid Pulp and Potassium Titanate Whiskers in the Automotive Friction Material, Wear, Vol. 251, pp. 1484-1491, 2001.
3. Kim, S.J., Lee, J.Y., Jang, H., Effect of Humidity on Friction Characteristics of Automotive Friction
Materials, KSTL International Journal, Vol. 2, pp. 150-153, 2001.
4. Ertan, R., Yavuz, N., An Experimental Study on the Effects of Manufacturing Parameters on the
Tribological Properties of Brake Lining Materials, Wear, Vol. 268, pp. 1524-1532, 2010.
5. Satapathy, B.K., Bijwe, J., Composite Friction Materials Based on Organic Fibers: Sensitivity of
Friction and Wear Operating Variables, Composites Part: A, Vol. 37, pp. 1557-1567, 2006.
6. Kim, S.J., Jang, H., Friction and Wear of Friction Materials Containing Two Different Phenolic Resins Reinforced with Aramid Pulp, Tribology International, Vol. 33, pp. 477-484, 2000.
7. Gurunath, P.V., Bijwe, J., Friction and Wear Studies on Brake-Pad Materials Based on Newly Developed Resin, Wear, Vol. 263, pp. 1212-1219, 2007.
8. Kumar, M., Bijwe, J., Role of Different Metallic Fillers in Non-Asbestos Organic (NAO) Friction
Composites for Controlling Sensitivity of Coefficient of Friction to Load and Speed, Tribology International, Vol. 43, pp. 965-974, 2010.
9. Gopal, P., Dharani, L.R., Blum, F.D., Fade and Wear Characteristics of A Glass-Fiber-Reinforced
Phenolic Friction Material, Wear, Vol. 174, pp. 119-127, 1994.
10. Bijwe, J., Nidhi, Satapathy, B.K., Influence of Amount of Resin on Fade and Recovery Behaviour of
Non-Asbestos Organic (NAO) Friction Materials, Transaction of the Indian Institute of Metals,
Vol. 57, pp. 335-344, 2004.
11. Zhang, H., Zhang, Z., Friedrich, K., Effect of Fiber Length on the Wear Resistance of Short Carbon
Fiber Reinforced Epoxy Composites, Composites Science and Technology, Vol. 67, pp. 222230, 2007.
12. Subramaniam, N., Sinha, B.R., Blum, F.D., Chen, Y.R., Dharani, L.R., Glass Fiber Based Friction
Materials, International Journal of Polymeric Materials, Vol. 15, pp. 93-102, 1991.
13. Eriksson, M., Jacobson, S., Tribological Surfaces of Organic Brake Pads, Tribology International, Vol. 33, pp. 817-827, 2000.
14. Nidhi, Bijwe, J., Mazumdar, N., Influence of Amount and Modification of Resin on Fade and Recovery Behavior of Non-Asbestos Organic (NAO) Friction Materials, Tribology Letters, Vol. 23, pp.
215-222, 2006.
15. ztrk, B., ztrk, S., Effects of Resin Type and Fiber Length on the Mechanical and Tribological
Properties of Brake Friction Materials, Tribology Letters, Vol. 42, pp. 339-350, 2011.
16. ztrk, B., Arslan, F., ztrk, S., Hot Wear Properties of Ceramic and Basalt Fiber Reinforced
Hybrid Friction Materials, Tribology International, Vol. 40, pp. 37-48, 2007.
17. Vishwanath, B., Verma, A.P., Rao C.V.S.K., Friction and Wear of A Glass Woven Roving/Modified
Phenolic Composite, Composites, Vol. 21, pp. 531-536, 1990.
18. Mosleh, M., Blau, P.J., Dumitrescu, D., Characteristics and Morphology of Wear Particles from Laboratory Testing of Disk Brake Materials, Wear, Vol. 256, pp. 1128-1134, 2004.
230

MECHANICAL
ALLOYING
www.turkishpm.org
231

The effect of reinforcement ratio on hardness of Al-Al2O3

composites fabricated by mechanical alloying technique
Aykut Canakci1, Temel Varol1, Saban Ertok1
Abstract
In this work, mechanical alloying technique was used to produce aluminum (Al) matrix composite reinforced with
alumina (Al2O3). A mixture of Al and 5, 10, 15 vol. % Al2O3 powders were milled in a high energy milling process.
The powder mixtures were milled in a planetary ball mill for different milling times of 0.5, 2, 5 and, 7 h. Ball mill velocity was 400 rpm and ball to powder weight ratio was 10: 1. Methanol was used as process control agent (PCA).
Mechanic alloyed composite powders were consolidated as compacts and sintering (under argon). Mechanical
alloying was followed by SEM, particle size and hardness. The results show that increase in volume fraction of reinforcement particles increases the work hardening, affecting structural evolution and hardness of the composites.
Moreover, The results show that physical properties of Al-Al2O3 composites depend strongly on milling time so that
increasing milling time causes to change the values of properties of composites.
Keywords: Mechanical alloying (MA); Aluminium-based metal matrix composites (Al-MMCs); Alumina (Al2O3)
1. Introduction
In recent years, alumium alloy based metal matrix composites are interested their importance for endustries like
automative and aerospace due to their engineered properties. Aluminum matrix composites (AMCs) are widely
used for light weight, unique mechanical properties [1,2]. MMCs can be formed from solid and molten states into
forging, extrusions, sheet and plate and casting. Conventional techniques like casting, spraying and forging have
problems like reinforcement segregation,unwanted interfacial chemical reactions, higher porosity and poor interfacial bonding. Due to the presence of alumina particles with high melting point, conventional melting and casting
is not suitable for producing dispersion-strengthened Al composites [3,4]. Alternatively, powder metallurgy ensures
the fine alumina dispersoid is well distributed within the Al matrix, which eventually gives good final mechanical
properties to the composite with sufficient physical properties. Mechanical alloying has also been employed to synthesize AMC. This method is relatively easy to produce composite powders with fine microstructure [5]. Mechanical
alloying (MA) that is a ball milling process where the powder particles are subjected to high energy impact have
been recently used in the production of aluminum base matrix composite. MA enables a uniform distribution of
the reinforcement particles into the aluminum matrix, the refining of the metal matrix and the fracturing of the hard
reinforcement particles [6].
The purpose of this study was to prepare Al-Al2O3 composite powder by mechanical alloying and to investigate the
influence of the milling time and the effect of reinforcement volume fraction on composite hardness and the structural evolution during MA.
2.1. Materials
The as-atomized Al alloy powders (Gndodu Exotherm Company, Turkey) with an average particle size of 377
m, Al2O3 powders (99,7 % purity, Wacker Ceramic Company, Germany) with an average particle size of 13 m
232

which varies between 5 m and 25 m and the density of 3.95 g/cm3 are used as raw materials. The chemical composition of the as-atomized Al alloy (in wt. %) is 1.230Fe, 1.000Si, 1.000Pb, 0.710Cu, 0.530Zn, 0.116Mn, 0.071Ti,
0.050Mg and Al (balance). Fig 1(a) and (b) shows the morphologies of the as received Al alloy matrix powder and
Al2O3 particles.
2.2. Milling
Composites powders of Al alloy matrix reinforced with different amount of Al2O3 (in vol. %5, %10 and %15) by highenergy ball milling for 0.5 h, 2 h, 5 h, and 7 h. The milling process was carried out in a planetary ball-mill (Fritshc
Gmbh, model Pulverisette Premium Line 7) at room temperature using tungsten carbide bowl and high argon
atmosphere. The milling medium was tungsten carbide balls, 10 mm in diameter. The ball-to-powder weight ratio
(BPR) and rotational speed were 10:1 and 400 rpm, respectively. A total of 1.75 wt. % of methanol (Merck) was
added to the ball-mill as process control agent (PCA). The milling atmosphere was argon which was purged into the
bowl before milling. To prevent over heating, ball milling experiments were stopped (every 0.5 h) and then resumed
when the temperature of the bowl decreased to the room temperature. Powders samples were withdrawn at time
intervals of 0.5, 2, and 5 h for morhological, microstructural and structural analyses.
2.3. Powder characterization
The size distribution of as-received and milled powders was quantified by a laser particle size analyzer (Malvern,
model Mastersizer Hydro 2000). The morphology and microstructure of raw and milled powders were investigated
by scanning electron microscopy (SEM) using Zeiss LS10. The microhardness of as-received and milled powders
was measured by a microhardness tester (struers microhardness tester) at 10 gr load.
2.4. Powder compaction
The as-received Al alloy powder, the conventionally mixed (CM) and the mechanically alloyed powders were uniaxially cold pressed in a cylindrical die at 500 and 700 MPa to block specimen with dimension of 30x20 mm, with
graphite as the die lubricant. The green compacts were sintered 600 oC for 3 h under high argon atmosphere. The
sintered compacts were cooled to room temperature in the sintering furnace.
2.5. Microscopic evaluation
To evaluate microstructure of produced composites the surface of samples were polished to achieve a rough surface of about 0.05 m. The microstructures of the conventially mixed and the milled Al alloy-Al2O3 composites were
examined by Zeiss scanning electron microscope.
3. Result and discussion
3.1. Particle size evaluation of milled powder
The effect of milling time on the particle size of ductile-ductile and ductile-brittle powders has been studied separately by previous authors [7-12]. The effect of milling time on the average particle size of monolithic Al alloy and Al
alloy-Al2O3 composite powders was shown in Fig. 2. Unlike most of the work related to mechanical alloying [13-16],
in this study, the particle size decreases continuously. This can be attributed to the initially used Al alloy powders
having ligamental shape. These powders can be easily deformed by high energy collisions at balls and they can be
233

easily fractured weakness regions. It should be noted that initial powder morphology is an important factor affecting
the change of the particle size. The average particle size (d0.5) of the monolithic Al alloy and Al-Al2O3 composites
powders were decreased same trend with increasing milling time (Fig. 2).
Fig. 2. The change of particle size of Al alloy and composite powders with milling time
The average particle size of the Al alloy-Al2O3 composite powders was lower than that of the Al alloy powders it was
reduced by increasing the reinforcement content. Indeed, the presence of the ceramic phase accelerates the rate at
which the milling process reaches completion. The presence of alumina particles increases local deformation which
improves the particle welding process. Beside this, the higher local deformation imposed by reinforcement particles
increases the deformation hardening, which helps the fracture process. The small hard brittle particles in the matrix
act as small milling agents, and thus the steady state the milling time is reduced. A similar behavior was observed
the ball milling of Al20 wt. % Al2O3 system [11] and Al-AlN system [9,10,17,18].
3.2. Milled powder characteristics

The as-received aluminum alloy matrix powders were irregular and ligamental shape (Fig. 1a). By continuing
milling process, these powders are deformed and transmitted to flatten and flake shapes and weld to each other.
Then these changes followed by fracture and rewelding, repeatedly [11]. After 0.5 h milling, the Al alloy powders
deform into a flake like shape (Fig. 3a). Due to ductile nature of the Al alloy powder, welding seems to be the
dominating mechanism over this stage of milling [7,10,11], and thus the 0.5 h milled particles have large size and
flattened shape (Fig. 3a). The large size and flatten shape like Al alloy powders are work hardened after 2 h milling,
hence fracture mechanism is activated (Fig. 3b).
Fig. 3. Morphology of the milled Al alloy powders for: (a) 0.5 h, (b) 2 h, (c) 7 h.
SEM micrographs of milled Al alloy powders showed that after 5 h milling, the morhology of Al alloy powders were
not completely equiaxed, which is the characteristic of Al alloy powders at steady state. Further milling up to 7 h has
no effect on the morphology (Fig. 3c); indeed at milling times longer than 5 h the steady state predominates.
The variation of Al alloy-Al2O3 powder shape during high energy ball milling as the function of milling time up to 7
h is shown in Fig. 4(ac). During the MA process, powders are subjected to high energy collision, which caused
severe plastic deformation, cold welding and fracturing of the powders. Plastic deformation and cold welding were
predominant during initial stage of high-energy ball milling, in which the deformation led to a change in particle
shape and cold welding led to an increase in average particle size. The addition of hard reinforcement particles
would accelerate the fracture process of the matrix powders, which was reported elsewhere [13]. The increased
234

fracturing tendency for high reinforcement was due to more collision with balls and more support from hard ceramic
particles [14]. In order to understand the effect of reinforcement ratio on the mechanical alloying process and composite properties, Al powders were milled with different amounts of Al2O3 (0, 5, 10, and 15 vol. %) for 0.5, 2, 5, and
7 h. If the presence of reinforcement results in a high deformation of the metallic matrix and advances the mechanic
alloying process, a higher reinforcement fraction will result in a still greater deformation of the metallic particles and
will accelerate the process even more. The reinforcement particles embedding into the Al powders during milling
lead to their fracture toughness reduction enhancing their fracture.
Fig. 4. Morphologies evolution of the Al alloy reinforced with different amount of Al2O3 (in vol. %5, %10 and %15)
by high-energy ball milling for 0.5 h, 2 h, 5 h, and 7 h: (a) 0.5 h, (b) 2 h, and (c) 7 h.
3.3. Microstructure
Fig. 5 shows the evolution of distribution of the Al2O3 particulates reaching milling time in the Al alloy matrix for
Al-Al2O3 composites.
Fig. 5. A schematic
view of the evolution of
distribution of the Al2O3
particulates reaching
milling time
in the Al matrix [19].
235

The main process which takes place in a mill during the MA method to produce quality powders with controlled
microstructure is the repeated welding, fracturing, and rewelding of a mixture of powders. The morphology of the
initial powders is modified when they are subjected to ball collisions [15]. Initial stages of MA, welding process
too much dominant than fracture because of that powders are exposed to high cold deformation. The presence
of reinforcement particles between the particles during welding increases local deformation in the around of the
reinforcement particle. An increase the local deformation improves the particle welding process and also increment
of reinforcement lead to improvement of fracture mechanism on continuous process. In other words, small hard
brittle particles in the mix act as small milling agents, with an improvement of the energy of the system. Therefore,
reducing the milling time necessary to achieve uniform dispersing of reinforcement particles. The effect of milling
time on the distribution of Al2O3 powders is investigated by SEM. Figs. 6-8 show the distribution of reinforcement
powders (5, 10, and 15 vol. % Al2O3) milled with different milling time (0.5, 2, and 7 h). SEM images show that most
of the reinforcement powders dispersed inside the Al matrix at the end of a long milling time while Al2O3 powders
werent showed a homogeneous distribution within the matrix in short milling time. In other words, the homogeneous distribution of the reinforcement powders provided with increasing milling time.
Fig. 6. Distribution of alumina particles of Al alloy-5 vol. % Al2O3 composites in the Al alloy matrix with milling time
after (a) 0 h, (b) 0.5 h, (c) 2 h, and (d) 7 h.
236

Fig. 7. Distribution of alumina particles of Al alloy-10 vol. % Al2O3 composites in the Al alloy matrix with milling
time after (a) 0 h, (b) 0.5 h, (c) 2 h, and (d) 7 h.
237

Fig. 8. Distribution of alumina particles of Al alloy-15 vol. % Al2O3 composites in the Al alloy matrix with milling time
after (a) 0 h, (b) 0.5 h, (c) 2 h,and (d) 7 h.
238

The particle distribution was not uniform at initial milling time (0 h, 0.5 h) and the distance between alumina particles
was too much. However, increasing milling time caused to fracture the brittle alumina powders and to embed them
into ductile Al powders. The distance between reinforcement particles decreases with increasing milling time (Figs.
6-8).
3.4. Hardness
The result of micro and macro-hardness for different milling time and different compact pressure is shown in Figs.
9-10. Micro and macro hardness values increases with increasing milling time and with the reinforcement content.
MA assists a high degree of deformation and reduces the grain size to finer level. As can be seen from figures,
increasing milling time fractures coarse powder particles into fine particles due to cold welding and plastic deformation. The rate of an increase in micro-hardness is high and becomes even greater after reaching 5h of milling.
The increase in hardness values can be explained more homogeneous distribution of reinforcement particles,
increasing work hardening decreasing grain size [10, 20-22]. In addition, as shown in the Figures; hardness values
increases with increasing compact pressure because of decreasing porosity. When particle morphology, particle
size and composite hardness examined it was observed that measurements done at the end of 5 and 7 h of milling
were close to each other. Based on this, it can be expressed mechanical alloying process reached virtually steadystate at the end of 5 h of milling.
Fig. 9. Micro-hardness of the Al alloy and composites versus milling time at different compact pressure (a) 500
MPa and (b) 700 MPa.
The Brinell hardness of the composites and matrix alloy was given in Fig. 10. It was seen from Fig. 10 that the
hardness of the composites increased with increasing particle volume fraction. As compared to the Al matrix alloy,
the hardness of the MMCs was found to be greater, and addition of Al2O3 particles increase the hardness of the Al
alloy [23-25].
Fig.10. Macro-hardness of the Al alloy and composites versus milling time at different compact pressure (a)
500 MPa and (b) 700 MPa.
239

4. Conclusion
In this work, Al2O3 reinforced Al alloy base composites were synthesized by mechanical alloying process. The milling time was varied from 0.5 h to 7 h while volume fraction was varied from 0% to 15%. Mechanical alloying appears
to be an ideal technique to produce composites in a variety of systems. The most impressive advantage of the mechanical alloying method is that a uniform dispersion can be succeed by optimizing the process parameters. It was
observed that higher hardness is obtained when volume fraction (reinforcement ratio) was increased. The results of
the macro-hardness measurements for Al-Al2O3 composites show a important increase in hardness as compared to
the unreinforced sample. Moreover, the average particle size, powder morhology, and hardness of properties of the
monolithic Al alloy matrix and the composites were reached virtually a steady state value at the end of 5 h of milling
tim by mechanical alloying process.
Acknowledgement
The authors are grateful to Karadeniz Technical University Research Fund for the financial supporting of this
research work (No: 2007.112.10.2 ). The researchers would also like to thank to Gundogdu Exotherm Service for
providing Al-alloy powders.
5. References
1. C. Padmavathi., Anish. Upadhyaya., Science of Sintering (2010) 42 363-382
2. C. Suryanarayana, Journal of Alloys and Compounds 529 (2010) 229-234
3. B. Prabhu, C. Suryanarayana, L. An, R. Vaidyanathan , Mater Sci Eng A (2006) 425:192-200
4-. G. ODonell, L. Looney, Mater Sci Eng A (2001) 303: 292301
5. S.M. Zebarjad, S.A. Sajjadi, Materials and Design 28 (2007) 2113-2120.
6. Grazziani Maia Candido, Vanessa Guido, Gilbert Silva, Ktia Regina Cardoso, Materials Science Forum Vols.
660-661 (2010) 317-324
7. Rodiguez A, Gallardo JM, Herrera EJ (1997) J of Mater Sci 32: 35353539
8. El-Eskandarany MS (2000) William Andrew Publishing, New York
9. Fogognolo JB, Velasco F, Robert MH, Torralba JM (2003) Mater Sci Eng A 342: 131143
10. Razavi Tousi SS, Yazdani Rad R, Salahi E, Mobasherpour, I Razavi M (2009) Powder Tech 192: 346351
11. Abdoli H, Salahi E, Farnoush H, Pourazrang K (2008) J of Alloys and Compounds 461: 166-172
12. Arik H, Turker M (2007) Mater and Design 28: 140146
13. Razavi Hesabi Z, Simchi A, Seyed Reihani SM (2006) Mater Sci Eng A, 428:159-168
14. Sivasankaran S, Sivaprasad K, Narayanasamy R, Vijay Kumar Iyer (2010) Powder Tech 201: 7082
15. Adamiak M (2008) J Achiev Mater Manuf Eng 31(2): 191196
16. Hashim J, Looney L, Hashmi MSJ (1999) J of Mater Process Tech 92:1
17. Fogognolo JB, Robert MH, Torralba JM (2006) Mater Sci Eng A 426: 8594
18. Fogognolo JB, Ruiz-Navas Elisa M, Robert MH, Torralba JM (2003) Mater Sci Eng A 355: 5055
19. L, Lu, M.O. Lai, C.W. Ng, Materials Science and Engineering A252 (1998) 203-211
20. I. Estrada-Guel, C. Carreno-Gallardo, D.C. Mendoza-Ruiz, M. Miki-Yoshida, E. Rocha-Rangel, R. MartinezSanchez, Journal of Alloys and Compounds 483 (2009) 173-177,
21. H. Arik, Materials and Design 25 (2004) 31-40,
22. E.M. Ruis-Navas, J.B. Fogagnolo, F. Valesco, J. M. Ruiz-Prieto, L. Froyen, Composites: Part A 37 (2006) 21142120,
23. Kok M (2005) J Mater Process Technol 161:381.
24. Purazrang K, Abachi P, Kainer KU (1994) Composites A 25(4):296.
25. A. Canakci, J Mater Sci (2011) 46:28052813.
240

PRODUCTION OF Al-[Al-Al3Ti] NANOCOMPOSITE

BY MECHANICAL ALLOYING AND TWO-STEP HOT PRESSING
Armin VAHID MOHAMMADI*, Hamid Reza MADAAH HOSSEINI**
* Department of Materials Science and Engineering, Sharif University of Technology, Tehran, Iran, arminvm@
gmail.com
** Department of Materials Science and Engineering, Sharif University of Technology, Tehran, Iran, madaah@
sharif.edu
ABSTRACT
Pure Al powder was mixed with 20 wt.% pure Ti powder to produce Al-Al3Ti composite powder by Mechanical Alloying (MA) for 12 hours. The produced composite powder was mixed with pure Al powder in 10, 15 and 20 wt.%.
Two-Step hot pressing was performed to produce Al-[Al-Al3Ti] bulk nanocomposites. The results show that effective
temperature range for first and second step of hot pressing was between 620 - 625 C and 570 - 585 C, respectively. Furthermore the highest density was achieved in the sample with 20 wt.% of pure Al.
Keywords: Al-Al3Ti, Nanocomposite, Hot Pressing, Mechanical Alloying
1. INTRODUCTION
Recent advances in producing nanostructured materials with novel material properties have stimulated research
to create multi-functional macroscopic engineering materials by designing structures at the nanometer scale. Motivated by the recent enthusiasm in nanotechnology, development of nanocomposites is one of the rapidly evolving areas of composites research [1]. According to this, recently most researches have focused on production of
composites and nanocomposites by using different sintering processes such as Hot Pressing, hot extrusion, and
hot isostatic pressing (HIP) [2]. Hot pressing is widely used in the manufacturing process of high strength materials
such as Al and Ti alloy and stainless steel [2-3]. However, grain growth occurs readily during the high temperature
consolidation of nanocrystalline materials [4,5], because nanocrystalline materials are thermally unstable. Thus,
the full benefit of nanocrystalline materials may only be preserved if the consolidated specimen maintains its nanosized grains. Two-Step Hot Pressing is a technique that in comparison to Single-Step hot pressing enables reaching
higher densities while controlling grain size [6,7].
Aluminum composites reinforced with trialuminide particles (Al3Ni, Al3Fe, Al3Ti, Al3Zr, etc.) possess high specific
strength, high specific modulus, and excellent properties both at ambient and elevated temperatures [7]. In comparison to most other aluminum-rich intermetallics, Al3Ti with higher melting point (~1623 K), relatively low density
(3.4 g/cm3) and high Youngs modulus (217 GPa; which are comparable with the properties of SiC) is the most considerable tri-aluminide for Al matrix composites [2,7,8]. Therefore, the presence of Al3Ti intermetallic phase is very
effective in increasing the strength and stiffness of aluminum composite and nanocomposites. The major strengthening mechanisms, which contribute to the high strength of AlAl3Ti alloys, have been suggested to include Orowan
strengthening mechanism, grain size strengthening, and load-shearing effects of Al3Ti particles [7-13].
In this research Mechanical Alloying was used to mix the Al and Ti powders and form the Al-Al3Ti composite nanopowder. Pure Al powder was added to the produced composite powder as a modification parameter to achieve a fully
dense structure. Furthermore, Two-Step hot pressing was performed to produce Al-[Al-Al3Ti] bulk nanocomposites
and effect of different parameters of hot pressing on the density of produced samples was investigated
241

Aluminum fine powder Merck (average particle size of 45-150 m) with 99.9% purity were mixed with 20 wt.% Titanium Powder Merck (average particle size of 10 m) with 99.9% purity by using mechanical alloying (High-energy
vibrating mill) for 12 hours. The produced Al-Al3Ti composite powder with average particle size of 100 nm was
degassed using a tunnel furnace in a vacuum atmosphere and again mixed with Pure Al powder in 10, 15 and 20
wt.%. Sample 1 consisted of 10% pure Al powder (9 g Al-Al3Ti + 1 g Al), Sample 2 had 15% pure Al powder (8.5 g
Al-Al3Ti + 1.5 g Al) and sample 3 had 20% pure Al (4 g Al-Al3Ti + 1 g Al).
Two-step hot pressing was performed for manufacturing the bulk nanocomposite by in situ reaction. In table 1 hot
pressing conditions for test samples have been shown. Hot press temperatures were chosen according to AlTi
binary phase diagrams, which would cause the formation of intermetallic phase Al3Ti [2]. Three different pressures
(110, 130, and 150 KN) at three different durations for first and second steps (10-30, 5-45, and 10-45 min) were
applied at the mentioned temperature. The pressing was performed by Gotech Testing Machines Inc. U60 with pressure rate of 3 mm.min-1. Apparent density measurement was performed according to ISO 3923-1:2008 standard
using Archimedes method and Theoretical density measerments was performed according to ASTM D854-92e1
standard using pycnometery method. SEM and EDS analysis were done by TESCAN VEGA scanning electron
microscopy and image analyzing was performed on SEM images.
Table 1. Two-Step Hot Pressing Conditions for samples.
Temperature (C)
Sample 1
Sample 2
Sample 3
Time (min)
First Step
625
10
Second Step
585
30
First Step
620
Second Step
570
45
First Step
620
10
Second Step
570
45
Pressure (MPa)/(KN)
339.5/110
462.9/150
401.2/130

Morphology changes of Al-Al3Ti composite powder is shown in fig. 1. SEM images taken in 1.5 and 12 hrs of
mechanical alloying showed that by increasing MAs time the morphology of composite powder changed from a
palette shape to a homogenous structure, while its size decreased. EDS data which are shown in fig. 2 proved the
formation of Al3Ti inter-metallic phase after 12 hrs of MA. Furthermore, Image analyzing on SEM images showed an
increase in volume fraction of this inter-metallic phase by increasing MA time.
Fig. 1. Morphological
changes of composite
powder. (a) after 1.5 hr
of MA (b) after 12 hr of MA.
242

Fig. 2. EDS data of composite powder after 12 hrs of MA which proves the formation of Al-Al3Ti intermetallic
phase.
In the following, effect of different parameters of Two-Step hot pressing on the density of the produced nanacomposites has been discussed.
3.1 Time and Temperature of First and Second Step of Hot Pressing
Table 2 shows the theoretical density and real density of produced samples. In the first step of two-step hot pressing due to higher temperature and more grain growth, decreasing time to a limit helps to produce a more dense
structure while keeping grain size in nano scale. Indeed in the first step the temperature range is near the melting
point of Al, so the growth rate of particles due to increasing of diffusion is very fast and decreasing time is a key
parameter to control the grain size of produced naonocomposite. In this research in the first step of hot pressing,
temperature (T1) range between 620 and 625 C in time period between 5 and 10 min was effective for achieving
higher densities while maintaining grain size in nano scale.
Table 2. Theoretical density and real density of produced samples.
Theoretical Density (g/cm3)
Real Density (g/cm3)
Density Percentage
3.0230
3.0050
2.9870
2.9287
2.8452
2.9006
96.68 %
94.68 %
97.1 %
Sample 1
Sample 2
Sample 3
In the second step of hot pressing, due to lower temperatures and slower grain growth, hot pressing duration
should be longer. In fact, according to Wang et al [6], second step temperature should be restricted within a range,
called the kinetic window, here the grain boundary or the volume diffusion operates while the grain boundary
motion is frozen. It is worthy to remark that the choice of temperature T2 is very important because the grain
growth may be generated when the setting T2 is too high; in contrary the densification is exhausted due to the
suppression of atomic diffusion and results in an incomplete densification. Therefore in this study effective temperature (T2) range for the second step was obtained between 570 and 585 C in duration of 30 to 45 min.
3.3 Hot Pressing Pressure
Both steps of hot pressing were performed at a constant pressure to minimize the probable sudden changes in
samples. In fig. 3 density percentage changes of samples vs. hot Pressing pressure is shown. As given in table 2
we see a few increase in the density of sample 3 which was hot pressed at 130 MPa compared to sample 1 that hot
pressed at 110 MPa. Meanwhile by increasing the pressure to 150 MPa in sample 2, we see a noticeable decrease
in the density. Although this decrease could be due to the other different factors, such as wt.% of secondary added
pure Al powder or sample weight (because of single-action hot pressing performed in this research) which are discussed in the following sections, it was concluded that the pressure had a effective range between 110 - 130 MPa
and increasing it more than an upper limit which was obtained 150 MPa would cause a less densification.
243

Fig. 3. Density percentage changes of samples to Hot Pressing pressure.

3.4 Secondary Added Pure Al Powder Wt.%
As indicated secondary added pure Al powder was used as a modification factor for reaching higher densities and
producing fully-dense Al-[Al-Al3Ti] bulk nanocomposite. The results given in table 2. with regard to samples hot
pressing conditions given in table 1. indicated that by increasing the amount of pure Al powder from 10 wt.% in sample 1 to 15 wt.% in sample 2 the density decreased. However, by increasing it from 15 wt.% to 20 wt.% in sample 3,
we see a increase in density which could be because of lower sample weight and also lower pressure.
3.5 Sample Weight
Due to single-action pressing used in this research, sample weight had very critical effect on the density of the produced samples. As given in table 2 we see an increase in the density of sample 3 while decreasing sample weight
from 10 g for sample 1 and 2 to 5 g for sample 3. This increase has happened in spite of decreasing the pressure
and increasing pure Al powder wt%, which means because of using single-action pressing, the decrease in the total
sample weight has caused this increase in the density despite of increased negative factors on the density. This also
proves the mentioned behaviors in the section 3.3 and 3.4.
3.5 Scanning Electron Microscopy (SEM) Analysis
Fig 4. shows the SEM images of sample 1. White phases in this SEM images represents Ti and dark gray phase
is Al. Also light gray phase which is mostly formed around Ti phase represents Al-Al3Ti intermetallic phase. In fig.
5. and 6. SEM images of sample 2 and 3 are shown. Also EDS analyses were performed to prove the formation of
Al-Al3Ti intermetallic phase in light gray regions. Fig. 7 shows the EDS dates of sample 3, analyzed point is marked
on the SEM image of sample 3 in fig. 6.
Fig 4. SEM images of sample 1. (a) Scale of 100 m (b) Scale of 20 m.
244

Fig. 7. EDS data of Sample 3 which proves the formation of Al-Al3Ti intermetallic phase in light gray regions.
4. CONCLUSION
The influence of time, temperature and pressure of tow-step hot pressing on density of Al-[Al-Al3Ti] nanocomposite
was investigated. SEM was utilized to study the morphology and structure of the different phases and EDS analysis
was performed to prove the formation of Al3Ti intermetallic phase. The conclusions derived from the results are as
follows.
Density measurements for samples revealed that for the first step of hot pressing, duration of 5 - 10 min at a temperature range between 620 - 625 C was effective for production of the bulk nanocomposite with a high density.
Also for the second step, duration of 30 - 45 min at a temperature range between 570 - 585 C proved to be a ideal
condition for maintaining the grain size at nano scale while reaching higher densities.
245

Furthermore, by increasing the hot pressing pressure from 110 to 130 MPa at different durations, the density gently
increased. Also for sample at 150 MPa, a considerable reduction was seen. The highest density achieved in sample
with 20 wt.% of secondary added pure Al. Moreover due to single action pressing, by decreasing sample weight
despite of an increase in the other negative factors, the density increased.
SEM images and EDS analysis proved the formation of Al3Ti intermetallic phase mostly around the Ti phase in the
bulk nanocomposites.
5. ACKNOLEDGEMENTS
The authors gratefully acknowledge Miss Sogol Palaseyed, RAZI research center and Ceramic laboratory of Sharif
University of Technology for their help and support of this research.
6. REFRENCES
1. Erik T. Thostenson, Chunyu Li, Tsu-Wei Chou, Nanocomposites in context, Composites Science and Technology, 65 (2005) 491516.
2. M. Nofar, H.R. Madaah Hosseini, N. Kolagar-Daroonkolaie, Fabrication of high wear resistant Al/Al3Ti metal
matrix composite by in situ hot press method, Materials and Design, 30 (2009) 280286.
3. K.T. Kim, H.C. Yang, Densification behavior of titanium alloy powder during hot pressing, Materials Science
and Engineering, A313 (2001) 4652.
4. H. Hahn, J. Logas, R.S. Averback, J. Mater. Res. 5 (1990) 609.
5. Kyoung Il Moon, Hee Sub Park, Kyung Sub Lee, Study of the microstructure of nanocrystalline Al5 at.% Ti
compacts prepared by reactive ball milling and ultra-high-pressure hot pressing, Journal of Alloys and Compounds, 325 (2001) 236244.
6. Chih-Jen Wang, Chi-Yuen Huang, Yu-Chun Wu, Two-step sintering of fine aluminazirconia ceramics, Ceramics International, 35 (2009) 14671472.
7. Karel Maca, Vaclav Pouchly, Pavel Zalud, Two-Step Sintering of oxide ceramics with various crystal structures,
Journal of the European Ceramic Society, 30 (2010) 583589.
8. S.S. Nayaka, S.K. Pabi, B.S. Murty, Al(L12)Al3Ti nanocomposites prepared by mechanical alloying: Synthesis
and mechanical properties, Journal of Alloys and Compounds, 492 (2010) 128133.
9. Nikitin VI, Wanqi JIE, Kandalova EG, Makarenko AG, Yong L., Preparation of AlTiB grain refiner by SHS
technology. Scripta Mater, 2000;42:5616.
10. C.J. Hsu, C.Y. Chang, P.W. Kao, N.J. Ho, C.P. Chang, AlAl3Ti nanocomposites produced in situ by friction stir
processing, Acta Materialia, 54 (2006) 52415249.
11. Feng CF, Froyen L. Acta Mater 1999;47:4571.
12. Wu JM, Zheng SL, Li ZZ. Mater Sci Eng A 2000;289:246.
13. Kwang-Min L, In-Hyung M. High temperature performance of dispersion-strengthened Al-Ti alloys prepared by
mechanical alloying. Materials Science and Engineering A, 1994, 185:165171.
246

THE EFFECT OF RARE-EARTH CATIONS ON THE STRUCTURAL

PROPERTIES OF BaFe12O19 HARD MAGNETS
Glten SADULLAHOLU*, Burcu ERTU*, Hasan GKE*, Baki ALTUNCEVAHR**, A. M. Ltfi VEOLU*
and Okan ADDEMR*
Istanbul Technical University, Metallugical and Materials Engineering,, 34469 Maslak,
Istanbul, Turkey, sadullahoglu@itu.edu.tr
*
Istanbul, Turkey, ertug@gmail.com
*
Istanbul, Turkey, gokceh@itu.edu.tr
**
Istanbul Technical University, Physics Engineering, 34469 Maslak, Istanbul, Turkey, altuncevahir@itu.edu.tr
*
Istanbul, Turkey, ovecoglu@itu.edu.tr
*
Istanbul, Turkey, addemir@itu.edu.tr
*
ABSTRACT
The samples of Ba0.85R0.15Fe12O19 (where R= Nd3+, Sm3+ and La3+ ions) were prepared by the solid state sintering using stoichiometric proportions of pure BaCO3, Fe2O3 and of R2O3 added compositions. The mixed powders
were milled for 10 h in toluen medium by using SPEX8000D with 1200 rpm. The pressed samples were sintered
at 1000oC for 1h and 5h and at 1250oC for 1 h under air. In the DTA analysis the onset temperature to form the
BaFe12O19 phase increased by inducing rare earths in barium hexaferrite composition. For the undoped sample reaction peak temperature is 985C and onset temperature is 800C corresponding to the formation of the BaFe12O19
phase. For the Sm, Nd and La substituted samples the onset temperatures are 880C, 850C and 900C respectively which are above that of the undoped composition.
Keywords: Barium hexaferrite, rare earth substitutions, mechanical alloying.
1. INTRODUCTION
Barium ferrite has a hexagonal crystal structure and fairly large uniaxial crystal anisotropy. There are five iron sublatices which are three octahedral (2a, 12k and 2b) and two tetrahedral (4f1 and 4f2) are coupled by superexchange
interactions through oxygen to form ferromagnetic structure [1,2]. The hexagonal c axis is the easy axis and the
crystal anisotropy constant K is 3.3x106 erg/cm3 or 330kJ/m3. The Ms is low, 380 emu/cm3 or or 72 emu/gr at room
temperature. The Curie point is 450oC. The hexagonal unit cell of barium ferrite contains 64 atoms, the Ba2+ and
O2- ions both are nonmagnetic, the only magnetic Fe3+ ions, each will a moment of 5 B. Of the 24 Fe3+ ions, 16 are
in one direction, 8 are arranged in the opposite direction, therefore, (16-8)(5)=40 B per cell or 20 B per formula.
This quantity corresponds to 100 emu/g and agrees axactly with the measured value of the saturation magnetization at 0 Kelvin [3,4].
Many researches have been performed to improve magnetic properties of MFe12O19 (M=Sr, Ba) ferrites by introducing di-tri- and tetravalent metal ions (Al, Mn, Co, Ti, Sn, e.c.) substituting to Fe3+ ions. Furthermore, in the early
investigations the occupation of the sublattice in the structure by trivelent RE ions (Nd3+, Sm3+, La3 or Pr3+) in stead
of Ba2+ or Sr2+ ions causes the valans change of Fe3+ to Fe2 on the 2a crystallografic sites where the strong Fe2
anisotropy leads to an increase in magnetocrystalline anisotropy or coercivity depending on the molar ratio of the
substitutional rare earth ion [5-13].
247

In order to extend these investigations the effects of RE cations (Nd3+, Sm3+ and La3+) were studied on the formation temperature of BaFe12O19 phase associated with the solubility properties of the substitutional additions in the
structure.
2. EXPERIMENTAL
A series of Ba0.85RE0.15Fe12O19 (RE=Nd,La and Sm) samples was prepared by mechanically alloying of the BaCO3,
RE2O3 , and Fe2O3 powders followed by heat treatment. The amounts of the prepared powder batches weighed in
a XB320M (PrecisaTM, Dietikon, Switzerland) sensitive balance were 56 g. MA experiments were carried out in
a vibrating ball mill SpexTM 8000 D Mixer/Mill,NewJersey,USA) with a speed of 1200 rpm in a hardened steel vial
(50 ml capacity) and hardened stainles steel balls with a diameter of 6.35mm (1/4 in.) with a ball-to-powder weight
ratio (BPR) of 10:1. Mechanical alloying duration was chosen 10 h. Toluene was used as the milling media to inhibit
agglomeration. At the end of the milling process, the wet powders were unloaded and toluene was vapourized
in the furnace at 200oC for 12 h under air. The dry powders were cold pressed into pellets with a diameter of 12
mm. Cold pressed samples were annealed for 1 h and 5 h at 1000oC, and for 1 h at 1250oC under air. Exothermic
and endothermic reactions were determined by DTA analysis by heating the as-blended and milled powders up
to 1200C with the heating rate of 10/min in air. The phase compositions of the milled powders and the sintered
samples were performed by X-ray diffraction (XRD) technique using a D8 Advanced Series Powder Diffractometer
(BrukerTM, Karlsruhe, Germany) with Cu-K (1.54060 A) radiation in the 2 range of 2080 with 0.02o steps at a
rate of 2/min. International Centre for Diffraction Data (ICDD) powder diffraction files were utilized for the identification of crystalline phases.
3. RESULTS AND DICSUSSION
Thermal Differential Analyses (DTA) of the stociometric MAd powders for 10 h are presented in Fig.1 The initial
exothermic peak was observed for the milled powders at about 250oC. This can be attributed the release of the cold
work energy in the system stored during the mechanical alloying process at low temperatures.
Figure 1. DTA patterns

of the MAd Fe2O3 and
BaCO3 powders for 10 h
with and without La, Sm
or Nd substitutions.
In the DTA thermograph of Fig.1, the curve belonging to the as-milled samples show an endothermic peak at
pertaining to the decomposition temperature of the precursors into the hexaferrite phase. For the undoped sample
endothermic peak temperature is 985C and onset temperature is 800C corresponding to the formation of the
BaFe12O19 phase. However, the other samples substituted with Sm, Nd and La the onset temperatures are 880C,
850C and 900C respectively which are above that of the undoped composition.
Table 1. Reaction onset temperature of the Fe2O3 and BaCO3 powders for 10 h with and without La, Sm or Nd substitutions.
Composition
Reaction onset temperature

(C)
BaFe12O19
800
Ba0.85La0.15Fe12O19
900
Ba0.85Nd0.15Fe12O19
850
Ba0.85Sm0.15Fe12O19
880
248

3.1. Effects of the substitutions on the structure

Figure 2 shows the XRD patterns of a series of Ba0.85RE0.15Fe12O19 (RE=Nd, La and Sm) samples and pure barium
hexaferrite revealing the peaks belonging to the Fe2O3 phase (Bravais lattice : Rhombohedral, space group : Rc; a
= b = 0.542 nm, c = 1.371 nm) and BaFe12O19 phase (Bravais lattice: simple hexagonal; space group: P63/mmc;
a = b = 0.586 nm, c = 2.309 nm). For all samples, the formation of the magnetic BaFe12O19 hard ferrite phase was
not completed after the heat treatment at 1000C for 1h. In the rare earth doped samples diffraction patterns show
lower intensities of peaks reflected from the BaFe12O19 phase. This can be attributed to the increase in the reaction
onset temperature of the rare earth added powders to form hexaferrite phase.
Figure 2. XRD patterns for the samples with Sm (a), Nd (b), La (c) substitutions and undoped Ba-hexaferrite
(d) sintered at 1000C for 1 h.
In Figure 3, diffraction peaks of the patterns reflected from BaFe12O19 hard ferrite and hematite (Fe2O3) phases
are more intense than those of the powders sintered at the same temperature for 1 h because of the grain growth.
But the hematite phase still exists in the structure of all the substances. Figure 3 shows the XRD patterns of these
samples substituted with Nd, Sm, La and pure Ba hexaferrite.
Figure 3. XRD patterns for the samples with Sm (a), Nd (b), La (c) substitutions and pure Ba-hexaferrite (d)
sintered at 1000C for 5 h.
249

Figure 4. XRD patterns for the samples with Sm (a), Nd (b), La (c) substitutions and pure Ba-hexaferrite (d)
sintered at 1250C for 1 h.
Figure 4 shows that after sintering at 1250C, a single BaM-type phase was obtained for all compositions. For the
pure barium hexaferrite, the diffraction peaks are more intense than those of the rare earth substituted samples.
The XRD patterns of the samples are in accordance with the DTA analysis, since the crystallization of the barium
hexaferrite phase starts at the lowest temperature of 800C and grain growth occurs for the undoped samples.
Therefore, the peak intensities are stronger than those of the rare earth added powders barium hexaferrite phase
which forms at the higher temperatures.
4. CONCLUSIONS
The effects of RE cations (Nd3+, Sm3+ and La3+) were studied on the formation temperature of BaFe12O19 phase by
using mechanical alloying method.
The onset temperature to start the formation of the BaFe12O19 phase increases by inducing rare earth additions in
barium hexaferrite composition. For the undoped sample endothermic peak temperature is 985C and onset temperature is 800C corresponding to the formation of the BaFe12O19 phase. However, the other samples substituted
with Sm, Nd and La the onset temperatures are 880C, 850C and 900C respectively which are above that of the
undoped composition.
The heat treatment of 1000C is not sufficient to form pure BaFe12O19 hard ferrite phase for all the samples. In the
XRD analysis, it was observed that for the rare earth doped samples diffraction patterns show lower intensities of
peaks reflected from the BaFe12O19 phase. This can be attributed to the increase in the reaction onset temperature
of the rare earth added powders to form hexaferrite phase. After sintering at 1250C, a single BaM-type phase was
obtained for all the compositions and it was observed that the XRD patterns of the samples are in accordance with
the DTA analysis. Since the crystallization of the barium hexaferrite phase starts at the lowest onset temperature
800C and grain growth is expected in the undoped samples while for the rare earth added powders barium hexaferrite phase forms at the higher temperatures.
REFERENCES
1. Z.F. Zi , Y.P.Sun, X.B.Zhu, Z.R.Yang, J.M.dai, W.H.Song, Structural and magnetic properties of SrFe12O19
hexaferrite synthesized by a modified chemical co-precipitation method, Journal of Magnetism and Magneric Materials, Vol. 320, pp. 2746-2751, 2008
2. R. Smomski and J.M.D. Coey, Permanent Magnetism, p.261, Bookcraft, UK, 1999
3. A. Goldman, Modern Ferrite Technology, p.104, 2nd edition, New York, USA, 2006
250

4. B. D. Cullity, C. D. Graham, Introduction to Magnetic Matreials, p.190,191,487 , John Wiley&Sons, New

Jersey, USA, 2009
5. H. Yamamoto, M. Nagakura, H. Terada, Magnetic properties of anisotropid Sr-La system ferrite magnets, IEEE Transactions on Magnetics, Vol. 26 (3), pp.1144-1148, 1990
6. A. Gonzales-Angeles, G. Mendoza-Suarez, A.Gruskova, R. Dosoudil, R. Ortega-Zempoalteca, Magnetic
Studies of Sn2+ - Sn4+ substituted barium hexaferrites synthesized by mechanical alloying, Materials Letters,
Vol. 58, pp.2906-2910, 2004
7. G.K. Thompson, B.J. Evans, Order-Disorder and Magnetic Exchange Interactions in Subsitututed Strontium
Hexaferrites SrAxFe12-xO10 (A=Ga, In), Journal of Applied Pyhsics, Vol.75, pp. 6643, 1994
8. G.Turilii, F.Licci, A.Paoluzi, NiTi substituted hexaferrites for magnetic recording, IEEE Transactions on
Magnetics, Vol.24 (4), pp. 2146-2149, 1988
9. G.Turilii, F.Licci, Anisotropy field measurement and magnetization reversal in (Co-Ti) substituted hexaferrites, IEEE Transactions on Magnetics, Vol.24 (6), pp. 2865-2867, 1988
10. H.Yamamoto, M.Isono and T. Kobayashi, Magnetic properties of BaNdCo system M-type ferrite fine particles prepared by controlling the chemical coprecipitation method, Journal of Magnetism and Magneric
Materials, Vol.295, pp.51, 2005
11. P. Sharma, R.A.Rocha, S.N.medeiros, B.Hallouche, A.Paesano Jr., Structural and magnetic studies on
barium hexaferrites prepared by mechanical alloying and conventional route, Journal of Magnetism and
Magnetic Materials, Vol.316 (2007) 29-33
12. S. Ounnunkad, Improving magnetic properties of barium hexaferrites by La or Pr substitution, Solid State
Communications, Vol.138, pp. 472-475, 2006
13. L. Lechevallier, J.M.Le Breton, A.Morel and P.Tenaud, On the solubility of rare earths in M-type SrFe12O19
hexaferrite compounds, Journal of Physics; Condensed Matterials, Vol.20, pp.175203, 2008
251

METALLIC
FOAM
www.turkishpm.org
252

TM YNTEMYLE BYK YZEY ALANLI METALK KPK

RETMNDE KPREBLRLK PROBLEMLER
Ersin BAHEC*, Yusuf ZATALBA** ve Mehmet TRKER**
* Kastamonu niversitesi, Cide Rfat Ilgaz M.Y.O. Kaynak Teknolojisi Blm, 37600, Kastamonu,
ebahceci@kastamonu.edu.tr
** Gazi niversitesi, Teknoloji Fakltesi, Metalurji ve Malzeme Mhendislii, 06500, Ankara, yusufoz@gazi.edu.tr,
mturker@gazi.edu.tr
ZET
Bu almada, byk kesit alanl (7500 mm2) kapal hcreli metalik kpk levhalarn toz metalurjisi yntemiyle retimi gerekletirilmitir. retim srecinde oluan problemler gzlenmi ve giderme areleri aratrlmtr. Al, %4 Si
ve % 1,2 TiH2 tozlar kartrlarak souk presleme, sinterleme, scak ekstrzyon ve scak/lk haddeleme ilemleri
uygulanarak kprtmeye hazr preform malzemeler retilmitir. Metalik kpk retiminde kullanlan byk boyutlu
preform levhalarn, frnda kprtme ilemi srecindeki etkileri incelenmi ve kprtme hatalar kategorize edilerek
sebepleri tartlmtr. Levha eklinde (250x250x30mm3) retilen metalik kplerin gzenek yaps ve gzenek oluumlar belirlenerek kprebilirlikleri kyaslanmtr. Kprtme srecindeki olumsuzluklar mimize etmek iin gelitirilen Yksek Enerji Metodu-X (YEM-X) ile endstriyel boyutlarda levha metalik kpk retimi gerekletirilmitir.
Anahtar kelimeler: Metalik kpk, Al kpk, Kapal hcreli, Kprebilirlik, Isl etki
Foamablity problems encountered during the production

of large surfaceD METALLIC FOAM by pm route
ABSTRACT
In this study large surfaced (7500 mm2) close cell metallic foams were produced by using PM route. The problems
encountered during production of such surfaced metallic foam were specified and tried to be solved. Al 4% Si,
1.2% TiH2 powders were mixed, cold pressed, sintered, extruded and then hot/warm rolled to produce foamable
precursor. During the foaming process, effect of large surfaced foams on the foamability behavior was instigated
and foaming problems were categorized and the reasons of problems were discussed. Pore formation and pore
structure of plate like foams (250x250x30 mm3) were determined and foamability behaviors were compared. In
order to minimize the problem encountered during the production of large surfaced industrial sized metallic foam
High Energy Method-X (HEM-X) was used and foams was produced successfully.
Keywords: Metalic Foam, Al Foam, Closed Cell, Foamability, Thermal Effect
1. GR
Metalik kpkler, iyi enerji absorbe zellii, yksek basma dayanm, dk zgl arlk ve yksek rijitlik gibi mekanik ve fiziksel zellikleri ile bilinir [1]. eitli mhendislik uygulamalarnda kullanm alan bulabilen malzemeler
olarak son yllarda olduka ilgi ekmektedir. zellikle Al esasl metalik kpkler, kapal hcre yaps ve ok hafif
olmas ile gze arpmaktadr. Al kpkler, darbe enerjisini plastik enerjiye dntrebilir ve birok metalden daha
fazla enerji absorbe edebilir [2, 3]. Bundan dolay ses ve enerjinin snmlenmesin de alminyum kpkleri fonksi-
253

yonel olarak kullanlmaktadr. Kullanm alanlar arasnda, hafifliin ve mukavemetin bir arada bulunmas gereken
otomotiv, uzay sanayi, demiryolu tamacl ve asansr gibi alanlar bulunmaktadr [4, 5]. Metalik levha kpkler
ayn zamanda atee dayankl yaplar olarak da retilebilmektedir. Plaka tr kpk snfnda olan metalik kpkler
yksek scaklklara kar yaltm malzemesi olarak kullanlmaktadr [6]. Bu zelliklerinden dolay savunma sanayisinde balistik ve/veya integral koruyucu zrh malzemeleri olarak kullanlmaktadr.
Toz Metalurjisi (TM) yntemi metalik kpklerin retimi iin en yaygn kullanlan yntemlerden biridir. Homojen bir
yap elde etmek iin gelitirilen bir yntemdir [7-9]. Bu yntem metal tozlarnn ve kprtc malzeme tozlarnn
kartrlmas ve preslenmesi ile kprebilir yar maml (preform) malzeme haline getirme ilemine dayanr. Bu
ilemlerle birlikte scak presleme, ekstrzyon, toz haddeleme, vb. metodlar ile preform haline getirilebilir. Preform
ergitme scaklnn zerinde bir scakla getirilerek kprtme ilemi gerekletirilir [10, 11]. Sv ynteme gre
homojen gzenekli kpk retebilme avantajnn yannda, byk kesitli preform malzemeden kprme ilemleri
srasnda karlalan zorluklarda mevcuttur. zellikle kprtme srecinde preformun d yzeylerinde ve kalpla
temas yzeylerinde balayan ve kprme reaksiyonu ile oluan gaz dolu hcrelerin, s iletiminde homojensizlie
sebep olmas byk kesitli metalik kpklerin retimini gletirmektedir.
Bu durumda kprtme srecinin kontrol nemlidir ve kprtme ilemi srasnda kontrol edilmesi zor deikenler
devreye girmektedir. Bunlardan iki tanesi deien gzenek boyutlar ve ona bal deien sl iletkenliktir. Oluan
malzemenin younluu ve gzeneklilii arasnda aadaki gibi bir eitlik bulunmaktadr [12].
(1)
Burada p gzeneklilik, V kpk hacmini, ve * preform malzeme ve kpk malzeme younluunu temsil etmektedir. Preform (kat) younluu ve gaz faz younluu kprme esnasnda kpn younluunu deitirmektedir. Bu
deiim sl iletimi deitirerek kprme karakteristiini belirlemektedir. Byk kesitli metalik kpk retimlerinde
bunun daha nemli bir parametre olduu tespit edilmitir.
Termal iletkenlik ve gzenek boyutu arasnda birka yaklam bulunmaktadr. Bu yaklamlardan bir tanesi Eitlik 2,
3 ve 4te gsterilmektedir. Yaklama gre gaz-kat, kat - sv veya sv-gaz gibi iki fazl sistemlerde s transferinin
gerekleme durumlar gsterilerek formlize edilmitir (ekil 1.1) [13].
ekil 1.1. ki fazl sistemlerde ak ve s iletiminin paralel ve seri yaplandrma yaklam [13].
(2)
(3)
Burada gaz, kat gaz ve kat termal iletkenlii sembolize etmektedir [12-14]. 1. ve 2. Eitliklerdeki hem seri hemde
paralel durum iki fazl yaplarda dnldnde 3 nolu bant oluturulmutur.
= p gaz + (1-p) kat
(4)
Her iki eitlik (1. ve 4.) birbiri ile dnldnde kprme esnasnda ierde oluan hcre boyutlar deitike hcre
duvarlarndaki sl iletkenliin de deitii dnlebilir [12-14]. Eitlik 2ye gre dnlecek olursa gzeneklilik (p)
arttka gazn termal iletkenlii kat ve/veya sv hcre duvarlarn iletkenliine gre daha belirgin rol oynamaktadr.
zellikle byk kesitlere sahip preformlardaki btn kesit ya da hacim boyunca s iletim fark ve homojensizlik
kprme srecinin de heterojenliine sebep olmaktadr. lk s girdisinin olduu preformun kenar, alt ve st yzey
blgeleri ile orta blgelerinin kprme sreleri deiir. lk sl girdinin preformun kenar ve yzeylerinde balatt
kprme reaksiyonu ile oluan ii hidrojen gaz dolu gzeneklerin ve hcre duvarlarnn Eitlik 4te belirtilen sl ilet-
254

kenliine bal olarak kprme reaksiyonu i blgelere yaylr. Is iletiminde yukarda belirtilen etkenlerin meydana
getirdii homojensizlik, homojen kprtme ve kpk retme ilemine engel olur. Bu nedenle kaln kesitlerde retilen kpk malzemelerde, kalnlk arttka homojen kprme problemleri ortaya kar. Kprme srecindeki s iletimini kalbn ekli, boyutu, sl iletkenlii ve preformun iletkenliinin belirledii tespit edilmitir [15]. Bu parametreler
ve frn ii scaklk dalm dikkate alndnda byk kesitlerde homojen kpk oluumu iin mmkn olduunca
e zamanl reaksiyon salanabilmelidir. Bu amala, Yksek Enerji Metodu-X (YEM-X) ile kprtme teknii gelitirilmitir. Bu metot ile preformun tm kesitinde kprmenin yaklak ezamanl balamas salanmtr. s iletimini
Bu almada toz metalurjisi yntemiyle byk kesit alanl, AlSi alam kapal hcreli levha kpklerin kprme
srecinde meydana gelen problemler ve giderme yntemleri aratrlm ve tartlmtr.
2.1. Malzeme ve Metot1
% 99,9 saflkta ve 160 m alt tane boyutundaki Al tozu, % 4 Si ve kprtc madde % 1,2 TiH2 tozu 3 eksenli
kartrma cihaznda (Turbola) kartrlp karm tozlar hazrlanmtr. Karm tozlar oda scaklnda preslenerek
80 mm apnda silindirik blok numuneler retilmitir. Blok numunelerin 1 saat sre ile sinterlenmesi ardndan 4:1
orannda scak ekstrzyon ilemi uygulanmtr (ekil 2.1-a). Ekstrze malzeme kademeli olarak scak/lk haddelenerek ekillendirilmi ve levha biimli 250x250x10 mm boyutlarnda preform levhalar retilmitir (ekil 2.1-b).
ekil 2.1. a) Ekstrzyon rn preform b) Haddelenmi preform levha

2.2. Kprtme lemi
ekil 2.2de imal edilen kpk retme ve ekillendirme kalbnn resmi verilmektedir. Kprtme ilemleri, zel tasarlanan ve imal edilen mufel tipi 600x600x300mm3 kamara hacminde, alt tablas srgl hareket edebilen 13 kW
gcndeki frnda yaplmtr.
ekil 2.2. Kprtme kalb

1
Bu alma konusunun ticari deeri sebebiyle sre, scaklk, basn vb. baz parametrelerin deerleri belirtilmemitir.
255

Preform levha malzemeler kalp ierisine yerletirildikten sonra kprtme scaklndaki (680-780C) frna yerletirilmitir. Kprtme scaklnda belirli sre bekletildikten sonra kalp boluunu dolduran metalik kpk, kalpla
birlikte frndan kartlarak sirklsyonlu havada soumaya braklmtr. Katlama tamamlandktan sonra metalik
kpk malzeme kalptan kartlmtr.
3. SONULAR ve TARTIMA
3.1. Kprtme Kusurlar
3.1.1. Tm Kesitte Kprme Tamamlanmadan kme
Kalp ierisinde ilk s iletimi salayan blgeler yzey alanlarnn kk olmasndan dolay kalp kenarlardr. ekil
3.1de kprtme ilemine tabi tutulmu olan levha eklindeki kpk malzeme gsterilmitir. Kprme srecinde
ilk kpren blgelerin kalp kenarlarna yakn olan blgeler olduu kenar tarma deliklerinden gzlenmitir. Is
iletiminin zamana bal ilerlemesi (ekil 3.1de A oklarnn yn) ile kprme, orta blgelerde de balamtr. Fakat
orta blgeler kprme srecine girene kadar A oklar ile gsterilen blgeler ar kprme srecine girmitir. En son
kprme blgesinin orta ksm olduu gzlenmitir. Bu sre tamamlanana kadar B oklar ile gsterilen blgelerde
kme gzlenmitir. Is iletiminin preform zerinden salanmas, kenar blgelerde hcre oluumu ile azalmtr
(Eitlik 4). Fakat kalp alt yzeyinden orta ksmdaki prefom malzemeye s transferi salandnda orta ksmda da
kprme gereklemitir.
ekil 3.1. Homojen olmayan kprme ile oluan levha kpk

3.1.2. Yaynm ve Ylma ile Katmanlama
ekil 3.2-Ide gsterilen levhada tam kprmeme ve ylma problemleri belirlenmitir. Kalp ierisinde kprtme
srecinde kalb dolduran kpk malzemenin kenarlardan merkeze doru ilerledii gzlenmitir (ekil 3.2-III). Bu
srete, yar kat durumda olan orta ksmdaki kprmemi malzeme, kprerek genleen ktle tarafndan yukar
itilmi ve dzlemsellikten sapmasna neden olmutur. Bu deiiklik ile preformun kalp alt yzeyi ile temasn kestii
gzlenmitir (ekil 3.2-IV). Bu srete s iletimi arlkl olarak kpren ksm olan blgeden gereklemektedir.
Gzenek oluumuyla azalan s iletimi, kenar blgelerin kprerek ilerleme ve genleme hzn artrmtr. Bunun
sonucunda orta ksmlar henz kprme srecine girmez iken kpren kenar blgelerin dzensiz gzeneklerle kalb doldurduu gzlenmitir. Ortam ve buna bal kalp scaklnn artmasyla kpren blgelerin drenaj azalmtr.
Bununla birlikte kpk hacimsel genleme artacandan kalp doldurma sresi ksalacaktr [10, 16]. ekil 3.2-IIIte
gsterilen kenar blgelerde gzenek boyutlar orta ksmlara gre daha byk ve hcrelerin birbiri ile birletii gzlenmitir. C oklaryla gsterilen ynde orta ksmlarda kprme sreci tamamlanmam malzeme zerine kpren
malzemenin hareketi ile katmanlama gzlenmitir (ekil 3.2-II).
256

ekil 3.2. I) Homojen kprmeyen levha kpk, II) st ksmda katmanlama

III) Levha kpk kesiti, IV) Levhann alt yzeyi
ekil 3.3te gsterilen kpk levha orta ksmda kprmeme problemi gzlenmitir. ekil 3.2de gsterilen levha
kpe benzer durum sergilemitir. Fakat dier numune kprtme ileminden farkl olarak tarma deliklerinden
kpk gelse dahi kprme srecine devam edilmitir. Bu bekleme kalp ierisini kpk doldurma ilemini artrmtr.
Fakat orta ksmda kprme sreci tamamlanmamtr (ekil 3.3-b). Kprtme srecinin uzatlmasyla kalp st
yzeyi arasna yaylan kprm malzemenin orta tarma deliklerinden tat gzlenmitir. Bu yaylma D oklarnn
gsterildii ynde gereklemitir. ekil 3.3-bde de F oklaryla bu srnme etkisinin gzenek hcre ekillerini ve
boyutlarn dzensizletirdii grlmektedir. E okuyla gsterilen ksmlarda ar kprme gzlenmi olup hcre
duvarlarnn birbiri zerine kt belirlenmitir.
ekil 3.3. a) Levha kpn genel grnm, b) Levha kpk kesiti
257

3.1.3. Kelerde kme

ekil 3.4te gsterilen kpk levha ke ksmlarnda kme problemi gzlenmitir. Bu levha kpk retiminde
kullanlan parametreler sabit olmakla birlikte, kalp st kapann kprme srecinde kapatlmas denenmitir. Kprme sreci tamamlanrken tavlanm kalp kapa vastasyla basn uygulanarak, kalp iindeki kpn scak
deformasyonuyla kalp boluunu doldurmas salanmtr. Bu ilemlerin sreci ok ksa tutulmutur. G oklaryla
gsterilen blgelerde, kpk hcrelerinin ekil deitirme esnasnda patlamas, birlemeleri ve skan hidrojen
gaznn kamasyla levha kelerinde ar kpk kmeleri ve malzeme ylmalar gzlenmitir.
ekil 3.4-IIde levha kpn kesit grnts verilmitir. ekil deiiklii ile levhann genelinde basn uygulanan
yne dik ynde hcreler deformasyona urayarak elipstik ekil almlardr. Bu ekilde oluan morfolojik dzensizlikler, hcre elipslii, homojen olmayan hcre duvar kalnl ve hcre boyut dalmnn plato blgesi gerilmesini
azatl belirlenmitir [17]. H oklaryla gsterilen blgelerde istenmeyen bu hcre yaplar belirtilmitir.
ekil 3.4. I) Levha kpn genel grnm ve ylma kesinin grnts, II) Levha kpk kesit grnts.
ekil 3.5te Yksek Enerji Metodu-X (YEM-X) ile retilen metalik levha kpk gsterilmitir. retilen kpk levhada
ayn kesit alanl nceki levhalara gre daha homojen ve e eksenli hcreler elde edilebilmitir. Levha kpn tm
kesiti ayn boyutlarda, ayn homojen hcre yapsnda ve dzgn geometrik yzeylere sahiptir. Kprme srecinde
preform malzemenin tm yzeylerinde salanan daha homojen ve hzl s iletimi ile e zamanl balatlan kprme
reaksiyonu, dzenli hcreli levha kpk retimini gerekletirmitir. Preform malzeme retim srecinde homojen olmayan Si ve TiH2 dalm, kprme srecinde de baz homojen olmayan gzenek dalmna da sebep olmaktadr.
Bu nedenle G oklaryla gsterilen birka hcrede, kprme srecinde hcrelerin balant duvarlarnn kaybolmas
ve birbiriyle birlemesi ile byk gzenekli hcreler olumutur.
ekil 3.5. YEM-X yntemi ile retilen metalik levha kpk
258

4. SONULAR
Bu almada, geni yzey alanl veya byk kesitli metalik kpklerin retimi srecinde meydana gelen metalik
kpk levhalardaki hatalar kategorize edilmi ve nedenleri tartlarak giderilme areleri aratrlmtr. Bu almann sonular olarak aada hususlar belirtilmitir;
1) Preform (kat) younluu ve gaz faz younluu kprme esnasnda kpk malzemenin younluunu deitirmitir. Bu deiim preformun s iletimini deitirerek kprme karakteristiini belirler. Toz metalurjisi teknii ile
levha boyutlarndaki byk kesitli metalik kpk retimlerinde s iletimindeki bu deikenlik nemli problemler
meydana getirir.
2) Byk kesitli levha kpk retim srecindeki oluan problemler;
- Kalp ierisinde tm kesitte kprmenin tamamlanmas srecinde erken kprme oluan blgelerde kme problemi meydana gelir.
- Kalp ierisinde tm kesitte tam kprmeme ve yaylma problemleri meydana gelir. Kprtme srecinde kalb dolduran kpk malzemenin kenarlardan merkeze doru yaylmasyla, kprmeyen preformun dzlemsellii
bozularak kalp alt yzeyi ile temas keser. Kprerek yaylan malzeme prefom malzemenin zerine doru
ilerleyerek katmanlama meydana getirir. Bu durumda, retilen kpk levhann orta ksmlarnda hcre oluumu
tamamlanmazken kenar ksmlarda byk ve homojen olmayan gzenekli yap meydana gelir.
- Kprme srecinde basn oluturarak kalp boluunun doldurulmas ilemlerinde, kalp kelerine malzemenin yaylmas srasnda hcrelerin deformasyonla patlamas, kapanmas, kme problemlerini oluturur. Kpk
malzemenin scak deformasyonu ise, uygulanan basma ykne dik dorultuda hcrelerin deformasyonuna ve
geometrisinin bozulmasna sebep olmaktadr.
- Yukarda belirtilen problemlerin giderilmesi iin gelitirilen Yksek Enerji Metodu-Xin uygulanmas bu problemlerin bir ounu elimine etmitir. Kprme srecinde preform malzemenin tm yzeylerinde salanan yksek enerjili homojen s iletimi sayesinde yaklak e zamanl balatlan kprme reaksiyonu, dzenli hcreli levha kpk
retimini gerekletirmitir. Levha kpn tm kesiti ayn boyutlarda, dier kpklere kyasla daha homojen ve
e eksenli hcre yapsnda ve dzgn geometrik yzeylere sahiptir.
TEEKKR
Yazarlar, Bilimsel Aratrma Projesi ( No: 107A016) kapsamnda bu almaya destek salayan TBTAKa teekkr eder.
KAYNAKLAR
1. Seitzberger, M., Rammerstorger, F.G., Degischer, H.P.,Crushing of axially compressed steel tubes filled with
aluminium foam, Acta Mechanica, 125: 95-103, 1997.
2. Hanssen A.G., Langseth, M., Happerstad, O.S., Static and dynamic crushing of circular aluminium extrusions
with aluminium foam filler, Int. J. of Impact Eng., 24 (5): 475-507, 2000.
3. Elbir, S., Ylmaz, S., Gden, M.,Kapal hcre alminyum kpk metallerin retim metodlar ve mekanik zellikleri, TMMO Metalurji Dergisi, 23 (120): 35-42, 1999.
4. Davies, G.J., Zhan, S., Review metallic foams, their production, properties and applications, J. Mat. Sci., 18:
1899-1911, 1983.
5. Simancik, F., Rajner, W., Laag, R., Alulight - Aluminum Foam for Lightweight Construction, SAE 2000 World
Congress, 2000-01-0337, pp. 1-7, Detroit, Michigan, 2000.
6. P. Schaeffler, W. Rajner, D. Claar, T. Trendelenburg, and H. Nishimura., Production, Properties and Applications of Alulight Closed-Cell Aluminum Foams, The Fifth International Workshop on Advanced Manufacturing Technologies, pp. 1-6, London, Canada, 2005.
7. John Banhart, Manufacturing Routes for Metallic Foams, Journal of the Minerals, pp. 22-27, 2000.
8. Chin-Jye Yu, Harald H. Eifert, John Banhart and Joachim Baumeister, Metal Foaming by A Powder Metallurgy Method: Production, Properties and Applications, Innovations in Materials Conference, vol:2, pp.
181188, 1998.
9. Mehmet TRKER, Toz Metalurjisi Yntemi ile Alminyum Kpk retimi, 5. Uluslararas leri Teknolojiler
Sempozyumu (IATS09), s.1-6, Karabk, 2009.
10. I. Duarte and J. Banhart, A Study of Aluminium Foam Formation Kinetics and Microstructure, Acta Materialia, 48, pp. 2349-2362, 2000.
11. By Frank Baumgrtner, Isabel Duarte and John Banhart, Industrialization of Powder Compact Foaming
Process, Advanced Engineering Materials, 2, No:4, pp. 168-174, 2000.
12. Hegman, N. and Babcsan, N., Specific Feature of Thermal and Electrical Transport In Cellular Media, Anyagok Vilaga Materials World, 6:1, 2005.
259

13. Singh, R., Kasana, H.S., Computational aspects of effective thermal conductivity of highly porous metal foams, Applied Thermal Engineering, 24, 18411849, 2004.
14. Sullins, A.,D. And Daryabeigi, K., Effective Thermal Conductivity of High Porosity Open Cell Nickel Foam, 35th
AIAA Thermophysics Conference, AIAA 2001-2819, 3-5, 2001.
15. Hans-Peter Degischer and Brigitte Kriszt, Handbook of Cellular Metals: Production, Processing, Applications,
Wiley- VCH, pp. 33-338, 2002.
16. S. Asavavisithchai, A.R. Kennedy, Effect of powder oxide content on the expansion and stability of PM-route
Al foams, Journal of Colloid and Interface Science, 297, 715723, 2006.
17. Elbir, S., Kapal Gzenekli Alminyum Kompozit Kpklerin Hazrlanmas ve karakterizasyonu, zmir Teknoloji Enstits, Yksek Lisans Tezi, 28-79, 2001.
260

TiCN Takviyeli 316L Paslanmaz elik Kpklerin retimi ve

zellikleri
Halil . BAKAN1 ve Kemal KORKMAZ2
TBTAK MAM Malzeme Enstits Pk 21 Gebze 41470 - KOCAEL
Gebze Yksek Teknoloji Enstits, Malzeme Bil. ve Mh. Bl. Gebze 41400 - KOCAEL
1
ZET
Arlka %5 TiCN ieren stenitik paslanmaz elik esasl metalik kpkler replikasyon ve toz metalurjisi yntemleri ile retildi. Bunun iin 316L tozlar ile balaycdan oluan sv karm, poliretan sngere emdirildi. Yzeyleri
metal tozlar ile kaplanm olan sngerlere srasyla kurutma ve bunu takip eden piroliz ilemi uygulanarak, snger
ve balayclarn ortamdan uzaklatrlmas saland. Bu ekilde poliretan sngerin ak gzenekli iskelet yaps
ak gzenekli metalik iskelet yapya dntrld. 1350 oC scaklkta gerekletirilen sinterleme ileminden sonra
ak gzenekli hcresel paslanmaz elik esasl metalik kpkler elde edildi. Sinterleme sonras elde edilen kpk
metalik malzemelerin gzenek dokusu optik mikroskop ve SEM ile incelendi. EDX ve XRD analizleri ile numunelerin
faz yaps karakterize edilmitir. Ayrca numuneler zerinde gerekletirilen basma deneyleri ile elde edilen kpk
metalin mekanik zellikleri irdelenmitir.
Anahtar Kelimeler: Metalik Kpkler, , Paslanmaz elik, Toz Metalurjisi,
Manufacturing and Properties of 316L Stainless Steels

Foams Reinforced with TiCN
ABSTRACT
Austenitic stainless steel based metal foams with 5 wt % TiCN were manufactured by using replication and powder
metallurgy techniques. Therefore, a polyurethane sponge, impregnated with stainless steel slurry prepared from
316L powders and binders, was subjected to drying and pyrolyzing to remove the polyurethane sponge and binders.
Thus, the complete transformation of open network of the polyurethane sponge to the metal network was carried
out. After sintering process at temperature of 1350 oC, open cellular 316L based metal foams were produced. The
porous structure of metallic foam materials obtained after sintering was investigated by using optical microscopy
and SEM. The phase structures of samples were characterized by XRD and EDX analysis. In addition, mechanical
properties were investigated by compression tests performed on the samples.
Keywords: Metal Foams, , Stainless Steel, Powder Metallurgy
1. GR
Metalik kpk malzeme tanm; hacimce % 50 - % 99 arasnda hava boluu ieren gzenekli ya da hcresel
ekilli bir yapya sahip metalik malzemelere verilen genel bir isimdir. erdikleri hava boluu sayesinde ok farkl
fiziksel zellikleri ayn anda gsterebilmektedirler. Bu malzemelerin en belirgin zellikleri ise ok dk younlua
sahip olmalar, basma ve eme dayanmlarnn ok yksek olmas, darbe ve titreim snmleme zelliklerinin
yksek olmas, s ve elektrik iletim zelliklerinin de dk olmasdr. Bu zellikleri nedeniyle yeni bir malzeme
snfn oluturmaktadrlar. erdikleri hava boluunun oran, hava boluunu meydana getiren gzeneklerin ekli
261

ve bu gzeneklerin birbirleri ile olan balantsna bal olarak gsterdikleri fiziksel zellikler ve potansiyel kullanm
alanlar deimektedir. Sahip olduklar bu zgn zellikler nedeniyle 21. yzylda uzay teknolojisinden otomotiv
teknolojisine, inaat teknolojisinden salk teknolojisine kadar ok deiik alanlarda kulanm potansiyelleri olduu
ngrlmektedir. Paslanmaz elik esasl kpk metallerin, alminyum esasl kpk malzemelere gre daha yksek
mekanik zelliklere sahip olmalar ve yksek scaklklarda uygulamalarnda kullanlma imkanlarnn bulunmas,
elik esasl metalik kpk malzemelere olan ilgiyi arttrmaktadr [1-5].
Ak gzenekli hcresel ekilli metalik kpklerin retimi replikasyon teknii ve toz metalurjisi yntemi ile gerekletirilmektedir. Metalik kpklerin ak gzenekli hcresel yaps, ayn ekle sahip olan ve balang malzemesi
olarak kullanlan polimerik sngerler sayesinde elde edilebilmektedir.
Replikasyon (kopyalama) ileminin gerekletirilebilmesi iin ncelikle metal tozlarnn uygun organik malzemeler
ile kartrlarak bir sv karmn elde edilmesi gerekir. Daha sonra bu sv karmn polimerik sngere emdirilmesi
gerekletirilmektedir. Daha sonra uygulanan piroliz ilemi ile polimerik snger ve organik malzemeler buharlatrlarak ortamdan uzaklatrlmaktadr. Bu ilem srasnda, balang polimerik sngerin ak gzenekli hcresel
yapsnn bir kopyas olan metal iskelet yapnn elde edilmesi gereklemektedir. Bu ilemden sonra uygulanan
sinterleme ile de ak gzenekli hcresel metalik kpkler retilmi olmaktadr [1-5].
Polimerik snger yzeylerinin metal tozlar ile kaplanmas bu prosesin ilk ve en nemli aamasn oluturmaktadr. Metal tozlarnn organik malzemelerle kartrlmasyla hazrlanm olan sv karmn mmkn olan en fazla
oranda metal tozu iermesi ve snger yzeylerine mmkn olan en fazla miktarda metal tozlarn yaptrabilme
zelliine sahip olmas gerekir. Bunun sonucunda; sinterlemenin daha iyi gereklemesi ve daha yksek sinterleme
younluklarnn elde edilmesi mmkn olabilir. Buna karn, sv karmn gereinden fazla metal tozu iermesi de
polimerik snger yzeylerinin metal tozlar ile tam olarak kaplanamamasna neden olur. Bu nedenle sv karmdaki
metal toz miktarnn optimum bir deerde olmas gerekir.
Paslanmaz elik tozlarnn yzeyinde bulunan ince bir krom oksit tabakas, bu malzemelerde normal kat hal sinterleme koullarnda yksek sinterleme younluk deerlerinin elde edilmesini imkansz hale getirmektedir. Buna karn sv faz sinterlenmesi ilemi ile bu malzemelerde yzde yz teorik younlua ulalmas mmkn olabilmektedir.
Younluk artyla birlikte mekanik zelliklerde de nemli artlar gerekleebilmektedir [6] Fakat tamamen ak
gzenekli metalik kpk malzemelerin retiminde sv faz sinterlenmesinin uygulanmas mmkn deildir.
nk sv faz oluumu ile birlikte metalik iskelet yapda yer yer kmeler ve ekil bozukluklar olumaktadr. Bu
nedenle bu malzemelerin retiminde kat hal sinterlemesi kanlmazdr. Bununla birlikte metalik kpk malzemenin
mekanik zelliklerini arttrmak iin deiik oranlarda karbr esasl katklar paslanmaz elik tozlarna ilave edilebilir.
Bu sayede ana yap ierisinde homojen olarak datlm sert karbr faz ya da oksit fazlar sayesinde, mekanik
zellikler nemli artlar salanabilir. Literatrde zellikle TiC, NbC, SiC, TiCN, Al2O3 ve Y2O3 katklar ile ilgili almalar bulunmaktadr [7-9]. Bununla birlikte TiCN takviyeli paslanmaz elik malzemeler ile ilgili almalar olduka
yenidir [10]
Bu nedenle daha stn mekanik zellilere sahip metalik kpkler retebilmek iin; mevcut almada arlka % 5
orannda TiCN ieren 316L paslanmaz elik tozlar kullanlarak, replikasyon ve toz metalurjisi yntemiyle hcresel
ekilli metalik kpklerin retimi gerekletirilmitir. retilen metalik kpk malzemenin mekanik zellikleri basma
deneyleri ile belirlenmi. Ayrca retilen kpk malzemenin mikroyap zellikleri optik ve taramal elektron mikroskobuyla (SEM) ve faz yaps da XRD ve EDX analizleri ile incelenmitir.
Bu almada gaz atomizasyon yntemiyle retilmi ve ortalama tane boyutu 25 m olan kresel ekilli 316L stenitik paslanmaz elik tozlar ve ortama tane boyutu 1 m olan dzensiz ekilli TiCN tozlar kullanlmtr. Kullanlan
316L tozlarn kimyasal bileimi arlka % Fe -16.96 Cr, 10.8 Ni, 2.04 Mo, 1.38 Mn, 0.4 Si, 0.03 C, 0.03 P, 0.003 S
dr. Arlka % 5 TiCN ieren homojen bir toz karmn elde edilebilmesi iin toz karm, aseton ieren bir kabn
ierisine konularak, Turbula tipi kartrc da saatlik bir kartrma ilemi uyguland. Daha sonra etvde uygulanan kurutma ilemiyle aseton toz karmndan uzaklatrld ve kullanma hazr 316L+ % 5 TiCN toz karm elde
edildi. Arlka % 5 TiCN ieren 316L paslanmaz elik esasl metalik kpk retimi replikasyon ve toz metalurjisi
yntemiyle gerekletirildi (ekil 1).
262

ekil 1: Hcresel ekilli paslanmaz elik

kpk malzemenin retim emas
Ak gzenekli hcresel ekilli kpk metalin elde edilebilmesi iin balang malzemesi olarak ierdii gzenek
miktar 10 ppi (pores per inch) poliretan sngerler kullanld. Metal tozlarnn poliretan sngere emdirilebilmesi
ve snger yzeylerinin metal tozlar ile kaplanabilmesi iin deiik molekler arlktaki Polietilen Glikol (PEG) ve
Karboksimetil selloz (Carboxy Methyl Cellulose, CMC) zeltisinden oluan balayc sistemi kullanld. ncelikle
Karboksimetil selloz zeltisine metal tozlar (arlka % 5 TiCN ieren 316L paslanmaz elik tozlar) azar azar
ilave edilerek bir saatlik kartrma ilemi uyguland. Daha sonra elde edilen karmn scakl oda scaklndan
75C scakla kartld ve deiik molekler arlktaki PEG (PEG600, PEG1500 ve PEG8000) karma eklendi. lave
edilen PEGler bu scaklkta tamamen ergitildikten sonra, balayc+metal tozundan oluan sv karm saat
daha kartrlarak homojen bir sv bir karm elde edildi. Elde edilen sv karmn iermesi gereken ideal metal
toz miktarn ve reolojik zelliinin belirlenmesi iin ayn artlarda hazrlanm ve ierdii metal toz miktar hacimce
% 45, % 50 ve % 55 arasnda deien karmlarn viskozite lmleri yapld. Viskozite lmleri srasnda ortam
scakl 75C olarak sabit tutuldu. Sv karmn iermesi gereken optimum metal tozu miktar belirlendikten sonra poliretan sngerler sv karma daldrlarak, snger yzeylerinin metal tozlar ile kaplanmas gerekletirildi.
Yzeyleri metal tozlar ile kaplanm olan sngerler daha sonra iki merdane arasndan geirilerek, fazlalk metal
tozlarnn sngerden uzaklatrlmas ve ak gzenekli yapnn korunmas saland. Bu ilemden sonra numuneler
belirli bir nem oranna sahip kabin ierisinde ve oda scaklnda iki gn kurutulmaya brakld. Numuneler kurutulduktan sonra poliretan snger ve organik balayclar 450C scaklnda ve Ar - H2 atmosferinde otuz dakika ierisinde buharlatrlarak numunelerden uzaklatrld. Hidrojen ortamnda ve 1350Cde gerekletirilen saatlik
sinterlemeyle ak gzenekli hcresel yapda 316L + %5 TiCN esasl metalik kpkler retildi. Elde edilen metalik
kpklerin mikro yaps ve yzey zellikleri optik mikroskop ve taramal elektron mikroskop (SEM) kullanlarak
aratrld. Numunelerin faz yaplar XRD ve EDX analizleri ile incelendi. Gerekletirilen basma deneyleri ile de
mekanik zellikler belirlendi.
3. DENEYSEL SONULAR VE RDELEME
Deiik oranlarda metal tozu ieren sv karmn 75C scaklkta gerekletirilen viskozite lm sonular ekil
2de grlmektedir. Metal tozlarnn polimerik yzeylere daha kolay yapmasnn salanabilmesi iin sv karma
yksek kayma hz uygulandnda karmn viskozite deerinin dk olmas arzu edilir. Fakat kayma hz dk
olduunda ise sv karmn viskozitesinin de yksek olmas gerekir. Bu durum metal tozlarnn polimerik snger
yzeylerine kolay ve daha iyi yapmasn salar. ekil 2 de grld gibi hacimce %45 metal tozu ieren sv
karmn viskozite deeri kayma hznn artmasyla belirgin bir ekilde azalmakta ve kayma dk olduu durumda
45 Pa.s olan viskozite deeri kayma hznn artmasyla birlikte dier karmlara gre ok daha hzl olarak dmekte ve 2 Pa.s gibi ok dk bir deere ulamaktadr. Dolaysyla hacimce %45 metal tozu ieren sv karm daha
ideal reolojik zellikler sahiptir.
ekil 2: Deiik oranlarda

(%45-55) metal tozu ieren sv
karmn 75Cdeki viskozite
deerlerinin kayma hzna gre
deiimi
263

Hacimce %45 metal tozu ieren (316L+%5 TiCN) sv karm PEG + CMC ekilde 1de grld gibi replikasyon
ve toz metalurjisi yntemleri ile arlka %5 TiCN ieren 316L paslanmaz elik esasl metalik kpkler baarl bir
ekilde retilmitir. Elde edilen gzeneklerin ekil ve yaplar balangta malzemesi olarak kullanlan poliretan
sngerin gzenek ve yapsnn birer kopyas gibidir. Ancak 316L paslanmaz eliklerin 1350C de gerekletirilen
kat hal sinterlenmesinin doal bir sonucu olarak mikroyapda mikro gzenekler bulunmaktadr (ekil 3). nk
paslanmaz elik tozlarnn yzeyinde doal olarak oluan ince oksit tabakas, kat hal sinterlenmesinde tam younlamann salanabilmesini engellemekte ve yapda mikro gzeneklerin olumasna neden olmaktadr. retilen
TiCN katkl 316L paslanmaz elik malzemenin younluu 0,70 g/cm3 ve TiCN katks iermeyen 316L paslanmaz
elik kpk malzemenin younluu ise 0.75 g/cm3 olarak llmtr (ekil 3a). Bu deerler retilen metal kpk
malzememizin ne kadar hafif bir malzeme olduunun ak bir gstergesidir. Younluktaki azalma yalnzca daha
hafif olan TiCN katksndan kaynaklanmad, ayn zamanda TiCN katks ile mikro yapda ilave olarak bir miktar
daha istem d meydana gelen mikro gzenek oluumu aklanabilmektedir. Bu durum mikroyap fotoraflarnda
da grlmektedir (ekil 3a-3b,). Buna karn TiCN katks sonucu kpk malzemenin sertlik deerinde bariz bir art
grlm ve 316L paslanmaz elik kpk malzemenin sertlik deerinin % 5lik TiCN katks ile 220 HV den 355 HV
ye ykseldii tespit edilmitir. Elde edilen kpk malzemenin sertlik deerindeki artn, mikroyapda homojen bir
dalm gsteren sert bir TiCN takviyesinin doal bir sonucu olduu grlmektedir.
ekil 3a) retilen TiCN katkl 316L metalik kpklerin deiik grnmleri
ekil 3b): retilen ak gzenekli hcresel 316L paslanmaz elik kpklerin SEM de
ekilmi mikro yap grnts
retilen hcresel 316L paslanmaz elik kpklerin ve TiCN katkl 316L paslanmaz elik kpklerin basma dayanm ekil deitirme erisi tipik bir basma dayanm ekil deitirme erisi eklindedir (ekil 4). Her iki metalik
kpk malzemenin basma erisi blmden olumaktadr. Birinci blmde ekil deiimi ile dorusal olarak deien bir gerilim sz konusudur. Elastik blge olarak isimlendirilen bu blgede hcre duvarlar eilmektedir. Elastik
blgeyi takiben ikinci blge ise gerilimin deimedii, buna karn uzun ve kalc bir ekil deiiminin olduu bir
plastik deformasyon blgesini gstermektedir. Bu blgede hcre duvarlarnn plastik ekil deitirmesi ile birlikte
gzenekler kapanmaktadr. Erinin nc ve son blgesinde ise boluksuz, bulk bir malzemedeki gibi kesit alannn giderek artmasna bal olarak gerilmede hzl bir art grlmektedir. 316L paslanmaz elik kpk malzemenin
basma dayanmnn % 5lik TiCN katks ile 30,56 MPa dan 45 MPa a artt grlmektedir. Bu artn mikroyapda
homojen olarak dalm olan sert TiCN fazndan kaynakland aktr.
264

ekil 4: retilen ak gzenekli hcresel 316L paslanmaz elik kpklerin basma erisi
Elde edilen %5 TiCN katkl 316L paslanmaz elik kpk malzemenin SEM de yaplan EDX analizi ekil 5 de grlmektedir. Kpk malzemenin stenitik paslanmaz elik (316L) esasl olmasndan dolay Fe, Cr, Ni ve Mo elementlerinin, %5 TiCN katkdan dolay da Ti elementinin tespit edildii aikardr. N elementinin tespit edilemeyecek kadar
az olmasna karn C elementinin hem stenitik paslanmaz elik ve hem de %5 TiCN iinde mevcut olmasndan
dolay tespit edilebildii dnlmektedir.
ekil 5: % 5 TiCN katkl 316L paslanmaz elik esasl metal kpk malzemenin SEM de elementel
(EDX) analiz sonular.
ekil 6: 316L paslanmaz elik esasl ve % 5 TiCN katkl metal kpk numunelerde XRD analiz sonular.
ekil 6 da ise %5 TiCN katkl ve katksz 316L paslanmaz elik kpk numunelerin, 2 = 20o ile 90o arasnda dakikada 2o tarama hz ile llen XRD analiz sonular verilmektedir. Her iki analizde de paslanmaz elie ait olduu
dnlen Fe- stenitik fazn (111), (200) ve (220) yansma dzlemlerinden elde edilen en belirgin pikleri grlebilmektedir. %5 TiCN katkl numunenin analizinde ise Fe- stenitik fazlarn yan sra titanyum karbonitrr (TiC0.7N0.3)
fazna ait olduu dnlen ve en iddetlileri (111), (200), (220) yansma dzlemlerinden elde edilen pikler olmakla
beraber (311) ve (222) deki piklerde ayrt edilebilmektedir.
265

4. SONULAR
Mevcut almada replikasyon (kopyalama) teknii ve toz metalurjisi yntemleri kullanlarak arlka %5 TiCN
katkl ve katksz olmak zere 316L paslanmaz elik esasl, ak gzenekli ve hcresel ekilli kpk malzemeler
baarl bir ekilde elde edilebilmitir. Elde edilen kpk malzeme elik esasl olmasna karn sudan daha hafiftir
ve gzenek ekli ve yaps asndan balang malzemesi olarak kullanlan ve 10 ppi gzenek miktarna sahip
poliretan sngerin bir kopyas eklindedir.
retilen TiCN katkl 316L paslanmaz elik malzemenin daha dk younlua sahip olmasna ramen daha iyi
mekanik zellikler sergiledii grlmtr. 316L paslanmaz elik kpk malzemenin sertlik deerinin % 5lik TiCN
katks ile 220 HV den 355 HV ye ve basma dayanmnn da 30,56 MPa dan 45 MPa a ykseldii tespit edilmitir.
Elde edilen kpk malzemenin mekanik zelliklerindeki artn sebebinin TiCN katksnn meydana getirdii ve
mikroyapda homojen bir dalm gsteren titanyum karbonitrr gibi sert bir faz oluumu sonucu olduu dnlmektedir.
KAYNAKLAR
[1] J. Banhart, Progress in Materials Science, Vol.46, pp.559-632, 2001
[2] L. J. Gibson and M.F. Ashby, Cellular Solids: Structure and Properties, Second Edition, Cambridge University Press, Cambridge, 1997.
[3] C. Park and S.R. Nutt, Materials. Science . and Engineering. A vol 288 , pp. 118-118, 2000
[4] L. P. Lefebvre, M. Gauther and M. Patry, International . Journal of. Powder Metalllurgy. vol,42, 3, 49-57,
2006
[5] S.V. Raj, L. J. Ghosn, B.A. Lerch, M. Hebsur, L. M. Cosgriff and J. Fedor, Materials. Science . and Engineering. A vol 456,1-2, pp.305-316, 2007
[6] H.I. Bakan, D. Heaney , R.M German, Powder Metallurgy, vol. 44-3 , pp. 235-241, 2001
[7] J.D Bolton. and A.J. Gant , International . Journal of. Powder Metalllurgy., vol 36, pp. 267-274,1993
[8] S.Lal and G.S.Upadhyaya., Powder Metalllurgy International vol.20,3 pp. 35-38, 1988
[9] S.K.Mukherjee., A.Kumar, and G.S.Upadhyaya. Powder Metalllurgy International vol 20,3 pp. 35-38, 1988
[10] H.. Glsoy. Powder Metalllurgy, vol.24, 2, pp 14841490, 2008
266

TOZ METALURJS YNTEMYLE RETLM TiNi KPKLERDE

YALANDIRMA ISIL LEMNN ETKLER
Tark AYDOMU* ve akir BOR**
Yznc Yl niversitesi, Mhendislik Mimarlk Fakltesi, Makina Mhendislii Blm, 65080, Van,
aydogmus@yyu.edu.tr
**
Orta Dou Teknik niversitesi, Mhendislik Fakltesi, Metalurji ve Malzeme Mhendislii Blm, 06531,
Ankara, bor@metu.edu.tr
*
ZET
Bu almada yalandrma sl ileminin farkl miktarda gzenek ieren TiNi kpklerin dnm scaklklar ve
mekanik zellikleri zerindeki etkisi incelenmitir. Ti-50.6 at. %Ni alam tozu ve boluk yapc olarak magnezyum
tozunun 400 MPa basn altnda basldktan sonra 1100 Cde 1 saat sinterlenmesiyle retilen tek fazl (stenit)
TiNi kpkler 400 Cde 1 saat sreyle yalandrma sl ilemine tabi tutulmulardr. Bu ilem sonrasnda kelen
Ti3Ni4 faznn TiNi ana fazndaki nikel miktarn azaltarak dnm scaklklarn nemli lde arttrd grlmtr. Yalandrma sl ilemi sonras mekanik zelliklerde belirgin bir deiiklik gzlenmemitir. Yalandrlm btn
TiNi kpkler ksmi sperelastisite sergilemi, tam sperelastisite ancak dngsel ykleme-boaltma sonucu elde
edilebilmitir. Bu sayede % 5e varan gerinim kazanmlar mmkn olmutur.
Anahtar kelimeler: TiNi Kpkler, Yalandrma, Sperelastisite, Faz Dnm Scaklklar, Mekanik zellikler.
EFFECTS OF AGING HEAT TREATMENT ON TiNi FOAMS PRODUCED BY

POWDER METALLURGY METHOD
ABSTRACT
In the present study, effects of aging heat treatment on transformation temperatures and mechanical properties of
TiNi foams have been studied. Single phase (austenite) TiNi foams, which were produced by sintering Ti-50.6 at.
%Ni powder and magnesium spacer particle mixtures at 1100 C for 1 hour subsequent to compaction under 400
MPa, were subjected to aging heat treatment at 400 C for 1 hour. It has been observed that, Ti3Ni4 precipitates
formed increased the transformation temperatures significantly by decreasing the nickel content of TiNi matrix phase. Aging was not effective notably on mechanical properties. Partial superelasticity was observed for all aged TiNi
foams. Complete superelasticity of samples strained up to 5% was observed only upon employing cyclic loading
and unloading.
Keywords: TiNi Foams, Aging, Superelasticity, Phase Transformation Temperatures, Mechanical Properties.
1. GR
Diilik ve ortopedi gibi biyomedikal uygulamalar iin gelecek vaat eden TiNi kpklerle [1] ilgili aratrmalar son 10
sene ierisinde nemli bir hz kazanmtr. Biyouyumlu [2,3] olduklar kantlanan bu kpkleri biyomedikal uygula-
267

malarn gerektirdii zelliklerde retilebilmek amacyla pek ok alma yaplmtr [4-23]. Her ne kadar gzenekli
metalik malzemeler kat hal ilemleri (toz metalurjisi), sv hal ilemleri (dkm), elektrolitik ilemler veya gaz fazndan biriktirme yntemlerinden biriyle retilebilseler [24] de hem daha pratik hem de kolay olan toz metalurjisi teknikleri TiNi kpklerin retilmesinde kullanlan esas yntemler olmutur. Zaten ikinci nemli alternatif retim yntemi
olan dkm, daha ok ergime scakl dk ve ergitilmesi kolay, reaktif olmayan metaller iin uygundur.
TiNi kpk retiminde bugne kadar kullanlan yntemlerin ortak problemleri istenmeyen, krlgan intermetaliklerin
olumas, homojen olmayan gzenek ekli ve dalm, bunlarn sonucu olarak dk mekanik zellikler ve yetersiz sperelastisite davran sergilemesi ve gzenek miktar ile boyutlarnn ayarlanmasnn zorluu olmutur. Bu
problemlerin hemen hepsi daha nceki almalarmzda [4,9,15,16] incelenmi ve eitli zmler nerilmitir. Bu
almada ise nceki almalarmzdaki gibi magnezyum (Mg) boluk yapc ve TiNi alam tozu kullanarak rettiimiz TiNi kpklerinde yalandrma sl ileminin pratik uygulamalar asndan son derece nemli olan faz dnm
scaklklar ve mekanik zellikler zerindeki etkisini ortaya koymaya altk.
TiNi alamlarna sklkla uygulanan sl ilemlerin banda souk ilem sonras ekil bellek zelliini kazandrmak
iin yaplan tavlama ilemleri gelmektedir. Bu sl ilem zellikle eit atomlu ve titanyumca zengin TiNi alamlar iin
uygundur [25,26]. nk artan nikel miktaryla souk deformasyon zorlamaktadr. Nikelce zengin TiNi alamlar
iin ise (Ni miktar 50.5 at. %) [25,26] ok daha uygun olan, yalandrma sl ilemiyle mekanik zelliklerin ve
dnm scaklklarnn kontrol edilmesidir. Literatrde yer alan, TiNi kpklerin yalandrma sl ilemi [19, 2737] sonucunda zelliklerinde meydana gelen deiimlere ilikin almalarda, sl ilem ncesi kpklerde byk
miktarda bulunan ikincil fazlarn zeltiye alma ilemi srasnda zndrlememesi nedeniyle tutarszlklar bulunmaktadr. Bu almada tek fazl TiNi kpkler kullanlarak sl ilemler gerekletirilmi ve daha tutarl sonulara
ulalmaya allmtr.
2. DENEYSEL YNTEM
2.1. Kullanlan Tozlar ve retim Yntemi
TiNi kpkleri retmek iin balang tozlar olarak nikelce zengin, Ti-50.6 at. %Ni alam tozlar kullanlmtr. Boluk yapc olarak ise kresel magnezyum (Mg) tozlar tercih edilmitir. Mg boluk yapc miktar hacimce % 20-50
aralnda olacak ekilde ayarlanmtr. Kullanlan tozlar ve retim yntemine ait geni bilgi nceki almalarmzda
[4,9,15,16] bulunabilir. % 50 Mgden daha az Mg ieren kompaktlar sinterleme esnasnda toplam Mg miktar % 50
olacak ekilde ekstra Mg, koruyucu olarak, ilave edildikten sonra sinterlenmitir. Sinterleme scaklna (1100 C)
stma hz 10 C/dak olarak sabit tutulurken, sinterleme sresi (1 saat) sonrasnda pota frnn souk blgesine
ekilerek, yaklak 60-75 C/dak bir hzda numunelerin oda scaklna soutulmalar salanmtr. retilen farkl
miktarda gzeneklilie sahip TiNi kpklerin sl ilem ncesi grnts ekil 1de verilmitir.
ekil 1. Farkl miktarda gzenek ieren sinterlenmi TiNi kpkler.
268

2.2. Yalandrma Isl lemi

Sinterleme sonras farkl gzeneklerde retilen tek fazl (B2 stenit), (ekil 2) TiNi kpkler, koruyucu argon atmosferi altnda 400 C scaklkta 1 saat sreyle yalandrma sl ilemine tabi tutulmulardr. zeltiye alma ilemi
yaplmamtr nk sinterleme sonras numuneler ekil 2den de grld zere zaten sadece istenilen stenit
fazn iermekteydiler. Yalandrma scakl ve sresi ayn kompozisyondaki hacimli (gzenek iermeyen) TiNi alamlarnda sperelastisite asndan en iyi sonularn elde edildii scaklk ve sre olarak seilmitir. Yalandrma
esnasnda olas oksitlenmeyi minimize etmek iin numuneler bir pota ierisindeki Mg tozu iine gmlerek sl ilem
gerekletirilmitir. Frnn souk blgesinde bekletilen numuneler scakln 400 Cye ulamas ve kararl hale
gelmesiyle birlikte scak blgeye indirilmitir. Yalandrma sresinin tamamlanmasyla birlikte pota tekrar souk blgeye ekilerek 3 dakika sreyle soumaya braklmtr. Daha sonra hemen frndan alnarak zerine alkol pskrtmek suretiyle oda scaklna soutulmalar salanmtr. Bu yntemle toplam soutma sresi 4 dakikadan daha az
olarak gereklemitir. Su verme ilemi nemli derecede oksitlenmeye neden olduu iin tercih edilmemitir.
ekil 2. (a) TiNi toz ve (b) % 38, (c) % 43, (d) % 51, (e) % 59 gzenekli TiNi kpe ait XRD patternleri.
2.3. Karakterizasyon
Sinterlenen numunelerin younluk ve gzenek miktar Arimet metoduyla llmtr. yapda oluan fazlar Rigaku D/Max 2200/PC model X n difraktometresi (XRD) yardmyla belirlenmitir. TiNi kpklerin dnm scaklklar Perkin Elmer Diamond diferansiyel taramal kalorimetresi (DSC) ile 10 C /dak stma ve soutma hzlar
kullanlarak belirlenmitir. Basma ve sperelastisite testleri 10X10 mmlik silindirik numuneler kullanlarak 30 kN
kapasiteli, stma haznesi olan Instron 3367 mekanik test cihaz yardmyla 0.1 mm/dak basma hzyla gerekletirilmitir. Elastik modl deerleri gerilim-gerinim diyagramnn dorusal ksmndan hesaplanrken, stenit-martensit
dnm gerilimi % 0.2-offset metodu ile hesaplanmtr. Sperelastisite testleri 0-250 MPa aralnda dngsel
ykleme ve boaltmalarla oda scakl (25 C), vcut scakl (37 C) ve stenit biti (Af) scaklnn 10-20 C
zerindeki bir scaklkta yaplmtr.
3. BULGULAR VE DEERLENDRME
3.1. Faz Dnm Scaklklar

Balang TiNi alam tozu, sinterleme sonras, ve akabinde yalandrma sl ilemine tabi tutulan kpklere ait DSC
erileri ekil 3de gsterilmektedir. Bu erilerden elde edilen [38] dnm scaklklarnn gzeneklilikle ilikisi ise
ekil 4de verilmitir. Yalandrlm numunelerde soutma esnasnda tek bir pik grnrken stma srasnda iki
ayr pik gzlenmitir. ekil 4den aka grld zere gzenekliliin dnm scaklklar zerinde ok fazla bir
etkisi bulunmazken, zellikle martensitik dnm scaklklarnn (martensit balang, Ms, ve martensit biti, Mf)
yalandrma sonras nemli lde ykseldii anlalmaktadr. Ms ve Mf scaklklarndaki art 41-65 C arasndayken (ortalama 46 C Ms iin ve 53 C Mf iin) Af scaklndaki art ortalama 23 C olarak gereklemitir. stenit
balang, As, scakl ise belirgin bir deiim gstermemi ve buna bal olarak martensitik dnm ile ters reaksiyon arasndaki histeresis azalmtr.
269

Istma srasnda gzlemlenen iki ayr pikin varl kpklerin kimyasal olarak homojen olmamasna atfedilmitir.
Yalandrma ilemi sonucu iyapda kelen Ti3Ni4 faz bu homojensizlie neden olmaktadr. Ti3Ni4 keltileri oluurken daha fazla Ni atomu tketildiinden TiNi matrix iindeki Ni miktar azalmaktadr. Ni miktarnn azalmas da
dnm scaklklarndaki art beraberinde getirmektedir. Ti3Ni4 keltileri 50.6 at.% Ni gibi grece az Ni ieren
TiNi alamlarnda homojen olmayan bir ekilde, sadece tane snrlar ve civarnda olumaktadrlar [39]. Bu kelme
davran neden As scaklnn yalandrma sl ilemi sonrasnda ayn kaldn aklamaktadr. keltilerin olumad tanelerin i ksm Nice daha zengindir ve stma srasnda daha nce stenite dnmeye balarlar. Bu da
piklerin genilemesine neden olmaktadr. Benzer durum soutma srasnda da grlr. Dikkat edilirse (ekil 3 (c))
bu piklerin de olduka geni olduu grlmektedir. Tek fark belirgin iki pikin olmamasdr. Ayrca kullanlan TiNi tozu
ve sinterlenen numunelerde de (ekil 3 (a) ve (b)) zellikle soutma esnasnda keskin pikler elde edilememitir.
Bunun yerine olduka geni ve yayvan piklerin gzlenmesi numunelerin iyapsnda Ni dalmnn homojen olmamasna balanmtr.
ekil 3. (a) ve (b) Sinterleme sonras, (c) ve (d) 400 Cde 1 saat sreyle yalandrlan TiNi kpklere ait DSC
erileri. (i) Istma ve (ii) Soutma erisi.
270

ekil 4. Gzenek miktarnn dnm scaklklar zerindeki etkisi.

Ti3Ni4 keltileri soutma srasnda R faznn olumasna neden olabilirler [39-41]. Bu durum DSC erilerinden iki
farkl pikin grlmesiyle anlalr. R faznn olumas sistemin enerjisini drebilir nk B2 stenitten R fazna
dnm latis gerinimini ok az artrmaktadr. te yandan B2den B19 martensite dnm 10 kat daha fazla latis
gerinimi yaratmaktadr. Koherent Ti3Ni4 keltilerinin gerinim alanlar martensit faznn ekirdeklenmesini kolaylatrmaktadr. Fakat ayn zamanda oluan martensitlerin bymesi iin engel tekil etmektedirler. Bu da tamamlanamam dnmlerle sonulanmaktadr. izelge 1den grld zere, bu kompozisyondaki tam bir dnm
iin 23 J/g civarnda olan [42], dnm ss (latent heat of transformation) deerleri olduka dktr. Bu yzden
ekil 5deki XRD diyagramnda (25 Cde elde edilmi) esas olarak martensit faz grlmesi gerekirken stenit faz
daha fazla miktarda bulunmutur. DSC sonularna gre ise Ms ve Mf scaklklar srasyla 65 ve 25 Cdir. R faznn
oluup olumadnn kesin tespiti iin TEM almalarnn yaplmas gerekmektedir. Bu faz termal analiz srasnda
oluuyor oabilir ama DSC erisi zerinde iki pik rttnden gzlemlenmeyebilir. Ayrca uygulanan ksa yalandrma sresi ve de inhomojen dalm kelti younluunun yetersiz olmasna dolaysyla TiNi matrixin yeterince
glendirilememesine neden olabilir. Bylelikle B2den B19a direkt dnm gerekleebilir. 100 nm [43] ve daha
byk boyutlarda olan Ti3Ni4 keltilerinin R faz oluumunu tetikledikleri bilinmektedir. Bu almada uygulanan
yalandrma sl ilemi ayn kompozisyondaki hacimli TiNi alamlarnda 30 nmden [25] daha kk keltilerin
olumasyla sonulanmtr. Gzeneklerin kelti oluumuna etki edecei dnlmemektedir dolaysyla benzer
boyutta keltilerin kpklerde de oluaca dnlrse R faznn olumad sonucu karlabilinir.
izelge 1. Yalandrlm TiNi kpklere ait martensitik ve ters dnmlerin slar.
Gzeneklilik
(%)
Latent heat of transformation, Dnm

ss
(H, J/g)
-Hileri
Hgeri
38
5.3
8.6
43
2.1
4.4
51
4.1
7.5
59
4.3
8.5
271

ekil 5. % 51 gzenekli yalandrlm TiNi kpe ait XRD diagram.

3.2. Mekanik ve Sperelastisite zellikleri
Ayn miktarda gzenee sahip (% 38) TiNi kpklerin iki farkl durumda, sinterleme ve yalandrma sonras, oda
scaklndaki gerilim-gerinim davranlar ekil 6da grlmektedir. Yalandrma sl ilemine maruz braklan kpkler oda scaklnda daha kt sperelastisite davran gsterdiklerinden farkl gzeneklilikteki dier yalandrlm numuneler 80 Cde dngsel basma testine tabi tutulmulardr. Bu scaklk numunelerin Af scaklklarndan
10-15 C daha fazladr ve normal koullarda tam sperelastisite davran beklenmektedir. Dnm scaklklarnn
ykselmesi nedeniyle oda scaklnda, yalandrlm TiNi kpklerin i yaps martensit ve stenit fazlarndan
olumaktadr. Bu scaklkta basma testi yapldnda mevcut martensit faz yeniden ikizlenme mekanizmas ile deforme olurken stenit faz da gerekli kritik gerilme deerine ulaldnda martensit fazna dnmektedir. Yeniden
ikizlenen martensitler ancak Af scaklnn zerine stlarak tekrar stenit fazna dntrlebilinir. Sabit scaklkta
(oda scakl) yaplan test sonucunda stenit fazna dnemediklerinden ekil kazanmna katklar olmamaktadr.
ekil kazanm ykn uzaklatrlmasyla yeniden stenite dnen gerilimle oluturulmu martensitlerden dolaydr. Bu yzden yalandrlm numuneler oda scaklnda daha kt sperelastisite zellii gstermektedirler. Ayn
zamanda daha dk mukavemetlidirler. Gerilim nedeniyle stenitten dnm ile oluan martensitlerin bir ksm
da yalandrlm numunelerin dnm scaklklarnn yksek olmas nedeniyle kararl hale geebilir ve yk uzaklatrldnda tekrar stenite dnmeyebilir. Bu da geri kazanlamayan gerinim miktarlarnda arta neden olur.

ekil 6. % 38 gzenekli TiNi kpn sinterleme ve yalandrma sonras oda scaklndaki

gerilim-gerinim davran.
Farkl miktarda gzenekli yalandrlm TiNi kpklerinin 80 Cdeki gerilim-gerinim davranlar ekil 7den takip
edilebilir. Oda scaklndaki ile karlatrlrsa daha yksek ekil kazanmnn (% 5 civarnda, ekil 7 (a)) olduu
grlecektir. Her ne kadar burada verilmese de, ayn miktarda gzeneklilie sahip ve sinterleme sonras oda ve
vcut scaklnda (37 C ) yaplan testlerden de daha iyi bir sperelastisite ve ekil kazanm salanmtr. Fa-
272

kat ayn gzeneklilikte, sinterlenmi ve baka ilem grmemi numuneler 60 C gibi Af scaklklarndan 10-15 C
daha yksek scaklklarda test edildiinde sinterleme sonras yalandrma ilemine tabi tutulmu ve 80 Cde test
edilmi numuneler ile ok benzer mekanik davran sergilemilerdir, ekil 7 (c). Koherent Ti3Ni4 keltileri mevcut
almadaki kompozisyonda sadece tane snrlar ve yakn evresinde olutuu iin TiNi matrixi yeterince glendirememi ve bunun sonucunda da nemli bir mukavemet artn salayamamtr. Bu keltilerin sperelastisite
zelliini iyiletirmeleri matrixdeki Ni ieriini azaltmalar ve arayzeyde gerilim alanlar oluturarak martensit faznn olumasn kolaylatrmalar ile aklanmaktadr. Ayn zamanda TiNi matrixi glendirerek dislokasyon hareketini zorlatrmaktadrlar. Bylelikle deformasyon srasnda kayma mekanizmasnn aktiflemesini engelleyerek
tamamen gerilim ile oluturulan martensit mekanizmas ile deformasyonun olmasn salamaktadrlar. Hacimli TiNi
alamlarnda basma yk altnda % 6ya [26] kadar olan gerinimler geri kazanlabilmektedir. Ne yazk ki gzenekli
TiNi alamlarnda farkl boyutlarda sinterleme boyunlarnn ve hcre duvarlarnn olumas nedeniyle % 3.5 gibi
dk bir gerinim deeri bile tamamen geri kazanlamaktadr, ekil 7(d). ekil 8de gsterildii zere kararl hale
gelen ve geri dnmeyen martensitler buna neden olmaktadrlar. Isl ilemin daha iyi sonu vermesi iin gerilim
altnda yaplmas ve bu sayede homojen olarak (tane snr ve ilerinde) koherent Ti3Ni4 keltilerinin oluturulmas
salanabilir.
ekil 7. Yalandrlm TiNi kpklerin 80 Cde gerilim-gerinim erileri, (a) % 38, (b) % 43, (c) % 51, (d) % 59
gzenekli.
ekil 8. % 43 gzenee sahip TiNi kpn

% 7 gerinime yklenip boaltldktan sonra
SEMde grntlenen mikroyaps: stenitik
TiNi taneleri iinde beyaz renkli kk martensitler yer almaktadr.
273

ekil 9 sinterlenmi ve yalandrlm numunelerde elastik modl-gzeneklilik-scaklk ilikisini gstermektedir.

Elastik modl deerleri artan gzeneklilik ile dorusal bir ekilde azalrken hacimli TiNi alamlarnda olduu gibi
artan scaklkla artmaktadr. Yalandrlm kpkler daha dk elastik modle sahiptirler. Koherent keltiler her
ne kadar homojen olarak dalmasa da yine de kritik gerilimi drerek martensitin olumasn kolaylatrmtr.
Bu almada % 10-15 aralnda sneklik deerleri elde edilmitir. Zhang ve arkadalarnn almasnda [20]
amonyum bikarbonat boluk yapc olarak kullanlm ve % 61 gzenekli TiNi alam retilmitir. Bu kpk % 3 gerinime kadar (15 MPa) dngsel olarak yklenildiinde ilk dngde krlmtr. Bu almadaki % 59 gzenekli TiNi
kpk ise 80 MPa sabit gerilime (ilk dngde % 6 gerinim) dngsel olarak 20 kez maruz braklm ve herhangi bir
atlak oluumu tespit edilmemitir. Dier btn retim yntemlerinde krlgan, mekanik ve korozyon dayancn dren ikincil intermetaliklerin, oksitlerin ve/veya karbonitratlarn olumas kanlmazdr. Ayn zamanda bu almadaki gibi lokal gerilim konsantrasyonlarn minimize edecek en uygun gzenek ekli olan kre, dier almalarda
elde edilememitir. Sabit basnta scak presleme ileminde mikro-gzenekler nerdeyse sfrlanmakta iken yine de
mukavemet deerlerinin [6,19,44] bu almadakiler ile ayn seviyede olmas gzeneklerin yap ierisinde homojen
olarak dalmamas ve oksitlenme gibi kirlenmeler ile aklanabilir. Dier yntemlerle bu almadaki sneklik deerlerine ulalmas ikincil fazlarn ve kirlenmenin olmas nedeniyle mmkn grlmemektedir.
ekil 9. Young modlnn scaklk, gzeneklilik ve yalandrma sl ilemi ile deiimi.
4. SONULAR
1. Yalandrma sl ilemi TiNi kpklerin dnm scaklklarn As dnda ok nemli oranda artrmaktadr. Ayn
zamanda, yalandrlm TiNi kpklerde faz dnmleri ksmi olmaktadr.
2. Yalandrma sl ilemine maruz kalm TiNi kpklerde Ms scakl, As scaklndan daha yksektir.
3. TiNi kpklerin basma ve sperelastisite davran hacimli TiNi alamlarnnkinden farkldr. Dorusal sperelastisite gsteren kpklerde elastik modl, dayan ve martensit oluturmak iin gereken gerilim deeri artan
gzeneklilikle azalmaktadr.
4. Btn kpklerde ksmi sperelastisite gzlenmi olup, yalandrma ve dngsel ykleme-boaltma sonras
% 5e varan gerinimler tamamen geri kazanlabilmitir. Kalnt gerilmelerin nedeni test scakl ya da farkl
geometrik yapda olan hcre duvarlar ve sinter boyunlarnn farkl gerilmelere maruz kalmas sonucu meydana
gelen martensit stabilizasyonuna balanmtr.
5. Yalandrma sl ilemi martensitik dnm iin gereken gerilim deerini drerek elastik modln de azalmasna neden olmaktadr.
TEEKKR
Bu alma Trkiye Bilimsel ve Teknolojik Aratrma Kurumu (TBTAK, Proje no: 108M118) tarafndan desteklenmitir.
274

KAYNAKLAR
1. Bansiddhi, A., Sargeant, T.D., Stupp, S.I., Dunand, D.C., Porous NiTi for Bone Implants: A Review, Acta Biomaterialia, Vol. 4, pp. 773-782, 2008.
2. Shabalovskaya, S., On the Nature of Biocompatibility and Medical Applications of Shape Memory and Superelastic NiTi-Based Alloys, Bio-Medical Materials and Engineering, Vol. 6,pp. 267-289, 1996.
3. Pelton, A.R., Stoeckel, D., Duerig, T.W., Medical Uses of Nitinol, Materials Science Forum, Vol. 327-328, pp.
63-70, 2000.
4. Aydomu, T., Bor, ., Gzenekli TiNi ekil Bellekli Alamlarnn retilmesi ve Karakterizasyonu, 15. Uluslararas Metalurji ve Malzeme Kongresi, Dzenleyen: TMMOB Metalurji Mhendisleri Odas, s. 665-675, stanbul,
2010.
5. Li, B.Y., Rong, L.J., Li, Y.Y., Gjunter, V.E., Synthesis of Porous Ni-Ti Shape-Memory Alloys by Self-Propagating
High-Temperature Synthesis: Reaction Mechanism and Anisotropy in Pore Structure, Acta Materialia, Vol. 48,
pp. 3895-3904, 2000.
6. Yuan, B., Zhang, X.P., Chung, C.Y., Zeng, M.Q., Zhu, M., A Comparative Study of the Porous TiNi Shape-Memory Alloys Fabricated by Three Different Processes, Metallurgical and Materials Transactions, Vol. 37A, pp.
755-761, 2006.
7. Kaya, M., Orhan, N., Kurt, B., Khan, T.I., The Effect of Solution Treatment under Loading on the Microstructure
and Phase Transformation Behavior of Porous NiTi Shape Memory Alloy Fabricated by SHS, Journal of Alloys
and Compounds, Vol. 475, pp. 378-382, 2009.
8. Tosun, G., Ozler, L., Kaya, M., Orhan, N., A Study on Microstructure and Porosity of NiTi Alloy Implants Produced
by SHS, Journal of Alloys and Compounds, Vol. 487, pp. 605-611, 2009.
9. Aydomu, T., Bor, A.., Production and Characterization of Porous TiNi Shape Memory Alloys, Turkish Journal
of Engineering and Environmental Sciences, Vol. 35, pp. 69-82, 2011.
10. Li, B., Rong, L.J., Li, Y.Y., Porous NiTi Alloy Prepared from Elemental Powder Sintering, Journal of Materials
Research, Vol. 13, pp. 2847-2851, 1998.
11. Zhu, S.L., Yang, X.J., Fu, D.H., Zhang, L.Y., Li, C.Y., Cui, Z.D., Stress-Strain Behavior of Porous NiTi Alloys
Prepared by Powders Sintering, Materials Science and Engineering A, Vol. 408, pp. 264-268, 2005.
12. Greiner, C., Oppenheimer, S.M., Dunand, D.C., High Strength, Low Stiffness, Porous NiTi with Superelastic
Properties, Acta Biomaterialia, Vol. 1, pp. 705-716, 2005.
13. Lagoudas, D.C., Vandygriff, E.L., Processing and Characterization of NiTi Porous SMA by Elevated Pressure
Sintering, Journal of Intelligent Materials Systems and Structures, Vol. 13, pp. 837-850, 2002.
14. Zhao, Y., Taya, M., Kang, Y.S., Kawasaki, A., Compression Behavior of Porous NiTi Shape Memory Alloy, Acta
15. Aydomu, T., Bor, ., Processing of Porous TiNi Alloys Using Magnesium as Space Holder, Journal of Alloys
and Compounds, Vol. 478, pp. 705-710, 2009.
16. Aydomu, T., Tarhan Bor, E., Bor, ., Phase Transformation Behavior of Porous TiNi Alloys Produced by
Powder Metallurgy Using Magnesium as a Space Holder, Metallurgical and Materials Transactions A, in press,
DOI: 10.1007/s11661-011-0714-z.
17. Bansiddhi, A., Dunand, D.C., Shape-Memory NiTi Foams Produced by Solid-State Replication with NaF, Intermetallics, Vol. 15, pp. 1612-1622, 2007.
18. Bansiddhi, A., Dunand, D.C., Shape-Memory NiTi Foams Produced by Replication of NaCl Space-Holders,
Acta Biomaterialia, Vol. 4, pp. 1996-2007, 2008.
19. Wu, S., Chung, C.Y., Liu, X., Chu, P.K., Ho, J.P.Y., Chu, C.L., Chan, Y.L., Yeung, K.W.K., Lu, W.W., Cheung,
K.M.C., Luk, K.D.K., Pore Formation Mechanism and Characterization of Porous NiTi Shape Memory Alloys
Synthesized by Capsule-Free Hot Isostatic Pressing, Acta Materialia, Vol. 55, pp. 3437-3451, 2007.
20. Zhang, Y.P., Li, D.S., Zhang, X.P., Gradient Porosity and Large Pore Size NiTi Shape Memory Alloys, Scripta
21. Grummon, D.S., Shaw, J.A., Gremillet, A., Low-Density Open-Cell Foams in the NiTi System, Applied Physics
Letters, Vol. 82, pp. 2727-2729, 2003.
22. Guoxin, H., Lixiang, Z., Yunliang, F., Yanhong, L., Fabrication of High Porous NiTi Shape Memory Alloy by
Metal Injection Molding, Journal of Materials Processing and Technology, Vol. 206, pp. 395-399, 2008.
23. Bertheville, B., Porous Single-phase NiTi Processed under Ca Reducing Vapor for Use as a Bone Graft Substitute, Biomaterials, Vol. 27, pp. 1246-1250, 2006.
24. Banhart, J., Manufacture, Characterisation and Application of Cellular Metals and Metal Foams, Progress in
Materials Science, Vol. 46, pp. 559-632, 2001.
25. Otsuka, K., Ren, X., Physical Metallurgy of Ti-Ni-based Shape Memory Alloys, Progress in Material Science,
Vol. 50, pp. 511-678, 2005.
26. Otsuka, K., Wayman, C.M., Shape Memory Materials, Cambridge University Press, Cambridge, UK, 1998.
27. Bansiddhi, A., Dunand, D.C., Processing of NiTi Foams by Transient Liquid Phase Sintering, Journal of Materials Engineering and Performance, Vol. 20, pp. 511-516, 2011.
275

28. Yuan, B., Chung, C.Y., Zhu, M., Microstructure and Martensitic Transformation Behavior of Porous NiTi Shape
Memory Alloy Prepared by Hot Isostatic Pressing Processing, Materials Science and Engineering A, Vol. 382,
pp. 181-187, 2004.
29. Chu, C.L., Lin, P.H., Chung, C.Y., Characterization of Transformation Behavior in Porous Ni-rich NiTi Shape
Memory Alloy Fabricated by Combustion Synthesis, Journal of Materials Science, Vol. 40, pp. 773-776, 2005.
30. Chu, C.L., Chung, C.Y., Lin, P.H., Phase Transformation Behaviors in Porous Ni-rich NiTi Shape Memory Alloy
Fabricated by Combustion Synthesis, Materials Science and Engineering A, Vol. 392, pp. 106-111, 2005.
31. Jiang, H.C., Rong, L.J., Ways to Lower Transformation Temperatures of Porous NiTi Shape Memory Alloy Fabricated by Self-propagating High-temperature Synthesis, Materials Science and Engineering A, Vol. 438-440,
pp. 883-886, 2006.
32. Wu, S.L., Liu, X.M., Chu, P.K., Chung, C.Y., Chu, C.L., Yeung, K.W.K., Phase Transformation Behaviour of
Porous NiTi Alloys Fabricated by Capsule-free Hot Isostatic Pressing, Journal of Alloys and Compounds, Vol.
449, pp. 139-143, 2008.
33. Li, B.Y., Rong, L.J., Luo, X.H., Li, Y.Y., Transformation Behavior of Sintered Porous NiTi Alloys, Metallurgical
and Materials Transactions A, Vol. 30, pp. 2753-2756, 1999.
34. Scalzo, O., Turenne, S., Gauthier, M., Brailovski, V., Mechanical and Microstructural Characterization of Porous
NiTi Shape Memory Alloys, Metallurgical and Materials Transactions A, Vol. 40, pp. 2061-2070, 2009.
35. Yuan, B., Zhang, X.P., Chung, C.Y., Zhu, M., Superelastic Properties of Porous TiNi Shape Memory Alloys Prepared by Hot Isostatic Pressing, Materials Science and Engineering A, Vol. 438-440, pp. 657-660, 2006.
36. Bassani, P., Giuliani, P., Tuissi, A., Zanotti, C., Thermomechanical Properties of Porous NiTi Alloy Produced by
SHS, Journal of Materials Engineering and Performance, Vol. 18, pp. 594-599, 2009.
37. Li, H., Yuan, B., Gao, Y., Chung, C.Y., Zhu, M., High-porosity NiTi Superelastic Alloys Fabricated by Lowpressure Sintering Using Titanium Hydride as Pore-forming Agent, Journal of Materials Science, Vol. 44, pp.
875-881, 2009.
38. ASTM F 2004-05, Standard Test Method for Transformation Temperature of Nickel-Titanium Alloys by Thermal
Analysis, ASTM, Philadelphia, PA, 2010.
39. Fan, G., Chen, W., Yang, S., Zhu, J., Ren, X., Otsuka, K., Origin of Abnormal Multi-stage Martensitic Transformation Behavior in Aged Ni-rich Ti-Ni Shape Memory Alloys, Acta Materialia, Vol. 52, pp. 4351-4362, 2004.
40. Khalil-Allafi, J., Ren, X., Eggeler, G., The Mechanism of Multistage Martensitic Transformations in Aged Ni-rich
NiTi Shape Memory Alloys, Acta Materialia, Vol. 50, pp. 793-803, 2002.
41. Khalil-Allafi, J., Dlouhy, A., Eggeler, G., Ni4Ti3-precipitation during Aging of NiTi Shape Memory Alloys and its
Influence on Martensitic Phase Transformations, Acta Materialia, Vol. 50, pp. 4255-4274, 2002.
42. Miller, D.A., Lagoudas, D.C., Influence of Cold Work and Heat Treatment on The Shape Memory Effect and
Plastic Strain Development of NiTi, Materials Science and Engineering A, Vol. 308, pp. 161-175, 2001.
43. Gall, K., Juntunen, K., Maier, H.J., Sehitoglu, H., Chumlyakov, Y.I., Instrumented Micro-indentation of NiTi
Shape Memory Alloys, Acta Materialia, Vol. 49, pp. 3205-3217, 2001.
44. Li, D.S., Zhang, Y.P., Eggeler, G., Zhang, X.P., High Porosity and High-strength Porous NiTi Shape Memory
Alloys with Controllable Pore Characteristics, Journal of Alloys and Compounds, Vol. 470, pp. L1-L5, 2009.
276

MODELING,
SIMULTATION AND
CHARACTERIZATION
www.turkishpm.org
277

FARKLI GEOMETRLERE SAHP GAZ ATOMZASYONU NOZUL

PERFORMANSLARININ HESAPLAMALI AKIKANLAR DNAM (CFD)
LE KARILATIRILMASI
Mustafa GLEEN*, Rahmi NAL** ve Melih C. KUHAN*
*
Eskiehir Osmangazi niversitesi, Mhendislik ve Mimarlk Fakltesi, Makine Mhendislii Blm, 26030,
Eskiehir, mgulesen@ogu.edu.tr, mckushan@ogu.edu.tr
**
Dumlupnar niversitesi, Mhendislik Fakltesi, Makine Mhendislii Blm, 43020, Ktahya,
runal@dpu.edu.tr,
ZET
Bu almada nozul tasarmnda nemli olan geometri ve gaz k alan deikenleri deitirilerek nozul veriminin
daha yksek olabilecei en uygun tasarm CFD zm yntemiyle bulunmaya allmtr. Bu amala 3 farkl yeni
tasarm yaplarak daha yksek verimli nozul tespit edilmeye allmtr. CFD sonularna gre en uygun tasarmn
Model 3 adl tasarm olduu anlalmtr. Bu tasarm metal ak borusu ucunda en yksek emme basncn oluturmakla birlikte en yksek hz deerlerine dk basnlarda dahi ulamaktadr. Ayrca gaz tketimi de bu tasarm iin
en dk deerdedir. Btn bunlardan dolay model 3 adl tasarm mevcut nozul performansna gre daha yksek
performansa sahiptir. Bu sonular ile CFD zmlerinin nozul tasarmnda kullanlabilecei ortaya konmutur. Bylece daha dk maliyet ve ksa srede daha yksek verimli nozul geometrisi gelitirmek mmkn olabilecektir.
Anahtar Kelimeler: Gaz atomizasyonu, Nozul tasarm, CFD
COMPARISON of DIFFERENT GEOMETRICAL GAS ATOMIZATION NOZZLE

PERFORMANCES BY COMPUTATIONAL FLUID DYNAMICS (CFD)
ABCTRACT
This study is important in the design of the nozzle geometry and gas output may be higher than the yield of field
variables by changing the nozzle design the most appropriate method of CFD model with the best solution. For this
purpose, a new design made of 3 different nozzle tried to determine a more highly efficient. According to the results
of the CFD model 3s design proved to be the most appropriate design. This design tip of the metal flow tube with
creating the highest suction pressure reaches the highest velocity values, even at low pressures. In addition, gas
consumption is also low for this design value. Because of this design available at Model 3 has higher performance
than the performance of the nozzle. These results suggest that the CFD solutions were used in the design of the
nozzle. Thus, lower cost and shorter time will be possible to develop highly efficient nozzle geometry.
Keywords: Gas atomization, Nozzle design, CFD (computational fluid dynamics)
1.GR
Gaz atomizasyon yntemi ok sayda atomizasyon deikenlerine sahiptir (sv metal debisi, gaz debisi, gaz basnc ve nozul geometrisi). Bu deikenlerden en nemlisi nozul geometrisidir [1]. Nozul en basit kelime anlamyla
simetri ekseni boyunca hareket eden akkann hzn artrrken basncn dren geometrik yapya verilen isimdir. Gaz atomizasyonunda kullanlan nozullar farkl geometrilere sahiptirler. Genel olarak kullanlan nozullar, sonik
(daralan) veya spersonik (daralan-genileyen) geometriye sahiptirler. Atomizasyon ileminde nozul, gazn kinetik
enerjisini sv metale aktarr. Yaplan almalar sonucu elde edilen bilgilere gre spersonik geometrili nozullar,
278

sonik geometrili nozullara gre daha iyi gaz genleme davran gsterirler. Bylelikle spersonik nozullarda daha
ince boyutta toz retimi gerekletirilir. Yksek verimli nozullar mmkn olduu kadar dk atomizasyon basnlarnda daha kk apta toz retimine imkan salarlar. Yakndan elemeli sistem ile toz retimi fiziksel olarak
olduka karmak bir ilemdir. Yakndan elemeli sistemlerde gaz dolam blgesi ve bu blgenin atomizasyona
olan etkisinin aratrma konusu olmutur. Gaz ak dinamii konularnda yaplan aratrmalar sonucu daha ince toz
boyut dalmna sahip tozlar retilmi ve atomizasyon ileminin verimi artrlmtr [2-7]
Akn olduu mhendislik sistemlerinin tasarm ve analizinde iki temel yaklam vardr: deney yapma ve hesaplama. Gnmz aratrmaclar hem deneysel analizi hem de CFD (hesaplamal akkanlar dinamii) analizini
uygularlar ve bu ikisi bir birini tamamlar. Hesaplamal akkanlar dinamii (CFD) ile laminer aklar kolayca zmlenebilirken, uygulamadaki trblansl aklar trblans modellerini kullanmakszn zmek imkanszdr. Ne yazk
ki genel bir trblans modeli yoktur ve bir trblansl CFD zm, sadece trblans modelinin uygunluu kadar
iyidir. Bu snrlamaya ramen, standart trblans modelleri uygulamadaki ou mhendislik problemlerinde makul
zmler verir. Saysal ve deneysel olarak bulunan genel byklklerin karlatrlmas yoluyla CFD zmlerini
dorulamak iin ounlukla deneysel veriler kullanlr. CFD, daha sonra, dikkatlice kontrol edilen parametrik incelemeler yoluyla, gerekli deneysel test saysn drerek tasarm srecini ksaltmak iin kullanlr [8].
Gaz atomizasyon ileminde nozul ak blgesinde atomizasyon gaznn scakl, hz ve basnc ergiyik metalin
ak zerine aktarlmas, kinetik enerjiyi ve soutma etkisini belirler ve dolaysyla retimi nemli lde etkiledii
gibi balang boyutu, ekli, damlacn uu yn ve radyal dalm etkiler. Nozula yakn blgede gaz ak analizi, saysal simlasyon/modelleme hesaplamal akkanlar dinamii (CFD) kodlar yardmyla yaplabilir. Bu kodlar
genellikle sktrlamaz ve/veya sktrlabilir aklar zer ve trblans modelleri kullanlr. Nozula yakn blgede
atomize gazn ak ve hz blgelerinin modellenmesi atomizasyon parametrelerinin optimizasyonu iin temel kurallar salar. Bu durumda modelleme sonular farkl atomizasyon ilemlerinin modellenmesinde balang koullar
salar [9].
Bu almada Aydn ve naln [ 1,10-11] yaptklar almalar farkl geometrilere sahip atomizasyon ilemlerinin
modellenmesinde balang koullarn salamtr. CFD modelin deneysel verilere yaklam en iyi olacak ekilde
model zerinde eitli parametrelerin etkileri incelenmitir. Nozul tasarmnda nemli olan geometri ve gaz k
alan deikenleri deitirilerek nozul veriminin daha yksek olabilecei en uygun tasarm bulunmaya allmtr.
Yeni tasarmlar yaplarak daha yksek verimli nozul elde edilmeye allmtr.
2. FZKSEL MODELN TANIMI
Model geometrilerinin oluturulmasndan nce DPU Makine Mhendislii laboratuarndaki gaz atomizasyon nitesinde kullanlan mevcut nozulun geometrisi ekil 1de gsterilmitir. Burada nozul as, A knt mesafesi ve
R boaz akl olarak tanmlanmtr. Nozul yksek basnl tpe bal orta bir giri ile tek bir manifoldu vardr.
Atomizasyon gaz olarak azot kullanlmtr. Nozul 0.2 mm boaz akl, 5 mm knt mesafesine ve 260 lik nozul
asna sahiptir. Oluturulan geometrilerde, boaz akl, knt mesafesi ve nozul as deerleri deitirilerek 3
farkl nozul geometrisi oluturulmutur (ekil 2).
ekil 1. Nozulun ematik gsterimi.
279

ekil 2. Farkl geometrilere sahip nozullar.

Mevcut nozul geometrisine gre Model 1de nozul as () 260 sabit tutulmu, boaz akl (R) 0.3 mm karlm
ve knt mesafesi (A) 6 mm olarak arttrld grlmektedir. Model 2de boaz ksmanda gazn kat edecei mesafe
arttrlm boaz akl 0.2 mm, nozul as 160 ve knt mesafesi mevcut nozuldaki gibi 5 mm alnmtr. Model
3te daralan-genileyen ksmlarn alar mevcut nozulla ayndr. Fakat daralan ksmda gazn kat edecei mesafe
arttrlm boaz akl 0,2 mm ve knt mesafesi 6.84 mmye karlmtr.
Atomizasyon gaz ak modeli olutururken aadaki kabuller alnmtr.
Gaz ak srekli bir rejimdir.
Atomizasyon nozul sisteminin simetrik ekle sahip olduu iin hesaplama iki boyutlu eksenel simetrik olarak
zlmtr.
Gaz ak izentropik sktrlabilir ve ideal gaz yasas kanunu kabul edilmitir.
Gaz ak trblansl ak ve ak katmanlar arasnda momentum ve enerji transferi vardr.
Yerekimi ihmal edilmitir.
3. SAYISAL MODELLEME VE HESAPLAMA METODU
3.1 Temel Denklemler
Atomizasyon sistemin sadece gaz akn simle edilmesi ile atomizasyon gaz basncnn etkileri zerine modelleme almas, CFD yazlmnn paket program FLUENT 6.3 kullanlarak yerine getirilmitir. FLUENT 6.3 program
seilen denklemlerin zmnde sonlu hacim yaklamn kullanr. CFD gibi byle nmerik modelleme teknikleri
ak ve s transferi problemlerini simule etmek iin gl bir aratr. Ktlenin korunumu veya sreklilik denklemi,
momentumun korunumu veya NavierStokes transport denklemi ve enerjinin korunumu denklemi nmerik olarak
zlebilir. ki boyutlu eksenel simetrik geometriler iin sreklilik denklemi; [12]

(1)
Burada gaz younluu, x eksenel koordinat, r radyal koordinat, vx eksenel hz, and vr radyal hzdr. Sm kaynak
terimi ise ayrlm ikinci fazdan (sv damlacklarnn buharlamas nedeniyle gibi) srekli faza ilave edilen ktle
ve herhangi bir kullanc tarafndan tanmlanm kaynaktr. Denklem (1) sktrlabilir ve sktrlamaz aklar iin
kullanlan ktlenin korunumu denkleminin genel formudur. ki boyutlu eksenel simetrik geometriler iin eksenel ve
radyal momentum korunum denklemleri aada verilmitir.
(2)
280

ve
Burada;
(3)
Burada p statik basn,

gerilim tens, vz swirl hz,
faz ile etkileimden ykselme gibi).
(4)
ve
Reynolds stress model (RSM) gre trblans kinetik enerji

mitir.
srasyla yerekimi kuvveti ve d kuvvettir (ayrk

ve trblans yitim hz
denklemleri aada veril(5)
ve
(6)
Burada;
= 0:82,
= 1,
= 1:44,
fonksiyonu olarak llm deerler ve
and
= 1:92,
Yerekimi vektrle alakal lokal ak ynnn bir
kaynak terimlerdir.
Sktrlabilirlik etkilerine yksek hzlardaki gaz aklarnda ve/veya byk basn deiimlerinde karlalr. Ak
hz gazn ses hzna yaklat ya da at zaman veya sistemde basn deiimi (p=p) byk olduu zaman
basnla gaz younluunun deiimi ak hz basnc ve scakl zerinde nemli bir etkiye sahiptir. Sktrlabilir
aklar iin, ideal gaz kanunu aadaki formda yazlr;
(7)

Burada pop iletme basnc (operating conditions panelinde tanmlanr), p iletme basncna gre bal lokal statik
basn, R niversal gaz sabiti, ve Mw molekler arlktr. Scaklk T enerjinin korunum denkleminden hesaplanabilecektir.
3.2 A Yapsn Oluturma
Nozul iki boyutlu ve eksenel simetri olmak zere GAMBIT 2.4.6 programnda izilmi ve a yaps (meshleme)
oluturulmutur (ekil 3). ki boyutlu eksenel simetrik geometrili zm, iki boyutlu ve boyutlu geometrilere gre
hassasiyet asndan bakldnda daha avantajldr. nk grid saysnn azl zaman tasarrufu salayaca gibi,
alan bana den grid miktar dierlerine gre olduka yksektir.
ekil 4te nozulun yaknsak-raksak blgesinin grid yaps ve hesaplanan alan gsterilmitir. Nozulun en dar blgesi
(boaz) 0.2 mm. Ak daha iyi analiz edebilmek iin nozul blgesi ince meshlenmitir. Bu almada incelenen tm
durumlar iin, gen a yaps tercih edilmitir. Oluturulan a yaps ak zelliklerini ve ak tahminleri, sktrlabilir ak teorileri ve literatrle tutarl bir ekilde yakalamak mmkndr [13].
281

ekil 3. Mesh yaps ve snr artlar.
ekil 4. Kritik blgelerdeki ve cidarlardaki mesh yaplar.

3.3 Snr artlar
CFD simlasyonlar basnca dayal, kararl durum ayrlm tam zc kullanlarak yapld. Ak trblansl, viskoz
model olarak Reynolds stres model (RSM) kullanlarak simlasyon yapld. Model sabitleri default deerler uyguland. Programn zc tipi seiminde seilenler ise pressure based, implicit yaklam, standart duvar fonksiyonu
ve steady (kararl) zmdr. Akkan olarak azot gaz, younluk iin ideal gaz kanunu ile sktrabilir gaz gibi
modellendi ve NIST verilerine gre gaz sabitleri Tablo 1 de verilmitir[14]. NIST verilerine gre azot gaznn sktrabilirlik faktr 11 Atmosfer basncnda ve 300 K scaklkta 0,998 dir. Bu durumda ideal gaz kanunu bu simlasyon
kullanmak makuldr. Snr artlar ekil 3te gsterilmitir. Atomizasyon basnc 0.8, 1.0, 1.3 ve 1.7 MPa deerler
CFD modelleme esnasnda gaz giri basnc olarak kullanld. Gaz giriindeki scaklk 300 K alnd. Gaz kn
CFD modelde basn k olarak belirtildi ve atmosfer basn deeri alnd. Tm duvar scaklklar 300 K alnd.
Sutherland vizkosite kanunu ideal gazlarn kinetik kuram ve idealize edilmi bir molekller aras kuvvet potansiyeline dayanmaktadr. Bu forml iki veya katmanldr. Bu almada katmanl Sutherland kanunu kullanlmtr.
katmanl Sutherland kanunu;
(8)
Burada viskozite (kg/ms), T statik scaklk (K), 0 bir referans deer (kg/ms), T0 bir referans scaklk (K), ve S
ise gazn karakteristii olan Sutherland sabiti olarak isimlendirilen bir efektif scaklk (K). Scaklk ve basncn orta
deerlerinde hava iin, 0= 1.7894x0-5 kg/ms, T0 = 273.11 K, and S = 106.67 K [15].
282

Tablo 1 Saysal simlasyon iin azot gaznn zellikleri

Fiziksel zellikler
Deer
Younluk (kg/m3)
1.138
C (J/(kg.K))
1040.67
Termal iletkenlik (W/(m.K))
0.0242
Referans viskosite (kg/(m.s))

Referans scaklk (K)
1.663 10-5
273.11
Efektif scaklk (K)
106.67
Molekler arl (kg/(kg.mol))
28.0134
Standart hal entropisi (J/(kg.mol.K))
191494.8
3.4 zm Metodu
zme balama aamasnda programn kullanc kitabndan olduka yararlanlmtr. Yksek basnl almalarda zme balamada nerilen yollarn kullanlmas nem arz etmektedir. Aksi takdirde zme ulalamamaktadr.
Bunun iin zellikle 200 iterasyonda kararl bir yaknsama salanmas iin enerji denklemleri seilmemitir. Balang deeri iin hz deeri programn hesaplad deerden daha dk girilmitir. Ayrca rahatlatma faktrleride
(under-relaxation factor) basn iin 0.4, momentum iin 0.3, younluk iin 0.3, enerji iin 0.9 seilmitir ve dierleri
default deerleri olarak ayn kalmtr. Yaknsama da kararl bir grnt salandktan sonra (200 iterasyon sonra)
enerji denklemi almtr. zm iin 1.dereceden denklemler (first order upwind) seilmitir. RSM ayrklatrma
zmnde 2. dereceden denklemler (second order upwind) altnda simlasyonun yaknsamas olduka zordur[14].
Yaknsama kriteri olarak ise enerji denkleminin 10-6 hata oran esas alnmtr. Ayrca giri ve k arasndaki ktlesel debiler arasndaki farknda 10-6 orannda bir farka ulamas yaknsama kriteri olarak gz nne alnmtr.
4. BULGULAR ve DEERLENDRME
Bu almada simlasyonun doruluu naln deneysel verilerinden yararlanlmtr [1,17-18]. Aydn ve nal yaptklar almada saysal zmlemeleri ile deneysel verilere bakldnda nozul gaz basnlar arasndaki fark tm
basnlarda ayn olduu, deneysel verilerde nozul u basnc daha az olmakla birlikte, Realizable model sonular
ile arasndaki fark %11-15 arasnda deitiini tespit etmilerdir [11]. Reynolds stres model ile deneysel verileri kyaslandnda %3-11 arasnda deiirken, %11 fark sadece 1.0 MPa basn altnda elde edilmitir. 1.3, 1.7, 2.2 ve
2.7 MPa basnlarda deneysel verilere yaknl %3-5 arasndadr (ekil 6). Bu sonuca gre Reynolds stres model
deneysel verilere en yakn sonucu vermitir. Elde edilen bu sonuca gre tasarlanan modeller de Reynolds stres
modele (RSM) gre zm yaplmtr. zm sonular Tablo 2de verilmitir.
ekil 5. Nozul u basncnn CFD ve deneysel veriler ile karlatrlmas[11].
283

Atomizasyon basncna gre metal ak borusu u basn deerlerinin karlatrlmas ekil 6da verilmitir. Model
3 adl nozulun dierlerine gre belirgin bir ekilde daha yksek negatif basn oluturduu grlmektedir. Bu basn
sv metalin nozula ekilmesini salayarak atomizasyon ileminin yerekimi etkisiyle yaplabileceini gstermektedir. Eer u basn pozitif olursa sv metalin yerekimi etkisiyle ak mmkn olmadndan ergitme odasnn
kapal olarak yaplmas ve st basn uygulamak gerekecektir. Gaz basncna gre gaz debisinin deiimi ekil 7de
verilmitir. Bu deerlerin incelenmesi sonucu model 2 ve model 3 adl tasarmlarn debi asndan da en uygun tasarmlar olduu grlmektedir. Gaz debisinin daha az olmas gaz tketimini azaltacandan dolay dierlerine gre
daha verimli bir nozul tasarm olduu sylenebilir.
Tablo 2. Nozullarn CFD zm deerleri
Model 3
Model 2
Model 1
Mevcut
Nozul [9]
Nozul
Nozul
As
26
26
16
26
Boaz
akl
(mm)
0,2
0,3
0,2
0,2
Boaz
Alan
(mm2)
8,5
12,7
11
11
knt
Mesafesi
(mm)
6,84
alma
Basnc (bar)
Gaz Hz
(m/s)
Mach
Says
Gaz Debisi
(kg/dak)
U Basnc
(mbar)
597
2,61
1,06
1002
10
613
2,77
1,72
1023
13
622
2,88
2,24
1070
17
626
2,94
2,95
1166
580
2,51
1,74
965
10
592
2,58
2,14
1007
13
608
2,69
2,84
1086
17
624
2,81
3,54
1176
590
2,57
1,13
1009
10
605
2,72
1,42
1027
13
629
2,96
1,84
1061
17
647
3,21
2,46
1144
594
2,84
1,08
956
10
623
2,88
1,61
971
13
636
3,05
1,94
974
17
646
3,23
2,64
1023
ekil 6. Atomizasyon basncna gre nozullarn u basn deiimi.
284

ekil 7. Atomizasyon basncna gre nozullarn gaz debisi deiimi.

Gaz basncna gre Mach saysnn deiimi ekil 8de verilmitir. Mach saysnn en yksek olduu tasarm Model
3 adl tasarmdr. Bu tasarmda Mach saysnn dk basnlarda dahi daha yksek olduu grlmektedir. Mach
saysnn yksek olmas bu tasarmda gazn daha iyi hzlandn ve dolaysyla daha yksek bir kinetik enerjiye
sahip olduu anlamna gelmektedir. Bu da daha yksek verimli bir atomizasyon ileminin gereklemesini salayacaktr. Sonuta dk basnlarda daha kk toz retmek mmkn olabilecektir.
ekil 8. Atomizasyon basncna gre nozullarn Mach says deiimi.

Gaz basncna gre gaz hznn deiimi ekil 9da verilmitir. Burada da model 3 adl tasarm baz basnlarda en
yksek gaz hzna sahip olmakla birlikte dier tasarmlar ile arasndaki fark ok belirgin deildir. Ancak basnca gre
deiimi daha azdr. Model 3 adl tasramda 1.3 MPa basnta dahi 636 m/s gibi yksek hza ulamas tasarmn
dierlerine gre stnln gstermektedir. Atomizasyon basncna gre Mach/gaz debisi orannn deiimi ekil
10da verilmitir. Model 2 ve Model 3 dier tasarmlara gre daha stn gzkmektedir. Dk gaz debisinde yksek hzn elde edilmesi nozulun verimini arttracaktr.
285

ekil 9. Atomizasyon basncna gre nozullarn hz deiimi.
ekil 10. Atomizasyon basncna gre nozullarn Mach says/gaz debisi orannn deiimi.
Daha az gaz debisi ile yksek hzn elde edilmesi tketimin az olmasna karn kinetik enerjinin yksek olmas anlamna gelmektedir. Buda daha kk tozun retilebilmesine imkan verir. Btn karlatrmalar dikkate alndnda
en iyi tasarmn Model 3 adl tasarm olduu grlmektedir. Mevcut nozul 1.0 MPa basnta 613 m/s hz, 2,77 Mach
says, 1,72 kg/dak debi ve 1023 mbar u basn deerlerine sahip iken model 3 adl tasarm 1.0 MPa basnta 623
m/s hz, 2,88 Mach says, 1,61 kg/dak debi ve 971 mbar u basn deerine sahiptir.
5. SONULAR
Bu almada farkl geometrilere sahip nozullarn performanslar CFD yntemi ile incelenerek en uygun tasarmn
bulunmas hedeflenmitir. Bu amala 3 farkl geometri karlatrlarak en uygun tasarm belirlenmitir. CFD sonularna gre en uygun tasarmn Model 3 adl tasarm olduu anlalmtr. Bu tasarm metal ak borusu ucunda
en yksek emme basncn oluturmakla birlikte en yksek hz deerlerine dk basnlarda dahi ulamaktadr.
Ayrca gaz tketimi de bu tasarm iin en dk deerdedir. Btn bunlardan dolay model 3 adl tasarm mevcut
nozul performansna gre daha yksek performansa sahiptir. Bu sonular ile CFD zmlerinin nozul tasarmnda
kullanlabilecei ortaya konmutur. Bylece daha dk maliyet ve ksa srede daha yksek verimli nozul geometrisi gelitirmek mmkn olabilecektir.
286

KAYNAKLAR
1. Unal R. Improvements to close coupled gas atomization nozzle for fine powder production Powder Metallurgy, 50(1): 66-71, 2007.
2. LE T., and Henein, H., , Effect of nozzle geometry and position on gas atomization, The international journal
of powder metallurgy, Volume 32, No 4, 353-363, 1996.
3. http://www.cstl.nist.gov/div836/836.01/PDFs/1998/EPMA_US.pdf
4. Ting J, Peretti M W, Eisen W B. The effect of wake-closure phenomenon on gas atomization performance,
Mater Sci Eng A, 326(1): 110121 2002.
5. Mates, S. P., and Settles, G. S., A flow visualization study of the gas dynamics of liquid metal atomization nozzles, Proceedings of the 1995 International Conference on Powder Metallurgy and Particulate Materials,
Seattle, May 14-17, 1995.
6. Ting J, Anderson IE, A computational fluid dynamics (CFD) investigation of the wake closure phenomenon,
Materials Science and Engineering A, 379: 264-276, 2004.
7. Strauss, J.T., Hotter gas atomization increases atomization efficiency, Metal Powder Report, Volume 54,
Issue 11, 24-28, 1999.
8. engel Y A., Cimbala J M., Akkanlar Mekanii Temelleri ve Uygulamalar, Birinci baskdan eviri, 2008.
9. Liu H., Science and engineering of droplets Fundamentals and applications, Noyes publications, New Jersey,
USA, 2000.
10. nal, R., Investigation of the Metal Powder Production Efficiency of a New Convergent-Divergent Nozzle in
Close-Coupled Gas Atomisation, Powder Metallurgy, Vol.50, No.4,p.302-306, 2007.
11. Aydn O., Unal R., Experimental and numerical modeling of the gas atomization nozzle for gas flow behavior,
Computers and Fluids, 42, 37-43, 2011.
12. Fluent 6.1 Users Guide, Fluent Inc., Centerra Resource Park, 10 Cavendish Court, Lebanon, NH 03766, USA,
2003.
13. White F.M., Fluid Mechanics, McGraw-Hill Book Co. 2nd Ed., 1988.
14. NIST Reference Fluid Thermodynamic and Transport Properties Database (REFPROP) version 7.0, National
Institute of Standards and Technology, Boulder, CO 80305-3328, USA.
15. Fluent Inc., GAMBIT Users Guide, Fluent Inc., Lebanon, 2002.
16. Gimbun, J., at all, The influence of temperature and inlet velocity on cyclone pressure drop; a CFD study
Chemical Engineering and Processing 44 7 12, 2005.
17. Aksoy A, nal R. Effects of gas pressure and protrusion length of melt delivery tube on powder size and
powder morphology of nitrogen gas atomized tin powders Powder Metall, 49(4): 349354, 2006.
18. Unal R. The influence of the pressure formation at the tip of the melt delivery tube on tin powder size and gas/
melt ratio in gas atomization method Journal of Materials Processing Technology, 180: 291-295, 2006.
19. Gleen M., nal R., Aydn ., Gaz atomizasyonu nozulunun hesaplamal akkanlar dinamii (CFD) ile nmerik modellenmesi, 6th International Powder Metallurgy Conference, 2011
287

Hesaplamal Akkanlar Dinamii (CFD) Yntemi ile

Gaz Atomizasyon Nozul Geometrisinin yiletirilmesi
zer Aydn and Rahmi nal
Dumlupinar University, Engineering Faculty, Mechanical Eng. Dept.,
43100 Kutahya-Turkey ozaydin@dpu.edu.tr, runal@dpu.edu.tr
ZET
alma kapsamnda Fluent program kullanlarak CFD yaklam ile metal tozu retiminde kullanlan
gaz atomizasyon nozulunun teorik modellemesi yaplmtr. ncelikle, TBTAK 105M033 nolu projede
gelitirilen ve toz retiminde kullanlan nozulun deneysel verileri ile modellemenin doruluu tespit edilmeye allmtr. Deneysel verilerde nozul u basnc daha az olmakla birlikte CFD sonular ile arasndaki fark %11-15 arasnda deimektedir. CFD ile modellenen nozulda elde edilen veriler ile deneysel
verilerin karlatrlmas sonucunda CFD yaklamnn nozul tasarm iyiletirilmesinde kullanlabilecei
ortaya konmutur. Daha sonra nozul tasarmnda nemli olan geometri ve gaz k alan deikenleri
deitirilerek nozul veriminin daha yksek olabilecei en uygun tasarm bulunmaya allmtr.
Keywords: Gaz atomizasyonu, nozul tasarm, CFD
ABSTRACT
In this study, gas atomisation nozzle for metal powder production was modelled with a CFD approach
by using Fluent programm. First of all, the powder production data of the nozzle designed and used for
metal powder production in the project of TUBTAK with the number of 105M033 was compared with
the CFD modelling data to confirm the theoretical modell. CFD modell was improved by changing the
modelling parameters. The difference between the experimental data and the CFD modell data for the
nozzle melt tip base pressure varies about 11-15%. With comparison of the experimental data and the
theoretical data obtained from the CFD study of the nozzle it was concluded that this CFD modell can be
used for the design of the nozzle. Then, the geometry and the nozzle throat gap were changed and the
effect of these parameters were determined to find out the best efficient nozzle design parameters.
Key Words: Gas Atomization, Nozzle Design, CFD.
1. GR
Metal tozu retimi iin farkl yntemler kullanlmaktadr. Bu yntemlerden en geni ve ticari olarak kullanma sahip olan atomizasyon yntemidir. Atomizasyon ile retilmi tozlar dier retim yntemleri (mekanik yntemler, elektroliz, kimyasal yntemler) ile elde edilemeyecek zelliklere ve avantajlara sahiptir.
Atomizasyon, sv metal demetinin basnl akkanlar ile veya mekanik olarak paralanmasyla oluan
damlacklarn katlama davran gstererek metal tozu haline gelmesidir. Basnl akkan olarak gazn kullanld atomizasyon trne gaz atomizasyonu, suyun kullanld atomizasyon trne su atomizasyonu denir. Gaz atomizasyonu sistemleri genel olarak serbest dmeli ve yakndan elemeli olmak
zere ikiye ayrlr. Yakndan elemeli atomizasyon sistemleri daha iyi kinetik enerji transferi salad
iin serbest dme ynteminden daha stndr [1-3]. Yakndan elemeli sistemlerde daha ince boyutlarda ve daha dar dalma sahip tozlar retmek mmkndr.
288

Gaz atomizasyon yntemi ok sayda atomizasyon deikenlerine sahiptir (sv metal debisi, gaz debisi,
gaz basnc ve nozul geometrisi). Bu deikenlerden en nemlisi nozul geometrisidir. Nozul en basit
kelime anlamyla simetri ekseni boyunca hareket eden akkann hzn artrrken basncn dren
geometrik yapya verilen isimdir. Gaz atomizasyonunda kullanlan nozullar farkl geometrilere sahiptirler. Genel olarak kullanlan nozullar, sonik (daralan) veya spersonik (daralan-genileyen) geometriye
sahiptirler. Atomizasyon ileminde nozul, gazn kinetik enerjisini sv metale aktarr. Gazn hz, basnc,
scakl ve younluu gibi zellikleri nozulun yapsna, tasarmna ve verimliliine baldr. Yaplan almalar sonucu elde edilen bilgilere gre spersonik geometrili nozullar, sonik geometrili nozullara gre
daha iyi gaz genleme davran gsterirler [4-7]. Bylelikle spersonik nozullarda daha ince boyutta toz
retimi gerekletirilir. Yksek verimli nozullar mmkn olduu kadar dk atomizasyon basnlarnda
daha kk apta toz retimine imkan salarlar. Yakndan elemeli sistem ile toz retimi fiziksel olarak
olduka karmak bir ilemdir. Paralanma mekanizmasnn karmaklndan dolay bu ilem bugne
kadar tam olarak anlalm deildir. Bu nedenle, toz retim kabiliyetinin gelitirilmi nozul tasarm ile
iyiletirilme konusunda byk bir potansiyel vardr ve gnmzde almalar bu ynde devam etmektedir [8-11].
Bu alma kapsamnda Fluent program kullanlarak CFD yaklam ile nozulun teorik modellemesi
yaplmtr. ncelikle daha nce blmmz laboratuarnda gerekletirilen toz retim almalarnda
kullanlan nozulun deneysel verileri ile modellemenin doruluu tespit edilmeye allmtr. CFD modelinin deneysel verilere yaklam en iyi olacak ekilde model zerinde eitli parametrelerin etkileri
incelenmitir. Daha sonra nozul tasarmnda nemli olan geometri ve gaz k alan deikenleri deitirilerek nozul veriminin daha yksek olabilecei en uygun tasarm bulunmaya allmtr.
2. YNTEM
2.1. Deneysel alma
Atomizasyon ileminin kararl bir ekilde gerekleebilmesi iin nozul ierisine yerletirilen sv metal
ak borusu u noktasnda meydana gelen basn nemlidir ve bu basncn bilinmesi gerekir. Sv metalin
atomizasyonu srasnda bu basncn lm mmkn olmadndan dolay genellikle sadece atomizasyon gaz verilerek u basn lmleri yaplr. Bu amala kurulmu dzenek ekil 1de gsterilmitir.
ekil 1. Spersonik geometrili nozulun ematik gsterimi ve metal ak borusu u basncnn lm

sistemi.
Burada metal ak borusunun st tarafna yerletirilen bir basn alglaycsndan (pressure transmitter)
alnan sinyaller sinyal alc tarafndan mbar deerine evrilerek okunmaktadr. Farkl atomizasyon basnlarnda llen deerler kaydedilerek u basn grafikleri izilmitir.
Gaz atomizasyonu ileminde ekonomiklilik nemli bir parametredir. Bu parametre retilen toz iin tketilen gazn debisini ifade eder. Yaplan deneylerde spersonik nozul iin farkl atomizasyon basnlarndaki gaz debisi deerleri llmtr. lmler SIEMENS marka Strans F C Massflo Mass 2100 tipi
ktlesel debi lm cihaz ile gerekletirilmitir.
289

2.2. Model Geometrisinin Oluturulmas

Nozulun modellenmesi saysal akkanlar dinamii alannda (Computational Fluid Dynamics - CFD) bir
paket program olan FLUENT 6.3.26 ile yaplmtr [FLUENT INC., 2003]. Nozul iki boyutlu ve eksenel
simetrik olmak zere GAMBIT 2.4.6 programnda izilmitir. Model geometrisinin oluturulmasnda daha
nce toz retiminde kullanlan nozul lleri esas alnmtr. ncelikle iki boyutlu, iki boyutlu eksenel
simetrik ve boyutlu geometriler (yarm ve eyrek geometrilerde dahil) oluturulmutur. ki boyutlu
eksenel simetrik geometri zm hassasiyeti asndan bakldnda dierlerine gre daha avantajldr.
nk dier geometrilere gre grid saysnn azl zaman tasarrufu salayacaktr. Ayrca dier geometrilere gre alan bana den daha fazla grid saysna ulalmasna olanak salamaktadr. Bylece
zmn grid saysndan bamsz olduu optimum grid saysnn tespit edilmesi bu geometrik yap ile
daha uygun tespit edilmi olacaktr. ekil 2de iki boyutlu eksenel simetrik geometri ve snr blgeleri
gsterilmitir.
ekil 2. CFD Model geometrisi ve snr blgeleri.

2.2.1. Model Geometrisinde A Yapsnn Oluturulmas (Meshleme)
Model geometrisinde saysal zme olanak veren a yapsnn oluturulmas (meshleme) aamasnda
farkl mesh saylar oluturulmutur. Burada ama optimum mesh saysn tespit etmektir. Yani saysal
zmn belli bir mesh saysndan sonra deimeyecei ispatlanmaldr. Bu amala farkl mesh yaplar
oluturulmutur. Farkl mesh yaplar ile yaplan zmlerde nozul u basncnn deneysel deerlere
olan yaknlna baklmtr. Geometride mesh yaplrken dikkat edilecek dier bir hususta geometrinin
en dar blgesi olan nozul blgesinin meshlenmesidir. Bu alanda yaplacak yetersiz meshleme zmn
hassasiyetini ok etkileyecektir. Ayrca yine zmn hassasiyetini etkileyecek dier bir noktada cidarlarn meshlenmesidir. Bu nedenle cidarlara yakn blgeler daha sk meshlenmelidir. Sk meshlenmesi
iyi olacak dier bir blge ise akn olduu blgedir. Gelime raporunda da belirtildii gibi 344196 mesh
sayl bir zmn deneysel sonulara yakn olduu belirtilmitir. Fakat bu mesh saysnda yksek basnlarda (17, 22 ve 27 bar) elde edilen zmler deneysel deerlerle rtmemektedir. Bu nedenle 2
090 381 mesh saysna kadar klmtr (ekil 3). Ayrca nozul cidarlar ve burun blgesi cidarlar daha
da sk meshlenmitir (ekil 4).
290

ekil 4. Kritik blgelerdeki ve cidarlardaki mesh yaplar

2.2.2. Saysal zm
Snr artlar : Giri blgesi pressure inlet snr art olarak tanmlanmtr. Buradan azot gaz girmektedir. Deneysel verilerle kyaslanmak zere deneylerdeki farkl giri basn deerleri iin (10, 13, 17, 22
ve 27 bar) model almalarnn da ayn basn deerleri ile yaplmas gerekecektir. Bu yzden FLUENT
programnda giri art olarak bu basn deerleri tanmlanmtr. nce 10 bar basn deerinde almaya balanlmtr. Gaz girii iin Pressure inlet snr art seilerek gauge total pressure 10 bar (106
Pa), turbulent viscosity ratio ve intensity 10 olarak tanmlanmtr. k iin pressure outlet snr
art seilmitir. Deer olarak bu blgeler atmosfere ald iin atmosfer basnc (101.325 Pa) girilmitir. k iin dier deerler programdaki default deerler kullanlmtr. Orta eksen izgisi eksen olarak
tanmlanmtr. Bu snr blgesi dndaki tm blgeler cidar olarak tanmlanmtr. Bu blgeler iin
FLUENT programnda scaklk art olarak 300 K alnmtr.
Seilen Modeller: eilen tm modellerde almamza yakn uluslararas makalelerdeki seilen modeller gz nnde bulundurulmutur. Bu aamada programn kullanm kitaplarndan problemimizle ilgili
rnekler ve seilen modeller incelenmitir. Bu incelemelerin nda problemimize uygun modellerin seilmesine zen gsterilerek aada belirtilen modeller seilmitir. Oluturulan geometri iin programda
2D eksenel simetrik zm (2D Axisymmetric) seilmelidir. Programn zc tipi seiminde seilenler
ise pressure based, implicit yaklam ve steady (kararl) zmdr. Akkan olarak azot gaz seilmi ve ideal gaz olarak tanmlanmtr. Viskozite panelinde ise sutherland law tanmlanmtr. Ayrca
ak modelleri iinde programn iindeki mevcut ak modellerinden k epsilon modeli seilmitir.
zme Balama: Bu aamada programn kullanc kitabndan olduka yararlanlmtr. Yksek basnl almalarda zme balamada nerilen yollarn kullanlmas nem arz etmektedir. Aksi takdirde
zme ulalamamaktadr. Bunun iin zellikle 100 iterasyonda kararl bir yaknsama salanmas iin
enerji denklemleri seilmemitir. Balang deeri iin hz deeri programn hesaplad deerden daha
dk girilmitir. Ayrca rahatlatma faktrleride (under-relaxation factor) basn iin 0.4, momentum iin
0.3, younluk iin 0.3, enerji iin 0.9 seilmitir ve dierleri default deerleri olarak ayn kalmtr. Yaknsama da kararl bir grnt salandktan sonra (100-200 iterasyon sonra) enerji denklemi almtr ve
basn iin rahatlatma faktr 0.7 olarak deitirilmitir. zm iin ncelikle 1.dereceden denklemler
(first order upwind) seilmitir ve yaknsama kriteri olarak ise enerji denkleminin 10-6 hata oran esas
alnmtr. Ayrca giri ve k arasndaki ktlesel debiler arasndaki farknda 10-6 orannda bir farka
ulamas yaknsama kriteri olarak gz nne alnmtr. Bu aamadan sonra ise second order denklemleri seilerek eski zm zerinden tekrar iterasyon yaptrlarak son zm salanmtr.
291

2.2.3. Saysal zm Teorisi

Fluent program seilen denklemlerin zmnde sonlu hacim yaklamn kullanr. CFD gibi byle nmerik modelleme teknikleri ak ve s transferi problemlerini simule etmek iin gl bir aratr. Ktlenin
korunumu veya sreklilik denklemi, momentumun korunumu veya NavierStokes transport denklemi ve
enerjinin korunumu denklemi nmerik olarak zlebilir. Ktlenin korunumu ya da sreklilik denklemi
aada gibi yazlabilir [FLUENT INC., 2003].
1
Burada gaz younluu, v gaz hzn ifade eder. Sm kaynak terimi ise ayrlm ikinci fazdan (sv damlacklarnn buharlamas nedeniyle gibi) srekli faza ilave edilen ktle ve herhangi bir kullanc tarafndan
tanmlanm kaynaktr. 1 numaral denklem ktle korunum denkleminin genel formudur ve sktrlabilir
aklarda olduu kadar sktrlamaz aklarda da geerlidir. ki boyutlu eksenel simetrik geometriler iin
sreklilik denklemi;
2
Burada x eksenel koordinat, r radyal koordinat, vx eksenel hz, and vr radyal hzdr.
Bir atalet (ivmelenme olmakszn) referans erevesinde momentumun korunumu;
3
Burada p statik basn, gerilim tens (aada tanmland), ve
ve
srasyla yerekimi kuvveti
ve d kuvvettir (ayrk faz ile etkileimden ykselme gibi). daima poroz ortam ve kullanc tanml kaynaklar gibi baka model baml kaynak terimler ierir. Gerilim tensr aadaki gibi ifade edilir.
4
Burada
molekler viskozite, I birim tensr, ve sa taraftaki ikinci terim hacim genileme etkisidir.
ki boyutlu eksenel simetrik geometriler iin eksenel ve radyal momentum korunum denklemleri aada
verilmitir.
ve
Burada;
7
ve vz swirl hzdr.
292

Sktrlabilirlik etkilerine ile yksek hzlardaki gaz aklarnda ve/veya byk basn deiimlerinde karlalr. Ak hz gazn ses hzna yaklat ya da at zaman veya sistemde basn deiimi (p=p)
byk olduu zaman basnla gaz younluunun deiimi ak hz basnc ve scakl zerinde nemli
bir etkiye sahiptir.
Sktrlabilir aklar iin, ideal gaz kanunu aadaki formda yazlr;
8
Burada pop iletme basnc (operating conditions panelinde tanmlanr), p iletme basncna gre bal
lokal statik basn, R niversal gaz sabiti, ve Mw molekler arlktr. Scaklk T enerjinin korunum denkleminden hesaplanabilecektir.
Enerjinin korunum denklemin aadaki gibi yazlabilir;
9
Burada E toplam enerji, H entalpi ve s aks vektr.
Sktrlabilir aklar tipik olarak akn toplam basn p0, toplam scaklk T0 tarafnca karakterize edilir.
deal gaz iin bu byklkler aada verildii gibi statik basn ve scaklkla ilikilendirilebilir:
10
Cp iin;
11
12
Hz (Mach says) isentropik artlar altnda deiirken ak iindeki statik basn ve scakln deiimini
bu bantlar tanmlar.
Sktrlabilir aklar Mach saysnn deeri ile karakterize edilebilir :
13
Burada, c gaz iindeki ses hz:
14
ve
zgl slarn orandr. (cp/cv).
Sutherland viskozite kanunu iki ya da katsayl kullanmyla belirtilir.

ki katsayl Sutherland kanunu;
15
Burada viskozite (kg/m-s), T statik scaklk (K), ve C1 ve C2 katsaylardr. Scaklk ve basncn orta
deerlerinde hava iin C1 = 1.458x10-6 kg/msK1/2, and C2 = 110.4 K.
293

katsayl Sutherland kanunu;

16
Burada viskozite (kg/ms), T statik scaklk (K), 0 bir referans deer (kg/ms), T0 bir referans scaklk
(K), ve S ise gazn karakteristii olan Sutherland sabiti olarak isimlendirilen bir efektif scaklk (K). Scaklk ve basncn orta deerlerinde hava iin, 0= 1.7894x0-5 kg/ms, T0 = 273.11 K, and S = 106.67 K
[FLUENT 6.1.22, Users Guide, 2003].
3. Sonular ve Deerlendirme
3.1 CFD Sonular ile deneysel verilerin karlatrlmas
Bir problemin CFD yardmyla zlmesinde seilen modellerin uygunluunun tespiti iin CFD sonularnn deneysel verilerle kyaslanmas gerekir. CFD sonularnn deneysel verilere yaknlk derecesi
ve deneysel verilerle ayn karakteristik zelliklerine sahip olup olmad incelenir. Gaz atomizasyonu
almalarnda teorik zm ile deneysel almann karlatrlmas nozul ucunda yaplan u basn
lmleriyle yaplabilmektedir. nk nozul ucunda meydana gelen u basn gaz atomizasyonunda
olduka nemli bir etkiye sahiptir. CFD zmde nozul u basnc; nozulun u blgesinden balayarak
aralklar 1 mm olan lm izgisi zerindeki deerlerin ortalamas alnarak elde edilmitir. Deneysel
lmde boru i ap 3mm olduundan dolay her lm izgisi radyal ynde 1.5 mm uzunluuna sahip
olup bu uzunluk zerinde 10 lm noktas seilmitir. Bu adet lm izgisi zerinde elde edilen
deerlerin ortalamas deneysel verilerle kyaslama iin nozul u basn deeri olarak alnmtr. ekil
5de nozul u basncnn CFD ve deneysel kyaslanmas verilmitir. Giri basncna bal olarak nozul u
basncndaki deiim deneysel verilerle ayn karakteristik zellii tamaktadr. CFD ile deneysel verilere
bakldnda nozul gaz basnlar arasndaki fark tm basnlarda ayndr. Deneysel verilerde nozul u
basnc daha az olmakla birlikte CFD sonular ile arasndaki fark %11-15 arasnda deimektedir. Espina ve Piomelli yaptklar almalarnda saysal zmlemeleri ile deneysel verilere genellikle %10-20
arasnda yaknlk elde etmilerdir [Espina 1998]. Bu nedenle bu simlasyonlar deneysel verilerle Espina
ve Piomelli tarafndan yaplan daha nceki almalardan daha iyi rtmektedir. Bu sonu nozul u
basncnn belirlenmesinde CFD modelin kullanlabileceini gstermektedir [12]. ekil 6 da gaz ktlesel
debisinin CFD ve deneysel veriler ile kyaslamas verilmitir. Deneysel veriler ile CFD sonular arasndaki fark hemen hemen sabit olup %30 civarndadr. Bu fark nozulun yzey zelliklerinden ve gerek
boaz kesit alan ile nozulun tasarmndaki boaz kesit alan arasndaki farktan kaynaklanm olabilir.
Yine bu konuda Anderson ve Terpstra [Anderson 2002] yaptklar almada teorik debi ile deneysel
debi arasnda basncn artmasyla birlikte giderek artan bir fark tespit etmiler ve teorik debi deerleri ile
deneysel debi deerleri arasnda ok byk fark bulmulardr. Anderson ve Terpstra bu farkn nedenini
aklayamamlardr. Bu almada elde edilen deerler arasnda hemen hemen sabit bir farkn olmas
yaplan hesaplamann deneysel veriler ile rttn gstermektedir. Ayrca CFD almasnda gaz
scakl sabit tutulmutur. Deneysel almada ak esnasndaki gaz scakl zamanla azalmaktadr.
Bu durum nozulan geen gazn gerek ktlesel debisini de etkileyebilir.
ekil 5. Nozul u basncnn CFD ve deneysel veriler ile karlatrlmas
294

ekil 6. Gaz ktlesel debisinin CFD ve deneysel veriler ile karlatrlmas.

3.2 Nozul Tasarmn yiletirme almalar
nceki blmde akland zere CFD modelinin deneysel veriler ile uyum ierisinde olduunun tespit
edilmesinden sonra mevcut nozul tasarmnn iyiletirilmesi amacyla farkl artlarda nozul davran
incelenmitir. Bu amala yaplan almalarda nemli tasarm kriteri olarak nozul u basnc, gaz hz,
gaz debisi ve gazn enerjisi esas alnmtr.
3.2.1. Nozul Geometrisinin Etkisi
Burada mevcut nozulun as ve boaz k alan deitirilerek nozul davranndaki deiim tespit
edilmitir. Elde edilen deerler Tablo 1de verilmitir.
Tablo 1. Farkl nozul alar ve darboaz aklnda gaz hz ve u basn deerleri.
Nozul
as
Darboaz
akl
(mm)
alma
Basnc
(bar)
Gaz Hz
(m/s)
Mach
Says
Gaz
debisi
(kg/dak)
U
Basnc
(bar)
Dzeltilmi
U basn
(bar)
10
0,2
13
616,3
2,78
2,099
0,896
0,784
10
0,3
13
598,7
2,59
2,821
0,901
0,788
10
0,4
13
588,0
2,48
3,533
0,988
0,865
13
0,2
13
633,4
2,99
2,259
0,939
0,822
13
0,3
13
622,1
2,85
2,942
0,961
0,841
13
0,4
13
612,7
2,74
3,668
1,178
1,031
16
0,2
13
643,6
3,13
2,435
1,078
0,943
16
0,3
13
631,7
2,96
3,172
1,159
1,014
16
0,4
13
620,8
2,83
3,876
1,372
1,201
0,4
13
600,9
2,61
3,441
1,037
0,907
ekil 7de nozul boaz aklna ve farkl nozul alarna gre gaz hznn deiimi 1.3 MPa atomizasyon basn deeri iin grafik halinde verilmitir. En yksek gaz hz 16 al ve 0,2 mm darbogaz
aklnda elde edilmitir. Bu artlarda nozul ucunda az da olsa negatif basn oluumu gzlenmitir.
Fakat 16 al nozulda meydana gelen u basn deerleri 0,3 ve 0,4 mm darboaz aklnda pozitif
295

kmtr. Dolaysyla bu nozullarda metalin ak mmkn olmayacaktr. Bu nedenle bu nozullarn 0,3

ve 0,4 mm darboaz aklnda kullanm mmkn olamayacaktr.
ekil 7. Nozul boaz aklna gre gaz hznn 1.3 MPa basnta farkl nozul alarna gre deiimi.
ekil 8de 1.3 MPa gaz basncnda farkl nozul boaz akl ve farkl nozul asna gre Mach saysndaki deiim verilmitir. 10, 13, 16 derece al nozullarda Mach says srasyla 2,78, 2,99 ve 3,13
olarak tespit edilmitir. 16 derece al nozulda en yksek deer elde edilmitir. ekil 9da ayn artlarda
gaz debisindeki deiim verilmitir. Nozul boaz aklnda art olduu zaman hzdaki deiim ok
fazla olmamtr. 16 derece al nozulda 02, 03 ve 0,4 mm darboaz aklnda srasyla gaz hzlar
643.6, 630.7 ve 620.8 m/s iken gaz debileri 2.435, 3.172 ve 3.876 kg/dak olarak hesaplanmtr. Bu
karlatrma gstermektedir ki boaz aklnn art ile gaz hznda ok nemli bir azalma olmaz iken
gaz debisi daha fazla miktarda art gstermektedir. rnein 16 derece al nozulda 0,2 mm darboaz
aklk deeri 0,4 mmye karlrsa gaz hz yaklak %4 azalrken gaz debisi %59 orannda artmtr.
Bu karlatrma ile aka grlmektedir ki nozul geometrisine gre boaz aklk deeri olduka kritik
bir neme sahiptir.
ekil 8. Darboaz aklk deerine gre Mach saysndaki deiim (nozul alar 10, 13, 16).
296

ekil 9. Darboaz aklk deerine gre gaz debisindeki deiim (nozul alar 10, 13, 16)
Gaz atomizasyon ilemi gaz enerjisinin sv metale aktarlmas sonucu sv metalin ok kk damlacklar halinde paralanmas olaydr. Paralanma mekanizmas Weber saysna (we) gre deiiklik
gstermektedir. ekil 10da We saysna gre sv metalin paralanmas farkl ekilde meydana gelmektedir.
ekil 9. Weber saysna gre paralanma mekanizmalar

Weber says eitlik 17de verilmitir.
17
Burada, dpart sv metal demeti ap, ve sv metalin younluu ve yzey gerilmesi deeridir, urel ise
gazn sv metale arpt andaki hzdr. Buradan grld gibi hzn karesi alndndan gaz hz ok
byk bir neme sahiptir. Dolaysyla ayn artlarda en yksek gaz hzna ulaan nozul tasarm daha
baarl sonu verecektir. Bylece nozul verimlilii artacaktr. Bu nedenlerle nozul tasarmnda boaz
aklnn fazla olmas durumunda gaz kullanm artacaktr, fakat toz boyutunda nemli bir klme
gzlenmeyecektir. Tablo 1de verilen nozul deerleri yukarda yaplan deerlendirmeler nda incelendiinde en iyi artlar 10 dereceli ve 0,2 mm akla sahip nozul salayabilecektir. nk hem nozul
ucunda iyi bir emme basnc olumakta hem de atomizasyon gaz 613 m/s ile olduka makul bir debide
akmaktadr.
297

4. SONULAR
Proje kapsamnda Fluent program kullanlarak CFD yaklam ile nozulun teorik modellemesi yaplmtr. ncelikle daha nce blmmz laboratuarnda gerekletirilen toz retim almalarnda kullanlan
nozulun deneysel verileri ile modellemenin doruluu tespit edilmeye allmtr. CFD modelinin deneysel verilere yaklam en iyi olacak ekilde model zerinde eitli parametrelerin etkileri incelenmitir.
Daha sonra nozul tasarmnda nemli olan geometri ve gaz k alan deikenleri deitirilerek nozul
veriminin daha yksek olabilecei en uygun tasarm bulunmaya allmtr. Yaplan deerlendirmeler
sonucunda elde edilen sonular aada maddeler halinde verilmitir;
Deneysel verilerde nozul u basnc daha az olmakla birlikte CFD sonular ile arasndaki fark %1115 arasnda deimektedir. Elde edilen teorik ve deneysel deerler arasnda hemen hemen sabit bir
farkn olmas yaplan hesaplamann deneysel veriler ile rttn gstermektedir.
Nozul boaz aklnn artmas ile nozul hznda ok nemli bir deiiklik meydana gelmemektedir.
Ancak gaz debisi ok yksek oranda artmaktadr. 16 dereceli eski tasarmda 0,2 mm boaz aklk
deeri 0,4 mmye karlrsa gaz hz yaklak %4 azalrken gaz debisi %59 orannda artmtr.
Bu almada elde edilen veriler mevcut nozul tasarmlarnn CFD ile iyiletirilebileceini ortaya
koymutur..
Teekkr
Bu alma TUBITAK tarafndan 107M189 nolu proje ile desteklenmitir.
KAYNAKLAR
1. A.M. Mullis, N.J. Adkins et al., High frame rate analysis of the spray cone geometry during closecoupled gas atomization, PM 2007,
2. J. Mller, Flow field Simulation of a High Pressure Gas Atomization using CFD,
3. I.E. Anderson, R.S. Figliola & H. Morton, Mater. Sci. Eng. A, 1991, vol. 148, pp. 101-114.
4. I.E. Anderson & R.L. Terpstra, Mater. Sci. Eng. A, 2002, vol. 326, pp. 101-109.
5. nal R., Aksoy A., Effects of Gas Pressure and Protrusion Length of Melt Delivery Tube on Powder
Size and Powder Morphology of Nitrogen Gas Atomised Tin Powders, Powder Metallurgy, Vol.49,
No.4, pp. 349-354, 2006.
6. nal R., Improvements to a close-coupled gas atomisation nozzle for fine powder production,
Powder Metallurgy, Vol.50, No.1, pp 66-71 , 2007.
7. nal R., The Influence of The Pressure Formation at The Tip of The Melt Delivery Tube On Tin
Powder Size And Gas/Melt Ratio In Gas Atomization Method, Journal of Materials Processing Technology, Vol.180, No.1-3, pp. 291-195, 2006.
8. NIST Reference Fluid Thermodynamic and Transport Properties Database (REFPROP) version 7.0,
National Institute of Standards and Technology, Boulder, CO 80305-3328, USA.
9. N. Zeoli, S. Gu, Numerical modelling of droplet break-up for gas atomisation, Computational Materials Science 38 (2006) 282292.
10. P.I. Espina and U. Piomelli, numercal smulaton of the gas flow n gas-metal atomzers, Proceedings of FEDSM98, 1998 ASME Fluids Engineering Division Summer Meeting, June 21-25, 1998,
Washington, DC, USA.
11. Espina, P. I., and Piomelli, U., A Validation of the NPARC Code in Supersonic Base Flows, AIAA
Paper, 97-0032, 1997.
12. Aydn . and nal R., Experimental and numerical modeling of the gas atomization nozzle for gas
flow behavior , Computers and Fluids, Volume 42, Issue 1, March 2011, Pages 37-43.(2011).
298

AA 2014 ALAIMININ MKROYAPISAL KARAKTERZASYONU VE

AINMA DAVRANIINA ETKS
Sedat TOMRUK*, Hakan GKMEE** ve Blent BOSTAN***
Milli Eitim Bakanl, Mehmet Rfat Breki lkretim Okulu, Mamak, 06320, Ankara,
sedat tomruk@yahoo.com
**
hakangokmese@gazi.edu.tr
***
bbostan@gazi.edu.tr
*
ZET
Bu almada ticari AA 2014 alminyum alamna ait, ortalama toz boyutu 95 m olan alam tozlar kullanlmtr.
Bu tozlardan 650 MPa presleme basncnda, tek ynl souk pres de anma numuneleri retilmitir. Preslenen
numuneler 550 C de, 224 saat aralnda sl ileme tabi tutulmutur. Daha sonra numunelerin sertlik deerleri
llmtr. Ayrca 600 C sinterleme scaklnda 268 gn sl ilem yaplarak numunelerin anma davranlar
incelenmitir. Isl ilem sresinin artmas ile birlikte sertlik deerlerinde de art olduu belirlenmitir. Anma kayma
mesafesine bal olarak, 400 mnin zerinde en az anma kayb 6 gn sl ilem grm numunelerde gereklemitir.
Anahtar Kelimeler: AA 2014, Karakterizasyon, Anma
MICROSTRUCTURAL CHARACTERIZATION OF AA 2014 ALLOY AND

EFFECT ON WEAR BEHAVIOR
ABSTRACT
In this study, It has been used alloy powders belonging to AA 2014 commercial alloy which avarege powder dimensions are 95mm. These powders have been pressed at 650 Mpa pressure and has been produced wear experiment samples. Pressed samples has been carry out to heat treatment at 550C between 2 and 24 hours. Later,
Hardness values of the samples have been measured. It has been investigated hardness value as dependent on
increasing of heat treatment time. In addition, It has been investigated wear behaviors of samples which to process
heat treatment 2-6-8 day at 600C. It has been confirmed that hardness value has also increaesed after inreasing
heat treatment time Depending on wear sliding distance, minimum wear lose has evuntuate samples that has been
applied 6 day heat treatment.
Key Words: AA 2014, characterization, wear
1. GR
Malzemelerin mekanik, kimyasal ve fiziksel zelliklerini iyiletirmede; kimyasal modifikasyon, sl ilemler, mekanik
ve termomekanik ilemler kullanlmaktadr. Gelien teknoloji ile ihtiyalarda farkllamtr. Toz Metalurjisi (TM) gibi
yeni retim tekniklerinin kullanmlar yaygnlamaya balamtr. TM yntemiyle retilmi malzemelerin yksek kullanm zelliklerini geleneksel metotlarla retmek neredeyse imknszdr [1].
Toz Metalrjisi metal tozu ve ondan ktlesel gereler ve ekillendirilmi paralar retme teknoloji ve sanatdr [2].
TM paralarn en yaygn olarak kullanld alan otomotiv sanayidir. Otomatik vites paralar, hareket dilileri, yalama pompa dilileri, debriyaj bask plakalar yllardr T/M teknolojisi ile retilmektedir [3]. Toz metalurjisi yntemi son
299

yllarda daha nemli bir hale gelmitir [4]. Son yirmi ylda yksek performansl toz metal alminyum alamlar (Al
alamlar) iin talep giderek artmtr [5]. Alminyum alamlarnn toz metalurjisi ticari olarak birka alam zerine
younlamtr. Kartrma esnasndaki potansiyel risklere kar, reticiler tarafndan nceden kartrlm, baz
yalayclar katlm alminyum alamlar retilmektedir. Alminyum alamlar, nispeten dk basnlarda (400480 MPa) preslenir. Alminyum esasl ticari alamlar yksek sktrlabilirlik gsterir ve yaklak 350 MPa basn
kullanlarak % 9095 arasnda teorik younlua ulalabilir [6]
Al alamlarnn anma oran hava ortamnda yksek olup, vakum ortamnda ise dktr. Al alamlar korozyon
ortamlarnda kullanlr ve Si ierenlerinin anma direnci dierlerinden fazladr [7,8]. Endstriyel uygulamalarda
anmaya dayankl malzemeler yaygn kullanm alanna sahip olup bu malzemelerin hafif olmalar ve evre artlarndan daha az etkilenmeleri beklenmektedir [9]. Makine paralarnn alma mrleri, anmaya kar direnci
yksek olan malzemelerin retilebilmesiyle arttrlabilmektedir. Makine hasarlarnn analizi, paralarn bozulmalarnn % 75 inin srtnen yzeylerin anmas sonucu olduunu gstermektedir. Yzeylerin mrlerinin uzamas iin,
malzemelerin anmaya kar direncinin arttrlmas gerekmektedir. Anma zorlamasnn yksek olduu ve yalamann yeterli olmad durumlarda anmaya kar direnli ve srtnme katsays dk malzeme seilir [10]. Bu
amala AA 2014 malzemesinin mikro yapsal karakterizasyonu ve anma davranlarnn belirlenmesi hususunda
almalar yrtlmtr.
Bu almada Gazi niversitesi Teknik Eitim Fakltesi Dkm A.B.D.de bulunan gaz atomizasyon nitesinde retilmi olan, ortalama toz boyutu 95 m olan tozlar kullanlmtr. Kullanlan tozlarn boyut analizleri Gazi niversitesi
Mimarlk Mhendislik Fakltesi Makine Mhendislii Blmndeki Malvern Mastersizer E Version 1,2 b, boyut analizi cihaznda yaplmtr. Taramal Elektron Mikroskobu (SEM) grntleri ile de, boyut analizi cihaznda karlalabilecek boyutsal sorunlarn olup olmad aratrlmtr. retilen tozun kimyasal bileimi izelge 1de verilmitir.
izelge 1. AA 2014 Alminyum alamnn kimyasal bileimi

Toz boyutu ortalama 95m olan karmdan 1gr toz kullanlarak 10 mm apnda tek ynl pres altnda farkl presleme basnlar denenerek uygun presleme basncna ulalmtr. Presleme sonras deney numunelerinin sl ilemleri atmosfer kontroll frnda 550C de 2, 4, 8, 12 ve 24 saat olmak zere farkl srelerde gerekletirilmitir.
Tane yaps ve gzenek oluumuna sl ilem sresinin etkileri tespit edilmeye allmtr. Isl ilem scakl ve
sresi temel alnarak, sl ilem ncesi ve sonrasndaki younluklar hesaplanm ve uygun sl ilem sresi tespit
edilmeye allmtr.
Numunelerin metalografik olarak incelenebilmeleri iin, Optik mikroskop ve SEM (Joel JSM - 6060 LV) cihazlarndan yararlanlmtr. Yaplan almalar dorultusunda sertlik sonularnn sl ilem scakl ve sresine bal olarak nasl deitii hususunda sertlik zerine etkileri incelenmitir. Sertlik lmleri SHIMADZU marka mikro sertlik
cihaznda yaplmtr ve kullanlan yk ise HV 0,1kg olarak belirlenmitir.
Deney numunelerine uygulanan presleme ve sl ilemler sonras, Karabk niversitesi Teknik Eitim Fakltesi
Dkm Eitimi Anabilim Dalnda bulunan anma cihaz kullanlarak kuru srtnme anma davranlar pin-on-disk
tipi anma cihaznda yaplmtr. Anma deneyleri kuru ortamda yaplmtr. Isl ilem uygulanm numunelere 15
N yk uygulanmtr. Bu ykler altnda numuneler 400, 800 ve 1200 m kayma mesafelerinde srtnme ve arlka kayplar hesaplanarak sonulara ulalmtr. Anma yzeylerine ait grntleme ilemleri 1200 m ardndan
yaplmtr. 600C scaklkta, 2, 6, 8 gn uygulanan sl ilemlerin ardndan elde edilen anma kayplar grafiklere
dntrlmtr. Anma kayplar ve kayma mesafesi ilikileri deneyler sonras irdelenmitir.
3. ARATIRMA BULGULARI VE DEERLENDRLMES
AA 2014 malzemesinin presleme basncnn belirlenmesi amal farkl presleme basnlar test edilmitir. Younlukpresleme basnc ilikisi asndan optimum deer olarak 650Mpa bulunmutur. Tm dier deneyler bu presleme
basncnda retilen numuneler kullanlarak gerekletirilmitir.
300

izelge 2. Isl ilem ncesi ve sonras younluk deiimleri

Numune Kodu
Isl lem
Scakl (C)
Isl ilem
Sresi (saat)
Isl lem ncesi

Younluk (g/cm3)
Isl lem Sonras

Younluk (g/cm3)
Numune 1
550
2h
2,77
2,62
Numune 2
550
4h
2,76
2,62
Numune 3
550
8h
2,75
2,66
Numune 4
550
12h
2,74
2,7
Numune 5
550
24h
2,73
2,69
izelge 2de sl ilem ncesindeki ve sonrasndaki younluklar gsterilmitir. izelge 2 ve ekil 1de gzlemlendii
gibi 550 C de farkl srelerde sl ilem uygulanan numunelerin, sl ilem sresinin art ile younluklarnda da
belli bir art tespit edilmitir.
ekil 1. 550C de sl ilem sonras younluk deiimi

12 saat sl ilem sonrasnda younluk artnda nemli bir deiim meydana gelmemitir. Toz metalrjisi yntemleri
ile tam youn para retimi ikincil ilemler veya sv faz sinterleme ile mmkndr. Bu balamda kullanm olduumuz AA 2014 malzemesinin teorik younluunun 2,75 g/cm3 civarnda olduunu gz nne aldmzda younluun % 98 civarna kadar kt grlmektedir. Bu da ikincil ilemler olmakszn younluk asndan olduka yksek
bir deerdir. Isl ilem scakl ve sresi temel alnarak, sl ilem ncesi ve sonrasndaki younluklar hesaplanm
ve uygun sl ilem sresi tespit edilmeye allmtr.
ekil 2. 550C de farkl srelerde sl ilem yaplm numunelerin optik mikroskop grntleri;
a) 4 saat, b) 8 saat, c) 12 saat, d) 24 saat
301

Isl ilem ile birlikte numunelerde oluan faz deiimlerinin kontrol iin (2 saatten 24 saate kadar olan srelerdeki)
optik mikroskop grntleri incelenmitir. nceleme sonrasnda 4 saat sl ilem uygulanan numunelerde gzeneklerin tane snrlarnn bulunduu nadiren de tane ilerinde bulunduu gzlemlenmitir (ekil 2a). Srenin artmasyla
birlikte tane snrlar ve ierisindeki gzenekliliklerin birlemeye balad ve genel itibariyle tane snrlarnda younlat gzlemlenmitir (ekil 2d).
ekil 2d de grld gibi sl ilem sresinin 24 saat gibi yksek srelere kmasyla birlikte daha ncesinde yaplan dk srelerdeki sl ilem uygulamalarna gre gzeneklerin tamam tane snrlarna doru yneldii ve resim
incelendiinde sinterleme teorisine gre sl ilemin bu sre iin yeterli olduu sylenebilir.
Farkl srelerde sl ilem grm numunelerin, farkl bytmelerdeki ekilmi olan SEM grntleri incelendiinde
(ekil 3), artan sl ilem sresinin etkileri aka grlmektedir. Ayn etkinin daha ksa srelerde gereklemesi iin
sl ilem scaklnn artnn etkili olaca sylenilebilir.
ekil 3. 550 C de farkl srelerde sl ilem grm numunelerin, farkl bytmelerdeki SEM grntleri;
a) ve b) 4 saat, c) ve d) 24 saat
ekil 4de 550C de 2, 4, 8, 12 ve 24 saat gibi farkl srelerde sl ilem grm numunelere ait sertlik deerleri
gsterilmitir. Isl ilem sresinin artmas ile birlikte sertlikte de bir art gzlemlenmektedir. 12 saatin zerindeki sl
ilem srelerinde sertlik deerinde ciddi bir deiikliin olmad grlmektedir. lk sl ilem srelerinde (2,4 saat)
sertlikte bir deiim olmamtr. Bunun nedeni balangta uygulanan enerjinin tozlarda ve toplam ktlede meydana
gelen toparlanma sreci gibi dnebiliriz. 4,8 ve 12 saatlerde ise sertlikteki art makro ve mikro gzeneklerin
kapanmas ile izah edilebilir.
ekil 4. Farkl sl ilem srelerindeki sertlik deerleri
302

ekil 5 de 600 C de 2, 6, 8 gn sl ilem uygulanm numunelerin anma kayma mesafesine bal olarak anma
kayplar verilmitir. lk 400 m kayma mesafesine kadar, bu numunelerin anma kayplarnn sl ilem zamannn
artmasyla daha az olduu grlebilir. Bunun muhtemel nedeni sl ilem zamannn artmasyla numunelerdeki
younlamann artmas ve buna bal olarak da sertliin artmas gsterilebilir.
ekil 5. 600 C de 2, 6, 8 gn sl ilem uygulanm numunelerin anma kayma

mesafesine bal olarak anma kayplar grafii
Bu numunelerde 400 m kayma mesafesinden sonra en az anma oran 6 gn sl ilem uygulanm numunede
olduu grlmektedir. Oysaki 400 m kayma mesafesi ncesinde en az anma oran en uzun sl ilem sresi
uygulanan numunede gereklemiti. Bu numunede anma kaybnn daha az kmasna muhtemel nedenler ya
kuru srtnmeden dolay numune yzeyindeki oksitlenmeye (Al2O3 filmi) bal olarak ya da Al alamlar gibi baz
yumuak ve YMK yapl malzemelerde anma yk altnda iken plastik deformasyona bal olarak sertliin yzeyde blgesel olarak artmas gsterilebilir.
ekil 6 da 600 C de 2, 6, 8 gn sl ilem uygulanm numunelerin 1200 m kayma mesafesi sonras anma yzeyleri srasyla verilmitir. 2 gn sl ilem uygulanm numunenin anma yzeyi incelendiinde ktle kayplarnn
ok daha fazla olduu derin anma izlerinden aka grlebilir. Bu numunede ktle kayplar adhesiv anma
mekanizmasna bal olduu anma izlerindeki snek yrtlmalardan anlalmaktadr.
ekil 6. 600 C de farkl srelerde sl ilem uygulanm numunenin anma yzeyi;

a) 2 gn, b) 6 gn, c) 8 gn
6 gn sl ilem uygulanm numunenin anma yzeyi incelendiinde ise ktle kayplarnn ok az olduu anlalmaktadr. Anma yzeyindeki anma izleri daha dz ve ok derin olmad grlmektedir. Ayn zamanda zellikle
toz metalurjisi yntemiyle retilen malzemelerde yzeye ak gzeneklerin anma esnasnda kopan ok kk paracklarn yzeye ak gzenekler tarafndan tutulmas da anma kayplarnn daha az olmasna neden olabilir.
8 gn sl ilem uygulanm numunenin anma yzeyi incelendiinde 6 gn sl ilem uygulanm numunenin
anma yzeyine gre daha fazla 2 gn sl ilem uygulanm numunenin anma yzeyine gre daha az olduu
grlmektedir. Isl ilem sresinin artmasna ramen anma kayplarnn yeniden artmasna neden olarak anma
esnasnda kopan byk boyutlu paralarn yzeye daha derin hasar verdii dnlebilir.
303

4. SONULAR
Bu alma kapsamnda TM gaz atomizasyon yntemiyle retimi gerekletirilen AA 2014 malzemesine ait deney
numunelerinin sl ilem scakl, sresi, sertlik ve anma deneyleri sonrasnda elde edilen sonular u ekilde
zetlenebilir;
Isl ilem sresinin artyla birlikte gzenek-yap etkileimi asndan 550 C deki uygun sl ilem sresi 24
saat olarak belirlenmitir.
Sabit scaklkta yaplan (550 C) sl ilem sresinin artmas ile birlikte sertlik deerlerinin de nemli derecede
art olduu belirlenmitir.
600 C de 2, 6, 8 gn sl ilem uygulanm numunelerin anma kayma mesafesine bal olarak anma kayplar ilk 400 m kayma mesafesine kadar sl ilem zamannn artmasyla daha az olduu tespit edilmitir. 400
mnin zerinde en az anma kayb 6 gn sl ilem grm numunelerde gereklemitir.
Numunelerin anma deneylerinde sklkla karlalan scaklk artna bal oksit oluumunun, anma kayplarn etkiledii tespit edilmitir. Benzer ekilde artan anma mesafelerine bal olarak gereklemesi muhtemel olan anma kayplar mesafe arttka dorusal bir art gstermemitir.
Artan sl ilem scakl ve zaman toz numunelerin gzenek miktarn etkiledii bilinen bir sonutur. Anmada
bu etki mesafeye bal olarak aa kan gzeneklerin anan paracklar tutarak sanki anma miktarnda bir
d varmasna bir etki yapt gzlemlenmitir.
TEEKKR
Bu almada kullanlan tozlarn retimi ve yaplan deneysel almalar, Gazi niversitesi Bilimsel Aratrma Projeler Birimi, 41/2010 04 nolu proje kapsamnda gerekletirilerek, desteklerinden dolay Gazi niversitesine teekkr ederiz.
KAYNAKLAR
1. Aksz, S., Al4C3 Faznn Karbon ve AA2014 Tozlarndan Kat Faz Reaksiyon Teknii le Oluturulmas ve
Yalanmaya Etkisi, Yksek Lisans Tezi, Gazi niversitesi Fen Bilimleri Enstits, Ankara,1-2, 2009.
2. Sarta, S., Toz Metalurjisi, TMMOB, Cilt:36, Say: 421, ubat, 1995.
3. Baaran, A., Toz Metal Paralara Isl ve Mekanik Yzey lemlerin Birlikte Uygulanabilirliinin Aratrlmas,
Doktora Tezi, Sleyman Demirel niversitesi Fen Bilimleri Enstits, Isparta, 29-32, 2007.
4. Sonoda, T., Watazu, A., Zhu, J., Sh, W., Kamiya, A., Kato, A., Asahina, T., Deposton Of Titanium Onto Alumnum Powder Ints Self-Convectve Moton By Dc Sputterng, 3rd International Powder Metallurgy Conference, September 4-8, Turkish Powder Metallurgy Association Gazi University, Ankara, TURKEY, pp.756-759,
2002.
5. Eki A., K., ,Bircan D., A., Sonsino, C., M., Alumix 431 Tozunun (Al7xxx) Souk ve Ilk Preslenmesi zerine
Bir alma, Gazi niv. Mh. Mim. Fak. Der., Cilt: 22, No: 2, 337-345, Ankara, 2007.
6. Gke, A., Yapsal Uygulamalar in Alminyum Esasl Malzemelerin Toz Metalurjisi Kullanlarak Gelitirilmesi, Yksek Lisans Tezi , Sakarya niversitesi Fen Bilimleri Enstits, Sakarya, 26-31, 2007.
7. nl, B., S., ahin, S., Akgn, S., Dkm ve T/M Yntemiyle retilmi Al2O3-SiC Takviyeli Al Kompozitlerinin Anma zelliklerinin ncelenmesi, 4th International Powder Metallurgy Conference, May 18-22,
Turkish Powder Metallurgy Association Sakarya University, Sakarya, TURKEY, pp. 615-621, 2005.
8. Bostan, B., Gaz Atomizasyon Yntemi le AA 2014 Alam Tozlarnn retilmesi ve Karakterizasyonu, 5. Ulusal Toz Metalurjisi Konferans, TOBB, Ankara, 1-8, 2008.
9. Ylmaz, R., Kurt, A., O., Seramik Kaplamalarn Anma Davranlarnn ncelenmesi, 4th International
Powder Metallurgy Conference, May 18-22, Turkish Powder Metallurgy Association Sakarya University, Sakarya, TURKEY, pp. 649-663, 2005.
10. Kksal, F., Al-Cu-SiC ve Al-Cu-B4C Kompozitlerin Scak Presleme Yntemi le retimi ve Anma zelliklerinin Aratrlmas, Yksek Lisans Tezi Sleyman Demirel niversitesi Fen Bilimleri Enstits, Isparta, 1-5,
2004.
304

MKRO YAPIDA BOYUTLU YZEYLERN GZENEKLLK VE

MKROSERTLNE RETM PARAMETRELERNN ETKS
Blent ZTRK1,2, mer Necati CORA2,3 ve Muammer KO 2,4
1
Trabzon, bozturk@ktu.edu.tr
2
NSF I/UCR Center for Precision Forming, Richmond, VA, USA
3
Karadeniz Teknik niversitesi, Mhendislik Fakltesi, Makine Mhendislii Blm, 61080, Trabzon,
oncora@ktu.edu.tr
4
stanbul ehir niversitesi, stanbul, mkoc@sehir.edu.tr
zet
Gzenekli metalik yzeyler, s eanjrleri, yakt hcreleri ve biyomedikal implant malzemeleri gibi alanlarda s
ve ktle transferi asndan geni uygulama alanna sahiptirler. Yaplan bu almada toz presleme ynteminde
sktrma scakl, sktrma basnc, toz boyutu ve sinterleme scaklnn retilen 3 boyutlu gzenekli numuneler
zerindeki gzeneklilik ve mikrosertlik zerine etkileri incelenmitir. almada iki tabakal fonksiyonel gzenekli
yzeylerin retimi baarl bir ekilde gerekletirilmitir. Elde edilen sonulardan; gzenekliliin genellikle artan toz
boyutu, azalan sktrma basnc ve scaklyla artt grlmtr. Ayrca, sinterleme scaklnn azalmasyla da
gzeneklilik deeri artmtr. Mikrosertlik deerlerinde ise retim parametrelerine bal olarak belirgin bir deiim
elde edilememitir.
Anahtar Kelimeler: Gzenekli Yzeyler, Mikro retim, Bakr Tozu.
EFFECTS OF MANUFACTURING PARAMETERS ON THE POROSITY AND

MICROHARDNESS OF MICRO-SCALE 3-D POROUS GRADIENT SURFACES
ABSTRACT
Porous metallic surface structures are used in wide range of applications including heat exchangers, fuel cells, and
biomedical implants for heat and mass transfer purposes. In this study, the effects of the compaction temperature,
pressure, powder size and sintering temperature were investigated on porosity and microhardness during powder forming process. Tests proved successful implementation of two-layered porous gradient surface. The results
showed that porosity increased with increasing powder size, decreasing compaction temperature and pressure.
Also, porosity increased with decreasing sintering temperature. Analyses showed that microhardness values did
not change significantly depending on the manufacturing parameters.
Keywords: Porous Surfaces, Micro Manufacturing, Copper Powders.
1. GR
Gzeneklilik (porozite), gzenekli malzeme tasarmnda en etkin faktrlerden biridir. Gzenekli yzeyler, ok deiik amalar iin farkl uygulama alan bulurlar. Bu yzeylere, gelimi s transfer uygulamalarndaki yzey alan
arttrlm alanlar, kemik byme ve hcre oalmasn salayan biyouyumlu implantlar, madde filtrasyonu vb. r-
305

nek olarak verilebilir. Mikro lekteki gzenekli yzeylerin, zellikle, s transferini gelitirdii ve iyiletirdii yaplan
almalarda ortaya konulmutur [1-3]. Litter ve Kaviany mikro-lekte, kresel bakr tozlar kullanarak rettikleri
gzenekli yzeylerdeki s transfer orann %300 deerinde arttrmlardr [4]. Benzer almalar yazarlar tarafndan
da yaplm olup, bu almalarda bakr alt tabaka zerine yksek scaklkta bakr tozlar preslenmi ve retim parametrelerinin etkileri incelenmitir [1-3, 5].
Bu alma, hem gelimi s transferi hem de kat oksit yakt hcresi (solid oxide fuel cell, SOFC) gibi enerji
dntrme sistemlerinde kullanlabilecek mikro yapda gzenekli yzeylerin retimini amalamaktadr. nerilen
yntem, kresel tozlar metal bir alt tabakaya presleyip kompakt hale getirerek farkl gzeneklilik deerlerine sahip
numuneler retmektir. Metal alt tabakaya bitiik alt yzeyin, madde transferini engellemek maksadyla sfra yakn
gzeneklilikle retilmesi istenirken, st yzeyin ise gaz difzyonunu iyiletirmek (SOFC durumunda) veya s transferini gelitirmek (s eanjrlerindeki buharlama) amacyla yksek gzeneklilik deerlerinde (~%40) retilmesi
amalanmtr. Alt tabaka malzemesi, uygulama alan ve kullanm amacna bal olarak bakr veya paslanmaz elik
olabilir. almada farkl aplara sahip kresel bakr tozlar gzenekli yzey retmek iin bakr alt tabaka zerine
farkl sktrma scaklklar ve basnlar kullanlarak sktrlm ve kompakt hale getirilmitir. Kompakt hale getirilmi olan numuneler farkl iki scaklkta sinterlenerek gzeneklilik ve mikrosertlikleri incelenmitir.
2.1. Numune retimi
Numune retiminde kullanlan bakr tozlar Acupowder International LLC (Union, NJ, ABD) firmasndan temin edilmitir. Tozlarn younluu, safl ve toz boyut dalm izelge 1de verilmitir. Numunelerin iki tabakal blge
eklinde retilmesi amalandndan st yzey blgesi iin nispeten byk toz boyutlu tozlar (-106+90 m), alt
yzey ve vadi blgesi iin srasyla farkl toz boyut aralna sahip tozlar (-63+45 m, -45+25 m ve -25+0 m)
kullanlmtr.
lk ksmda bahsedilen fonksiyonel gzenekli yzeyler retmek amacyla (a) niversal MTS ekme-basma makinesi
(Instron SATEC 5596-400HVL), (b) toz sktrma kalp seti (alt kalp/zmba, st kalp ve tayc, (c) stma elemanlar, (d) kontrol ve veri toplama sistemi kullanlmtr. Alt kalbn yzeyinde 100 adet delik (10x10) mevcut olup her
bir delik 0,5 mm derinliinde ve 1 mm apndadr. ekil 1de toz sktrma kalp seti verilmitir.
izelge 1. almada kullanlan tozlarn zellikleri.
Derece
Younluk
(g/cc)
%Cu min
83
5.1
99.82
103
155
5.16
4.98
99.78
99.83
+80
2 max
+100
20-50
+150
50- 75
2 max
Bal
Elek Analizi-Mesh- %
+200
+325
10 max
Tr
ekil 1. almada kullanlan kalp seti.
306
50-80
0.5 max
20-50
Bal
-325
10 max
95 min

Numune retiminde balangta -106+90 m toz boyut aralndaki tozlar st yzey blgesini retmek iin alt kalbn zerine delikleri dolduracak ekilde serbest olarak yerletirilmitir. Daha sonra toz boyutunun etkisini incelemek
amacyla srasyla farkl toz boyut aralklarndaki tozlar (45-63 m, 25-45 m ve 0-25 m) benzer ekilde alt kalp
zerine dklerek 200 m kalnlndaki bakr alt tabaka (substrate), tozlarn zerine yerletirilmitir. Kalp, istenen
scaklkla bal olarak (350, 425 ve 500C) stlmtr. Bu scaklklara ulaldktan sonra tozlar, farkl toz sktrma basn deerinde (20, 35 ve 50 MPa) ayr ayr sktrlarak kompakt hale getirilmitir. almada numune
retim artlarn minimuma indirmek iin MINITAB paket programndan istatistik deney tasarm (DOE: Design of
Experiments) yaklam kullanlmtr. Tozlarn birbirine balanmasn ve mukavemet artn salamak amacyla
kompakt hale getirilmi numuneler, bir tp frn ierisinde ve kontroll atmosfer ortamnda (%5 hidrojen + %95 azot)
1 saat sreyle srasyla iki farkl sinterleme scaklnda (600 ve 900 C) sinterlenmi ve numune retimi tamamlanmtr. retilen numunelerin ematik grnm ekil 2de, optik ve taramal elektron mikroskop (SEM) grntleri
ise ekil 3 (a-d)de verilmitir.
ekil 2. boyutlu gzenekli yzeyin ematik gsterimi.
ekil 3. retilen numunenin: (a) optik mikroskop; (b) A-A kesitinin; (c) stten ve (d) perspektif SEM grnts
(sinterleme scakl 900 oC, sktrma basnc: 50 MPa).
2.2. Gzeneklilik lmleri
Numune retiminde kullanlan tozlar farkl byklkte olduklarndan st yzey, alt yzey ve vadi blgeleri iin farkl
gzeneklilik deerleri llmtr. Gzeneklilik lmlerinde numuneler iki paraya ayrlm ve paralardan bir tanesi kalp ierisine alnmtr. Kalplanan numuneler daha sonra zmparalama ve parlatma ilemine tabi tutulmutur.
Zmparalama ilemi 240, 400, 800 ve 1200 nolu zmparalar kullanlarak yaplmtr. Daha sonra, numune yzeyleri
6 ve 1 m luk elmas pastalar yardmyla parlatlmtr. Parlatlm numunelerin yzey grntleri k mikroskobunda incelenmi ve fotoraflar ekilmitir. Bu resimler Image J ve Motic programlar vastasyla ilenerek numunelerin
gzeneklilik deerleri tespit edilmitir. Bu amala gzeneklilik lmleri iin alnan resimler ilk olarak siyah ve beyaz
alanlara dntrlm (binarization) daha sonra st yzey, alt yzey ve vadi blgeleri seilerek, bu blgelerdeki
307

her bir siyah ve beyaz alanlarn toplam, toplam alana oran tespit edilmitir. Numunelerin gzeneklilik deerleri 10
blgedeki farkl gzeneklilik deerinin ortalamas alnarak belirlenmitir. ekil 4 (a-f), farkl toz boyut aralna (0-25
m, 25-45 m ve 45-63 m) sahip tozlar kullanlarak retilmi numunelerin st yzey, alt yzey ve vadi blgelerin
optik mikroskop ve siyah ve beyaz alanlara dntrlm grntlerini gstermektedir.
ekil 4. st yzey, alt yzey ve vadi blgelerin optik mikroskop ve siyah ve beyaz alanlara dntrlm
grntleri: ((a), (b); toz boyut aral 0-25 m (c), (d); toz boyut aral 25-45 m ve (e), (f); toz boyut aral
45-63 m).
308

2.3. Mikrosertlik lmleri

Yzeyi parlatlm olan numunelerin Vickers mikrosertlikleri Duramin 4 mikrosertlik test cihaznda (Struers Co, Cleveland, OH, ABD) llmtr. Numunelere uygulanan yk 50 gram olup bekleme sresi 10 saniye olarak seilmitir. st yzey, alt yzey ve vadi blgelerinden alnan sertlik lm yerleri ekil 5de gsterilmitir.
ekil 5. Vickers mikrosertlik lm noktalar.

3.1. Gzeneklilik
ekil 6 (a-f), farkl toz boyutu, sktrma scakl ve basncnn gzeneklilik zerindeki etkisini gstermektedir. Sinterleme scaklklar srasyla ekil 6 (a,c,e)de 600C, ekil 6 (b,d,f) de ise 900 C dir. Numunelerin st yzey, alt
yzey ve vadi blgelerindeki gzeneklilik deerleri, sktrma basncnn 20 MPadan 50 MPaa artmas durumunda
dmtr. 20 MPa sktrma basnc, 0-25 m toz boyutu, 425 C sktrma scakl ve 600 C sinterleme scaklnda st yzey blgesi iin elde edilen gzeneklilik deeri yaklak %30 iken; bu deer ayn artlarda 50 MPa
sktrma basnc iin %24 olarak elde edilmitir. Ayn artlarda sadece toz boyutu deitirildiinde (45-63 m) st
yzey blgesi iin gzeneklilik deerleri 20MPa ve 50MPa sktrma basnlarnda srasyla %32 ve %28 olarak
bulunmutur. Sinterleme scakl 900 oC ye arttrldnda ise 20 MPa ve 50 MPa sktrma basnlarnda, 0-25 m
toz boyutu ve 425 oC sktrma scaklnda st yzey blgesi iin elde edilen gzeneklilik deerleri srasyla %18
ve %10 dur. 45-63 m toz boyut aralnda ise bu deerlerin benzer ekilde yaklak %25 ve %20 olduu grlmtr. Tozlarn bir kalp ierisinde sktrlmas esnasnda, balangta tozlar 4-6 komusu ile temasta (koordinasyon
says) bulunur. Artan basnla birlikte tozlar kalba daha iyi yerleir ve uygulanan basncn deerine gre de ekil
deitirebilirler. Artan basnla birlikte gzenekliliin azalmasnn nedeni toz paracklarndaki deformasyonun artmas ve bunun sonucunda da tozlar arasndaki mevcut boluklarn azalmasdr [6, 7].
Gzenekliliin sktrma scaklnn artmasyla genel olarak azald gzlemlenmitir. 600 oC sinterleme scakl,
20 MPa sktrma basnc, 25-45 m toz boyut aral iin; sktrma scaklnn 350 oC den 500 oC ye artmasyla
st yzey blgesi iin elde edilen gzeneklilik deerleri srasyla %32 ve %27 olarak elde edilmitir. Sktrma
basncnn 35 MPa olmas durumunda 0-25 m toz boyut aral iin gzeneklilik deerleri %30 ve %21; 45-63 m
toz boyutunda ise bu deerler %36 ve %26 dr. 900 oC sinterleme scakl, 20 MPa sktrma basnc ve 25-45
m toz boyutunda sktrma scaklnn 350 oC den 500 oC ye arttrlmasyla elde edilen gzeneklilik deerleri
srasyla %23 ve %19; ayn artlarda basncn 50 MPa artmasyla ayn toz boyutunda gzeneklilik deerleri %21 ve
%15 olarak bulunmutur. (ekil 6 a-f). Artan scaklkla birlikte gzeneklilik deerlerinin azalmasnn nedeni tozlarn
ve kat alt yzeyin yumuayarak snek hale gemesi, basnla birlikte tozlarn temas alanlarnn artmasyla paracklar arasndaki boluklarn azalmasdr [1,8].
309

ekil 6. Gzenekliliin retim parametrelerine bal olarak deiimi: (a, c, e sinterleme scakl 600C; b, d, f
sinterleme scakl: 900C).
600 oC ve 900 C sinterleme scaklklarnda sinterleme ile boyun verme (necking-growth) oluumunun taramal
elektron mikroskopu (SEM) grnts ekil 7 (a-b) de verilmitir. 600 C sinterleme scaklklarnda boyun oluumu
gzlenmezken, 900 C sinterleme scaklnda kresel tozlar arasnda kat halde boyun oluumu grlmektedir. Bu
tr boyunlama, mukavemetin ham mukavemete oranla artmasn salar.
ekil 7. Sinterleme ile boyun oluumunun SEM grnts (sol taraf dk bytme sa taraf yksek bytme): a)
sinterleme scakl 600 C ve b) sinterleme scakl 900 C.
310

Farkl sktrma scakl ve basncnn numunelerin st yzey gzenekliliine etkisi boyutlu olarak ekil 8de
verilmitir. 600 C sinterleme scaklnda sktrma scakl ve basncna bal olarak daha yksek gzeneklilik
seviyeleri ve deiimleri elde edilirken 900 oC sinterleme scaklnda gzeneklilik seviyeleri daha dk olmutur.
ekil 8. st yzey blgesi iin sktrma scakl ve basncnn gzeneklilik zerine etkisi: (a) sinterleme scakl
600 C ve (b) sinterleme scakl 900 C.
3.2. Mikrosertlik
ekil 9 (a-f), farkl toz boyutu ve sktrma scaklnn st yzey, alt yzey ve vadi blgelerinin mikrosertlik zerindeki etkisini gstermektedir. ekil 9 (a-f)de grld zere, st yzey alan iin elde edilen mikrosertlik deerlerinde sinterleme scaklnn 600 oCden 900 oCye arttrlmasyla, hem sktrma scaklnn hem de sktrma
basncnn arttrlmasyla belirgin bir deiim elde edilememitir. st yzey blgesi iin mikrosertlik deerleri 85-100
(Hv0,05) olarak tespit edilmitir. Ancak, alt yzey ve vadi blgelerinin mikrosertlikleri hem sktrma scaklnn ve
basncn artrlmasyla hem de sinterleme scaklnn arttrlmasyla artmtr.
311

ekil 9. Mikrosertliin retim parametrelerine bal olarak deiim;

(a, c, e sinterleme scakl 600C; b, d, f sinterleme scakl: 900C).
Farkl sktrma scakl ve basncnn numunelerin st yzey mikrosertlik zerindeki etkisi boyutlu yzey alan
olarak ekil 10da gsterilmitir.
ekil 10. st yzey blgesi iin sktrma scakl ve basncnn mikrosertlik zerine etkisi (a) sinterleme
scakl 600 C ve (b) sinterleme scakl 900 C.
4. SONULAR
Bu almada toz metalurjisi yntemiyle farkl toz boyutu aralklarnda bakr tozlar kullanarak boyutlu, gzenekli
yzeyler, farkl retim parametrelerine bal olarak retilmi ve retim parametrelerinin yzeylerin gzeneklilik ve
mikrosertlik zerindeki etkisi incelenmitir. almada gzenekli yzeyler, iki farkl toz boyutu aralna sahip olacak ekilde tozlar kullanlarak retilmitir. Elde edilen sonulardan gzenekliliin hem st yzey ve alt yzey hem
de vadi blgeleri iin artan toz boyutu, azalan sktrma scakl, basnc ve azalan sinterleme scakl ile artt
grlmtr. Ancak, numunelerin st yzey blgesi iin, mikro sertlik deerlerinde retim parametrelerine bal
nemli bir deiim gzlemlenmemitir. Ancak, alt yzey ve vadi blgeleri iin mikrosertlik deerleri, artan sinterleme
scakl, sktrma scakl ve basncyla artmtr.
TEEKKR
Bu alma, Amerikan Ulusal Bilim Konseyi (NSF) tarafndan desteklenen ENG/CMMI 0638522 nolu proje kapsamnda yaplmtr. Proje desteklerinden dolay Ulusal Bilim Konseyine teekkr ederiz.
KAYNAKLAR
1. Cora, .N., Usta, Y., and Ko, M., Micro-Manufacturing of Micro-Scale Porous Surface Structures for Enhanced Heat Transfer Applications An Experimental Process Optimization Study, Journal of Micromechanics
and Microengineering, Vol. 19, pp. 1-12, 2009.
2. Min, D.H., Hwang, G.S., Usta, Y., Cora, O.N., Ko, M., and Kaviany, M., 2-D and 3-D Modulated Porous Coatings for Enhanced Pool Boiling, International Journal of Heat and Mass Transfer, Vol. 52, pp. 2607-2613,
2009.
312

3. Cora, .N., Min, D., and Ko, M., Kaviany, M., Micro-scale Modulated Porous Surface Coatings-Fabrication
and Pool Boiling Heat Transfer Experiments, Journal of Micromechanics and Microengineering, Vol. 20,
pp. 1-12, 2010.
4. Liter, S.C, and Kaviany, M., Pool-boiling CHF Enhancement by Modulated Porous-Layer Coating: Theory and
Experiment, International Journal of Heat and Mass Transfer, Vol. 44, pp. 4287-4311, 2001.
5. Ko, M., Usta, Y., and Karako, A., Investigations on Thermo-Mechanical Fabrication of Micro-Scale Porous
Surface Features Journal of Power Sources, Vol. 179, pp. 592602, 2007.
6. Gupta, M., Tay, A.A.O., Vaidyanathan, K., Srivatsan, T.S., An Investigation of the Synthesis and Characterization of Copper Samples for Use in Interconnect Applications, Materials Science and Engineering: A, Vol.
454-455, pp. 690-694, 2007.
7. German, R.M., Toz Metalurjisi ve Parackl Malzeme lemleri Editrler: Sarta, S., Trker, M., Durlu, N.,
Trk Toz Metalurjisi Dernei Yaynlar: 05, Ankara, 2007.
8. Ahmed, Y.M.Z, Riad, M.I., Sayed, A.S., Ahlam, M.K., Shalabi. M.E.H., Correlation between Factors Controlling
Preparation of Porous Copper via Sintering Technique using Experimental Design, Powder Technology, Vol.
175, pp. 48-54, 2007.
313

POROUS
MATERIALS
www.turkishpm.org
314

TOZ METALURJS YNTEM LE RETLEN KRESEL EKLL

ALMNYUM KPKTE KPRTME SICAKLIININ VE TiH2 ERNN
KPRME DAVRANII ZERNE ETKS
Arif UZUN*, Mehmet TRKER**
Kastamonu niversitesi, Cide Rfat Ilgaz MYO, Kaynak Teknolojisi Blm, Kastamonu,
auzun@kastamonu.edu.tr
**
mturker@gazi.edu.tr
*
zet
Bu almada toz metalurjisi yntemi ile retilen kresel ekilli alminyum kpk paralarda kprtme scakl ve
kprtc madde (TiH2) miktarnn, kprme davran zerine etkileri aratrlmtr. Buna gre Alumix 231 tozuna
deiik oranlarda (% 0,5-0,75-1 ve 1,5) TiH2 tozu ilave edilerek kartrlm ve tek ynl preste 600 MPa basn
uygulanarak preslenmitir. Bunun sonucu 30x50x10 mm llerinde elde edilen taslak numuneler frn ierisinde
550oC scaklkta 180 dakika bekletilmi ve % 70 orannda deforme edilmitir. Elde edilen preform numuneler kare
eklinde kesilerek, 650oC ile 710oC scaklklar arasnda kprtme ilemine tabi tutulmutur. Burada kprtme scaklna ve TiH2 ieriine bal olarak kresel ekilli Al kpn hacimsel genleme oranlar, younluk ve gzenek
morfolojisi deiimleri belirlenmitir.
Anahtar Kelimeler: Kresel ekilli Al Kpk, Kprtme Scakl, TiH2
THE EFFECT OF TiH2 CONTENT AND FOAMING TEMPERATURE ON THE

FOAMING BEHAVIOUR OF SPHERICAL ALUMINUM FOAM PRODUCED BY
POWDER METALLURGY ROUTE
ABSTRACT
The effect of production parameters such as foaming duration and the amount on the foaming behavior of sphericalshaped aluminum foam parts was studied. Alumix 231 and various amount of foaming agent (0,5-0,75-1 and 1,5%
TiH2) were mixed, and then compacted at 600 MPa pressure by using a uniaxial action press to produce blanks with
50x30x10 mm dimensions. These blanks were pre-heated at 550C in a furnace for 180 min and then deformed by
70% by using an eccentric press. They were cut into square shape and foamed at temperatures between 650oC
and 710oC. It was determined that the linear expansion, density and pore morphology chances of spherical-shaped
aluminum foam depending on the foaming temperature and TiH2 content.
Keywords: Spherical-Shaped Al Foam, Foaming Temperature, TiH2
1.GR
Metalik kpkler mekaniksel, fiziksel ve akustik zellikleri son derece iyi olan ve retim yntemleri hzla gelitirilen
yeni bir malzeme grubudur [1]. Bu zelliklerinin kombinasyonundan dolay yapsal ve fonksiyonel uygulamalarda
315

sklkla kullanlmaya balanm ve bunun zerine birok aratrma yaplmtr [1-3]. Bu aratrmalara konu olan ve
metalik kpkler arasnda yeni saylabilecek malzeme trlerinden bir tanesi de kresel ekilli alminyum kpklerdir. Almanyada IFAM tarafndan gelitirilen kresel ekilli metalik kpk paralar ileri gzenek morfolojisi (APM)
teknii ile retilmektedir. Bu yntem esasen toz metalurjisi yntemindeki kpn genleme ve ekillenme ilemlerini birbirinden ayrmaktadr. Bu iki aama, farkl zamanlarda ve farkl yerlerde retici firmalar tarafndan ayr ayr
gerekletirilebilmektedir. Gerek IFAM, gerekse dier ticari firmalar tarafndan retilecek kresel ekilli alminyum
kpk paralar tketiciye maliyet ve iilik asndan nemli lde tasarruf salamaktadr. Bu teknikte kprtme
ilemi esnasnda kalp kullanlmamaktadr. retilen paralar genelde 1 cm3ten daha kk hacimlere sahiptir. Bu
malzemeler aralarn n takmlarndaki darbe dayanmn artrmak iin elik profillerin ierisine doldurularak kullanlabildikleri gibi basit yaptrma teknikleri ile birlikte kullanlmas, kullanclar iin maksimum ynde esneklik
salamaktadr [4, 5].
2.1. Malzemeler
Deneysel almalarda kresel ekilli alminyum kpk retimi iin matris malzemesi olarak % 99 saflkta ve <200
m parack ebadna sahip Alumix 231 tozlar (Al-%2,5Cu-%0,5Mg-%14Si) ve kprtc madde olarak da <45 m,
% 98 saflktaki TiH2 tozlar kullanlmtr.
2.2. Numune Hazrlama ve Kprtme lemi
almann ilk aamas preform malzeme retimi ile balamaktadr. Bu amala deiik oranlarda (% 0,5-0,75-1
ve 1,5) TiH2 tozlar, matrisi oluturan alminyum tozlarna ilave edilerek, boyutlu kartrcda 30 dakika sreyle
kartrlmtr. Daha sonra karm tozlar kalp ierisinde tek ynl preste 600 MPa basn uygulanarak preslenmi
ve 30x50x10 mm llerinde taslak numuneler haline getirilmitir. Elde edilen bu numuneler frn ierisinde 550oC
scaklkta, 180 dakika bekletilerek n stmaya tabii tutulmutur. Akabinde numuneler % 70 oranda deforme edilmi
ve 6x6 mm boyutlarda kare eklinde kesilerek kprmeye hazr hale getirilmitir. kinci aamada ise kprtme ilemi
gerekletirilmitir. Bunun iin kprmeye hazr hale gelen preform numuneler frn ierisinde 650oC, 670oC, 690oC
ve 710oC scaklklarda 2 ile 5 dakika arasnda 30 saniye aralklarla bekletilerek kprtme ilemine tabii tutulmutur.
Bu ilem srasnda herhangi bir kalp kullanlmadan serbest halde kprtme yaplmtr. Bu sayede frn ierisindeki
s, kalp duvarlar tarafndan engellenmeden preform malzeme ierisine dorudan nfus etmi ve yar ergiyik hale
gelen alminyumun, yzey gerilmesi neticesinde kresele yakn bir ekil almtr. ekil 1de kresel ekilli kpn
retimi esnasnda sahip olduu geometrik yapya benzeyen metalik kpn radyoskobik X-ray grnts verilmektedir.
ekil 1. Kresel ekilli kpn retimi esnasnda sahip olduu geometrik yapya benzeyen metalik kpn
radyoskobik X-ray grnts [6]
retilen kpk numunelerin younluklar ve hacimsel olarak genleme oranlar 0,1 mg hassasiyetteki terazi ve
younluk kiti ile llmtr. Buna gre younluk hesab E.1de verilen Arimet prensibi esasna gre yaplmtr.
Bu eitlikte, * kpn younluunu, mhava kpn havadaki arln ve msu kpn su ierisindeki arln
ifade etmektedir.
316

(1)
Genleme oran ise E. 2de verilen formle gre hesaplanmtr. Bu formlde V* kpn hacmini, V ise kprtme
ncesi numunenin ilk hacmini ifade etmektedir. Gzeneklilik oran ise E.3te verilen formle gre hesaplanmtr.
Burada , gzenek duvarlarn oluturan ana malzemenin younluunu belirtmektedir.
Hacimsel Genleme ( HG ) = (V*/V-1) x 100
(2)
Gzeneklilik (G)= (1 */) 100
(3)
Younluklar ve hacimsel genleme oranlar hesaplanan numuneler daha sonra makro boyutta gzenek yaplar
incelenmek amacyla 240lk zmpara ile su altnda andrlmtr. Daha sonra elde edilen alminyum kpklerin
gzenek ekli, gzenek boyutu ve gzenek dalm incelenmek amacyla dijital kamera ile makro yap fotoraflar
ekilmitir. Bylelikle kprtc madde miktarnn ve kprtme scaklnn kresel ekilli alminyum kpk retimine etkileri incelenmitir.
3. DENEY SONULARI VE TARTIMA
Tablo 1de kpk retim aamalarnda kullanlan deiken parametreler verilmitir. Bu parametreler birbirleriyle
kombine edilerek her trl deney art deerlendirilmitir. Bylece deneylerde kullanlan deiken parametrelerin,
kresel ekilli kpn younluk, hacimsel genleme, gzenek morfolojisi gibi zelliklere ne tr etkisi olduu belirlenmitir.
Tablo 1. Kresel ekilli alminyum kpk retiminde kullanlan deiken retim parametreleri
TiH2 miktar
(%)
Deformasyon
oran (%)
Kprtme
scakl (oC)
0,5
650
0,75
670
70
690
1,5
710
Kprtme
sresi (dak.)
2-2,5
3-3,5
4-4,5
5
3.1. Liner Genleme, Kresellik ve Younluk Deiimleri

ekil 2de farkl scaklklarda kprtme ilemine tabii tutulan numunelerin kprtc madde miktar ve kprtme
srelerine bal hacimsel genleme oranlar verilmitir. Buna gre, grafiklere bakldnda 650oC scaklkta numunelerde maksimum hacimsel genleme orannn % 400 at grlmektedir. Ancak bu noktaya ulatklar sreler
birbirinden farkldr. erisinde %1,5 TiH2 ieren numuneler, dierlerine oranla daha ksa srede ve % 431 ile maksimum oranda hacimsel genleme sergilemitir. Bu oran % 0,5 TiH2 ieren numunelerde % 422, % 0,75 TiH2 ieren
numunelerde % 434 ve %1 TiH2 ieren numunelerde % 449dur. 670 oCde kprtme ilemine tabii tutulan numuneler arasnda en fazla hacimsel genlemenin % 523 ile ierisinde %1 orannda TiH2 ieren numunelerde meydana
geldii grlmektedir. Bu scaklkta en dk maksimum hacimsel genleme ise % 400 ile ierisinde % 1,5 TiH2 bulunduran numunelerde elde edilmitir. Benzer ekilde 690 oCde kprtme ilemine tabii tutulan numuneler arasnda
da en fazla hacimsel genlemenin % 556 ile ierisinde %1 TiH2 ieren numunelerde meydana geldii grlmektedir.
Bu scaklkta en dk hacimsel genleme ise % 356 ile yine ierisinde % 1,5 TiH2 bulunduran numunelerde elde
edilmitir. Burada dikkat ekici husus, % 1,5 TiH2 ieren numuneler 650 oCde maksimum hacimsel genleme oranna sahipken, 670 oC ve 690 oC scaklklarda en dk hacimsel genleme oranlarna sahiptir. Bu fark hacimsel
genlemeye yalnzca kprtc madde miktarn deil, ayn zamanda scaklnda etkisi olduunu gstermektedir.
Literatrde genleme orann sadece kprtc madde miktarna bal olmad, ayn zamanda ergiyik viskozitesine
de bal olduu belirtilmitir [7-9]. Bu dorultuda scaklktaki artn, kprme ilemi srasnda ergiyik halde bulunan numunenin viskozitesini drd, bylelikle yap ierisinde bulunan hidrojen gaznn daha rahat genleme
gsterdii anlalmaktadr. Ancak bu genlemenin devam etmesi, kpk yapda hcre zarnn incelmesine ve zarn
yrtlmasna neden olmaktadr. Dolaysyla yap ierisinde hapsedilmi hidrojen gaznn bu blgelerden rahatlkla
uzaklat ve kntlerin balad grlmtr (ekil 3) [6]. Bunun sonucu olarak 710 oCde kprtme ilemine
tabii tutulan numunelerin hacimsel genleme oranlarnda azalmalar ve yapda dzensizlikler meydana gelmitir.
317

ekil 2. Farkl scaklklarda kprtme ilemine tabii tutulan numunelerin kprtc madde miktarna ve kprtme
srelerine bal hacimsel genleme oranlar
ekil 3. Kprtme ilemi srasnda yapda meydana gelen yrtlma

ekil 4te ierisinde deiik miktarlarda kprtc madde bulunan ve farkl scaklklarda kprtme ilemine tabii
tutulan numunelerin maksimum oranda hacimsel genlemeleri sonucu elde edilen kpk yaplar verilmektedir. Bu
resimler zerinden yaplan alansal ve evresel lmler elde edilen numunelerin teoride kresellik deerleri hakknda bilgi vermitir. Bunun iin aadaki eitlikten faydalanlarak hesaplamalar yaplmtr. Burada fkresel ekil faktr,
A alan ve P evre uzunluunu belirtmektedir.
f kresel = (4A)/P2x100
(4)
Elde edilen verilere gre 650 oC, 670 oC ve 690 oC scaklklarda maksimum hacimsel genleme sergileyen numunelerde % 90 ile % 95 arasnda deien kresellik deerlerleri mevcuttur. Ancak 710 oCde kpk yaplardaki dzensizlikler rahatlkla fark edilmekte ve kresellik oranlar dierlerine oranla ok daha dk olduu grlmektedir.
Dz bir zemin zerinde kprtlen numuneler yer ekimi etkisiyle tam bir kresellie sahip olmadndan geometrik
ekilleri elipse benzemektedir [10].
318

Maksimum oranda genleme sergileyen numunelerin younluklar karlatrldnda ise en dk younluk ierisinde % 1 TiH2 ieren ve 690 oCde kprtlen numunelerde elde edilmitir. Younluk, numunelerin hacmi ile ters
orantl olduundan hacimsel genleme oran maksimum olan bu numunelerde younlukta en dk seviyededir.
Kresel ekle yakn olan numunelerde younluk deiimi 0,41 - 0,52 g/cm3 arasndadr.
ekil 4. Farkl scaklklarda kprtme ilemine tabii tutulan numunelerin maksimum oranda hacimsel genlemeleri
sonucu elde edilen kpk yaplar
3.2. Gzenek Morfolojisi Deiimi
ekil 5te maksimum oranda hacimsel genleme sergileyen numunelerin gzeneklilik oranlar verilmitir. Gzeneklilik oran numune ierisindeki gaz boluklarn ifade etmektedir. Bu orann gzenek says ile kartrlmamas
gerekmektedir. Grafie bakldnda 650 oC, 670 oC ve 690 oC scaklklarda % 1e kadar TiH2 art gzeneklilik
orannda arta neden olurken, 710 oCde srekli azalan ynde etki etmitir. Benzer scaklklarda % 1,5 TiH2 ieren
numunelerde ise gzeneklilik orannda belirgin bir dn meydana geldii grlmektedir. Bunun sebebi, artan
scaklk ve kprtc madde miktar, kprtme ilemi srasnda gzeneklerin birlemesine ve yer yer hidrojen ka
ile kntlere neden olmasdr. Maksimum oranda gzeneklilik % 85 ile 690 oC scaklkta % 1 orannda TiH2 ieren
numunelerde elde edilmitir. En dk gzeneklilik ise 710 oC scaklkta % 1,5 orannda TiH2 ieren numunelerde
% 75 orannda elde edilmitir.
319

ekil 5. Maksimum oranda hacimsel genleme sergileyen numunelerin gzeneklilik oranlar

ekil 6da maksimum oranda hacimsel genleme sergileyen numunelerin ara kesit resimleri verilmitir. Numunelerin gzenek yaplar makro boyutta incelendiinde gzenek boyutu ve saysnda farkllklarn olduu aka grlmektedir. 650oC, 670oC ve 690oC scaklklarda kprtc madde miktar %1,5e ulatnda gzenek boyutlarnda
dierlerine kyasla belirgin bir art mevcuttur. Bu durum kprtme ilemi srasnda preform ierisinde youn halde
bulunan TiH2n znmesi sonucu aa kan gaz baloncuklarnn birlemesi ile olumutur. Ayrca artan scaklkla birlikte yap ierisindeki hidrojen gaz basncndaki art bu durumu daha etkin hale getirmektedir. Sz konu
etkenler ald zaman ise 710 oCde kprtme ilemine tabi tutulan numunelerde olduu gibi kmeler meydana
gelmektedir. Gzenek boyutu dalm asndan ierisinde % 0,5 ile % 1 arasnda TiH2 ieren ve 690oCde kprtlen numuneleri daha homojen olduu grlmektedir. Alminyum kpk retiminde TiH2 miktar genellikle % 0,6
ile % 1 arasnda seilmektedir.
ekil 6. 650oCde kprtme ilemine tabii tutulmu numunelerin gzenek yaplar
320

4. SONULAR
Bu almada toz metalurjisi yntemi ile retilen kresel ekilli alminyum kpk paralarda kprtme scaklnn
ve kprtc madde miktarnn, kprme davran zerine etkileri aratrlmtr. Elde edilen verilere gre kresel
ekilli alminyum kpklerdeki hacimsel genlemenin yalnzca kprtc madde miktarna bal olmad, ayn
zamanda scaklk ile ilikili olduu belirlenmitir. nk alminyum kpklerde artan scaklk ile birlikte ergiyik
viskozitesi dmektedir. Bundan dolay hem scaklk, hem de kprtc madde miktarndaki art yap ierisindeki
hidrojen gaz basncn artrmakta ve yapda daha rahat genleme salamaktadr. Ancak bu genleme belirli bir
noktadan sonra hcre zarnda incelmelere ve yrtlmalara neden olarak kresel ekilli alminyum kpn kmesine ve yapsal dzensizliklerin olumasna neden olmaktadr. Bu durumum 710oC scaklkta daha etkin olduu
belirlenmitir. Dolaysyla scaklk ve kprtc madde miktarndaki art ile kresel ekilli alminyum kpk retim
sreci kontrolnn azald aktr. 650oC, 670oC ve 690oC scaklklarda maksimum oranda genleme sergileyen
numunelerde teorik olarak % 90nn zerinde kresellik elde edilmitir. Fakat 710 oCde kresellik bu orann altndadr. Kresel ekle yakn olan numunelerde younluk deiimi 0,41 - 0,52 g/cm3 arasndadr. 650 oC, 670 oC ve 690
o
C scaklklarda % 1e kadar TiH2 art gzeneklilik orannda arta neden olmutur. 710 oCde ise srekli azalan
ynde etki etmitir. Benzer scaklklarda % 1,5 TiH2 ieren numunelerde ise gzeneklilik orannda belirgin bir d
meydana gelmitir. Bunun sebebi, artan scaklk ve kprtc madde miktar, kprtme ilemi srasnda gzeneklerin birlemesine ve yer yer hidrojen ka ile kntlere neden olmasdr. Maksimum oranda gzeneklilik % 85
ile 690 oC scaklkta % 1 orannda TiH2 ieren numunelerde elde edilmitir.
KAYNAKLAR
1. Ashby, M. F., Evans, A., Fleck, N. A., Gibson, L. J, Hutchinson J. W., Wadley, H. N. G.,Metal foams: a design
guide, Oxford, Butterworth, Heinmann, 2000.
2. Banhart, J., Manufacture, characterisation and application of cellular metals and metal foams, Progress in
Materials Science, 46:559-632, 2001
3. Degischer, H.P.; Kriszt, B., Handbook of Cellular Metals, Wiley- VCH, Weinheim, pp. 1521, 2002
4. Rausch, G., K. Stobener, Improving Structural Crashworthiness Using Metallic and Organic Foams, Porous
Metals and Metal Foaming Technology Conference Proceedings, Kyoto (Japan), JIMIC, 2005
5. Stbener, K., Baumeister, J., Rausch, G., Rausch, M., Forming metal foams by simpler methods for cheaper
solutions, Metal Powder Report, 60:12-16, 2005
6. Dudka, A., Garcia-Moreno, F., Wanderka, N., Banhart, J., Structure and distribution of oxides in aluminium
foam, Acta Materialia, 56:39904001, 2008
7. Yang, C.C., Nakae, H., Foaming characteristics control during production of aluminum alloy foam, Journal of
Alloys and Compounds, 313:188191, 2000.
8. Uzun, A., inici, H., Trker, M., Effect of deformation rate and foaming duration on the properties of spherical
aluminum foam produced by powder metallurgy, 5th International Powder Metallurgy Conference, Ankara,
801-807, 2008
9. Duarte, I., Banhart, J., A study of alumnum foam formaton knetcs and mcrostructure, Acta mater.,
48:23492362, 2000.
10. Stbener, K., Baumeister, J., Rausch, G., Busse, M.,Metal Foams with Advanced Pore Morphology (APM),
Fraunhofer IFAM, 26:231-237, 2007
321

YKSEK ORANDA GZENEK EREN DEMR ESASLI

KOMPAKTLARIN KARBON ERNN BASMA
DAVRANIINA ETKS
Nuray BEKZ*, Enver OKTAY*
*stanbul niversitesi Metalurji ve Malzeme Mhendislii Blm, Avclar,stanbul.
e-mail : nbekoz@istanbul.edu.tr, oktay@istanbul.edu.tr
ZET
Bu almada; %48-70 arasnda deien oranlarda gzenek ieren demir esasl kompaktlar; n alaml
Distaloy AE demir tozuna a. %0,3, 0,6 ve 0,8 orannda karbon katlarak toz metalurjisindeki boluk
yapc teknii kullanlarak retilmilerdir. Boluk yapc olarak 0,71-1,00 mm boyut aralna sahip dzensiz ekilli karbamit, karbon katkl Distaloy AE tozuyla kaplanm ve 200 MPa basn altnda tek
ynl preslenerek boy/ap oran yaklak 1,5 olan ham kompaktlar elde edilmitir. Ham kompaktlar ierisindeki karbamitin oda scaklnda suda zndrlmesi ile oluturulan gzenekli yaplar; hidrojen atmosferi altnda 1200 Cde 60 dakika sinterlenmitir. Karbon ilavesi kompaktlarn basma dayanmlarn
arttrmtr. Artan gzenek miktar ile kompaktlarn basma dayanmlar ve elastisite modlleri azalmtr.
Basma testi sonular, mikroyap karakterizasyon bulgular altnda tartlmtr.
Anahtar kelimeler: Gzenekli malzemeler, n alaml demir tozu, sinterleme, basma testi.
EFFECT OF CARBON CONTENT OF HIGHLY POROUS IRON BASED

COMPACTS ON THE COMPRESSION BEHAVIOUR
ABSTRACT
In this study; iron based compacts having porosities in the range 48-70% were produced from 0.3, 0.6
and 0.8 wt.% carbon added pre-alloyed Distaloy AE powders by the space holder technique in powder
metallurgy. For this purpose irregular shaped carbamide particles with the size distribution of 0.71-1.00
mm were covered by carbon added prealloyed iron based Distaloy AE powder and pressed uniaxially
at 200 MPa to produce cylindrical green compact with length to diameter ratio of about 1.5. Highly porous structures were obtained by removal of the carbamide in a water bath at room temperature and
sintered under hydrogen atmosphere at 1200 C for 60 minutes. Carbon additions increased the compressive strength values of the compacts. Compressive strength and the modulus of elasticity values of
the compacts decreased with increasing porosity. Results obtained by compression test were discussed
in light of the findings obtained by microstructure characterization.
Keywords: Porous materials, pre-alloyed iron powder, sintering, compression test.
1. GR
Toz metalrjisi yntemiyle retilen demir esasl malzemelerin mukavemetini arttrmak iin, demir tozlarna eitli alam elementleri ilave edilir. Karbon katks elastiklik zelliin aranmad durumda yk-
322

sek mukavemete sahip para retimini ekonomik olarak mmkn klmaktadr. Bu, parann her yerinde
demiri karbonla alamlandrarak elde edilir. Bu tip bir malzeme retiminin en yaygn yntemi demir
tozuyla grafiti kartrmaktr. Yaplan almalar, sinterleme srasnda stenit ierisine geen karbonun
souma esnasnda perlitik ve beynitik yapy oluturduunu ortaya koymutur [1-6]. Chawla ve dierleri
[7], Distaloy AB tozuna benzer bileimdeki alaml demir tozuna farkl oranlarda karbon ilave ederek
rettikleri youn numunelerde mikroyapnn perlit, beynit, martensit, nikelce zengin blge ve gzeneklerden olutuunu tespit etmilerdir.
Boluk yapc kullanarak toz metalurjisi yntemiyle yksek oranda gzenek ieren metal (kpks metal)
retimi; gzenek zelliklerinin, malzeme eklinin ve mekanik zelliklerin kontrolnde dier yntemlere
gre salad birok stnlkten dolay son yllarda kullanlan bir yntem olarak karmza kmaktadr.
Kullanlacak boluk yapc, malzemenin ierisinde kalnt brakmadan kolayca atlabilmeli ve metalle
reaksiyona girmemelidir. Karbamit, hem termal hem de suda zndrlerek yapdan uzaklatrlabildiinden; alminyum, titanyum, paslanmaz elik, nikel ve bunlarn alamlarndan yksek oranda gzenek ieren metal retiminde son yllarda baarl olarak kullanlmaktadr [8-11]. Mo ieren n alaml
demir tozlarndan retilen yksek oranda gzenek ieren malzemeler; yksek scakla ve sl oklara
kar dayanma sahip olmasndan dolay s kalkan olarak s yaltm ve soutma sistemlerinde, yanma motorlarnn yksek scakla maruz kalan k yerlerinde kullanm potansiyeline sahiptir [12-13].
Literatrde; Distaloy AE tozundan hareketle boluk oluturucu kullanlarak toz metalurjisi yntemiyle
kpks metal retimine ynelik bir alma bulunmamaktadr. Bu almada, boluk yapc kullanarak
toz metalurjisi yntemiyle Distaloy AE tozundan yksek oranda gzenek ieren numuneler retilerek;
karbon katksnn basma davran zerine etkisi mikroyap karakterizasyon bulgular altnda deerlendirilmitir.
2. MALZEME VE YNTEM
Deneysel almada; Hgans firmas tarafndan atomizasyon yntemi ile retilmi ortalama tane boyutu 90 m olan dzensiz ekilli n alaml Distaloy AE demir tozu kullanlmtr. Karbon ilavesinin
sinterleme sonras zelliklere etkisini incelemek iin Hgans firmas tarafndan retilmi sertletirici
ve yalayc zelliklere sahip ticari ismi UF4 olan grafit tozu kullanlmtr. Ham mukavemeti arttrmak
amacyla balayc olarak kullanlan parafin Merck firmasndan temin edilmi olup 46-48 C arasnda
erime scaklna sahiptir. Boluk yapc olarak; +710-1000 m boyut aralna sahip dzensi3z ekilli
teknik safiyette karbamit kullanlmtr. Karbamitin younluu; 1,34 g/cm , erime scakl 133 C ve 20
C scaklktaki suda znrl 108 g/mLdir. Deneysel almada kullanlan tozlarn kimyasal bileimleri Tablo 1de verilmektedir.
Tablo 1 : Tozlarn kimyasal bileimleri, % [3].
ekil 1-(a)da atomizasyon yntemiyle retilmi n alaml Distaloy AE tozunun, (b)de dzensiz ekilli
karbamitin Taramal Elektron Mikroskobu (SEM) grntleri verilmitir.
ekil 1 : Deneysel almada kullanlan (a) Distaloy AE tozunun ve (b) karbamitin SEM grnts
323

Deneysel almada kullanlan toz metalurjisi yntemi ile kpks metal retiminin temel ilem admlar
ekil 2de verilmitir.
ekil 2 : Toz metalurjisi yntemi ile kpks metal retiminin temel ilem admlar
Numunelerin retimi aamasnda ilk olarak; Distaloy AE tozuna a.%0,3, %0,6 ve %0,8 oranlarnda
karbon ilavesi yaplarak farkl karbon ieriklerinde demir esasl toz gruplar oluturulmutur. lave edilen
karbonun karm ierisinde homojen olarak dalmas iin tozlar, 30 kg kapasiteli 30 devir/dakika hza
sahip Apex marka laboratuar tipi kartrc ierisinde 30 dakika sreyle kartrlmtr. Ham numunelerin
mukavemetinin arttrlmas amacyla balayc olarak a.%3 orannda hazrlanan parafin zeltisi, n
alaml demir tozuna hac.%2 orannda katlarak oda scaklnda 30 dakika kartrlmtr. Karma;
hac.%50 ile %80 arasnda deien oranlarda karbamit ilave edilip turbula tipi kartrcda 1 saat sre
ile kartrma sonucu, karbamit paracklar demir tozlar ile kaplanmlardr. Demir tozlaryla kaplanm
karbamitin elik bir kalp ierisinde tek ynl preslenmesiyle 12 mm apnda ve yaklak 18 mm yksekliinde silindirik numuneler elde edilmitir. Optimum presleme basncn belirlemek amacyla 100-400
MPa arasnda basnlar uygulanmtr. Preslenen numuneler ierisindeki karbamitin zndrlerek numunelerden uzaklatrlmas oda scaklnda saf su banyosunda yaplmtr. 200 MPa altnda basnlar uygulanarak retilen ve yksek oranda karbamit ieren numunelerdeki karbamitin zndrlerek
uzaklatrlmas esnasnda yapnn kt; 200 MPa zerinde basnlar uygulanarak retilen daha dk oranlarda karbamit ieren numunelerde ise; karbamit uzaklatrldktan sonra kurutma esnasnda
numunelerin atlad grlmtr. Bu nedenlerden dolay tm numuneler 200 MPa basn uygulanarak
preslenmitir. zndrme sresi; hacimce %80, %70, %60 ve %50 karbamit ieren numuneler iin
srasyla; 3, 5, 8 ve 12 saat olarak gereklemitir. Numunelerin ierisinde kalan az miktardaki karbamit
ile balayc olarak kullanlan parafinin termal olarak giderilmesi ve sinterleme ilemi Lenton marka frnda yaplmtr. Seramik boru ierisine yerletirilen numuneler; ortamdan N2 gaz geirilerek nce 5 C/
dak stma hzyla 400 Cye stlm ve bu scaklkta 30 dakika tutulmu daha sonra ortamdan yksek
safiyette H2 gaz geirilerek 10 C/dakika stma hzyla 1200 Cde 1 saat sinterlenmitir.
Sinterlenmi numunelerin younluklar, ak ve kapal gzenek oranlar Arimed Yntemine gre belirlenmitir. Sinterleme sonras karbon katkl ve katksz numunelerdeki karbon ieriklerinin tayini; Leco
CS-600 marka C/S analiz cihaznda gerekletirilmitir. Numunelerin grnt analizleri Jeol JSM-5600
Taramal Elektron Mikroskobunda yaplmtr. Metalografik inceleme iin sinterlenmi numuneler Struers
Epvac marka vakumlu kalplama cihaznda epoksi reine ile kalba alnp Nikon FDX kamera balants
olan Olympus marka PME3 model k metal mikroskobunda incelenmitir. Sinterlenmi numunelerde
gzeneklerin kresel ap ve kresellik dalmlar; Clemex Vision PE-4.0 grnt analiz program kullanlarak SEM resimleri zerinde belirlenmitir. Basma testleri, ZWICK marka Z 050 PROLINE model
mekanik test cihaznda oda scaklnda 0,5 mm/dak. basma hzyla gerekletirilmitir. Gerilme- %ekil
deiim grafikleri ve hesaplamalar, Test-Xpert programnn V11-02 versiyonu kullanlarak elde edilmitir.
3. SONULAR VE DEERLEND RME
Karbamitin oda scaklndaki su banyosunda numunelerden uzaklatrlmas ile oluturulan yksek
oranda gzeneklilie sahip numuneler sinterleme sonrasnda da yaplarn korumulardr. retilen sinterlenmi numunelerin younluklar 2,32-4,08 g/cm3, toplam gzenek oranlar %.47,7-70,3, ak gzenek oranlar %.33,5-62,8 ve kapal gzenek oranlar %7,5-14,2 arasnda deimitir. Artan gzenek
miktar ile numunelerdeki ak gzenek oran artmtr. Bu art gzeneklerin birbirleriyle balant kurmasndan kaynaklanmtr. Gzenek miktar azaldka elde edilen gzenekler birbirinden izole olarak
kapal gzenekli yaplar elde edilmektedir.
Karbamit miktar arttka sinterleme sonras numunelerin gzenek oranlar da artmtr. Ancak ilave
edilen karbamit miktarna gre sinterleme sonras beklenen gzenek ieriklerinde azalma meydana gelmitir. Bu azalma hacimce %70 ve %80 karbamit ilave edilmesi durumunda daha fazla gereklemitir.
Sinterleme esnasndaki ekme ham younlukla ters orantl olduundan daha yksek miktarda karba-
324

mit kullanlarak retilen numuneler daha dk ham younlua sahip olup sinterleme sonucu nispeten
daha ok younlamlardr. Sinterleme sonras numunelerde meydana gelen hacimsel ekme %4,3 ile
%6,7 arasnda gereklemitir. Sinterleme sonras gzenek oran %48in zerinde olan numunelerde
karbon katksnn hacim deiimi zerine nemli bir etkisi olmamtr. %48 gzenek orannda ise tm
numunelerde gzenek duvarlarnn kaln olmasndan dolay artan karbon miktaryla bir miktar ekme
gereklemitir. %0,8 karbon katksnda hacimsel ekme daha belirginlemitir. Sinterleme esnasnda
meydana gelen boyutsal klme gzenek duvarlarnda sinterleme esnasnda meydana gelen ekmeden kaynaklanmaktadr.
Sinterleme sonras karbon katkl numunelerin belirlenen karbon ierikleri Tablo 2de verilmitir. Karbon
katksz sinterlenmi numunelerin karbon ierii %0,025 olarak bulunmutur.
Tablo 2 : Karbon katkl numunelerin sinterleme sonras karbon ierikleri
ekil 3de farkl miktarlarda karbamit ilave edilerek retilmi ve 1200 Cde 1 saat sinterleme sonras
yaklak (a) %49,0, (b) %54,2, (c) %61,4 ve (d) %70,1 gzenek ieren karbon katksz Distaloy AE numunelerin yzeylerinden alnan SEM fotoraflar verilmitir.
ekil 3 : (a) %49,0, (b) %54,2, (c) %61,4 ve (d) %70,1 gzenek ieren numunelerin
yzeylerinin SEM grntleri
ekil 3de verilen SEM grntlerinde belirgin bir ekilde kpks yapnn olutuu grlmektedir. Balangta ilave edilen karbamit miktarna bal olarak sinterleme sonras numunelerin gzenek miktarlar
deimektedir. Gzenekler birbirlerinden hcre duvarlaryla ayrlmlardr. Yaplarda atlak oluumlarna
rastlanmam ancak mikro gzenekler tespit edilmitir. Gzenek morfolojisinin karmak olmas kullanlan karbamitin dzensiz ekilli olmasndan ileri gelmektedir. Farkl oranlarda gzenek ieren karbon
325

katksz Distaloy AE numunelerindeki gzeneklerin kresel ap ve kresellik deerleri Tablo 3de verilmitir.
Tablo 3 : Karbon katksz numunelerdeki gzeneklerin kresel ap ve kresellik deerleri
Karbon katkl Distaloy AE tozundan elde edilen yksek oranda gzenek ieren numunelerin kresel
ap ve kresellik deerleri Tablo 3de verilen deerlere ok yakn bulunmutur. Gzenek miktarnn azalmasyla; maksimum ve ortalama kresel aplar azalm, kresellik artmtr. Dk gzenek miktarlarna doru ortalama kresel aplarn giderek azalmasnn nedeni gzenek duvarlarnda sinterlenmeden
kaynaklanan ekmenin baskn olmasdr. Yksek miktarlarda gzenek ieren numunelerde ortalama
gzenek boyutundaki art ve maksimum gzenek boyutunun kullanlan karbamitin boyutundan byk
olmas gzeneklerin birbirleriyle balant kurmas sonucudur.
ekil 4-(a) karbon katksz, (b) %0,3, (c) %0,6 ve (d) %0,8 karbon katkl Distaloy AE tozundan elde
edilen farkl gzeneklilie sahip numunelerin gerilme-%ekil deiim erileri verilmitir.
ekil 4 : (a) karbon katksz, (b) %0,3, (c) %0,6 ve (d) %0,8 karbon katkl farkl gzeneklilie sahip
numunelere ait basma erileri
Bu eriler kpks metallerin tipik basma davrann yanstmaktadr. Her bir eri elastik bir blgeye,
uzun bir plato blgesine ve gerilmenin hzla artt younlama blgesine sahiptir. Gzenek miktarnn
artmasyla; plato blgesinin uzunluu ve younlamann balad ekil deiimi artmaktadr. Numunelerin maksimum basma gerilmeleri (st akma gerilmeleri) ve plato gerilmeleri artan gzenek miktar
326

ile azalmaktadr. Elastik blgeden sonra numunelerde meydana gelen youn gzenek duvar krlmas
nedeniyle gerilmede ani dler gereklemitir. Yaklak ayn gzeneklilie sahip numunelerde, maksimum basma mukavemetleri ve plato gerilmeleri artan karbon miktaryla bir miktar artmtr. Gzenek
orannn azalmasyla karbon katksnn mukavemet zerine etkisi daha da belirginlemektedir. Ancak
karbon katksnn plato blgesinin uzunluu ve younlamann balad ekil deiimi zerine belirgin
bir etkisi olmamtr. ekil 5de karbon katksz, %0,3, %0,6 ve %0,8 oranlarnda karbon katkl Distaloy
AE tozundan elde edilen farkl gzeneklilie sahip numunelerin maksimum basma mukavemetlerinin
numunelerin ierdii gzenek miktarna gre deiimi verilmektedir.
ekil 5 : Farkl gzeneklilie sahip numunelerde karbon katksnn maksimum basma

mukavemetine etkisi
Numunelerin maksimum basma mukavemetleri ve elastisite modlleri srasyla; 23-133 MPa ve 0,703,43 GPa arasnda deimitir. Tm numunelerin maksimum basma mukavemetleri artan gzenek miktaryla azalmtr. Gzenek miktarnn artmasyla; maksimum ve ortalama kresel aplar artm, kresellik deerleri azalmtr. Ayn gzenek miktarlarnda numunelerin maksimum basma mukavemetleri artan
karbon miktaryla bir miktar artmtr. Azalan gzenek miktaryla; karbon katksnn maksimum basma
mukavemeti zerine daha belirgin etkisi olmaktadr. Yaklak %48 gzeneklilie sahip numunelerde
%0,8 karbon katks maksimum basma mukavemetini %10,8 arttrmaktadr. Yaklak ayn gzeneklilie
sahip numunelerin elastisite modllerinde artan karbon ieriine bal olarak nemli bir deiim gereklememitir. Ancak artan gzenek miktarna bal olarak elastisite modlleri azalmtr.
lave edilen karbon miktarnn yksek oranda gzenek ieren numunelerin maksimum basma mukavemeti zerine etkisini aklayabilmek iin mikroyap incelemeleri yaplmtr. Mikroyaplardaki fazlar toz
metalurji yntemi ile retilmi youn Distaloy AE kompaktlar iin literatrde verilen standart mikroyap
grntleri ile karlatrlarak teyit edilmitir [4]. ekil 6da yaklak %48 gzeneklilie sahip karbon
katksz ve farkl oranlarda karbon katkl Distaloy AE tozundan elde edilen farkl gzeneklilie sahip
numunelerin mikroyap fotoraflar verilmektedir. Mikroyap grntlerinde; Ferrit F, Perlit P, Beynit B ve
mikro gzenek G ile ifade edilmitir.
327

ekil 6 : (a) karbon katksz, (b) %0,3, (c) %0,6 ve (d) %0,8 karbon katkl numunelerin mikroyap
grntleri
Literatrde yksek oranda gzenek ieren n alaml demir esasl kompaklarda karbonun etkisinin
aratrld bir alma bulunmamaktadr. Yksek oranda gzenek ieren Distaloy AE numunelerinde;
youn kompaktlarda olduu gibi [4-6], karbon miktarnn artmasyla yapy oluturan gzenek duvarlarnda ferritik yapdan perlitik ve beynitik yapya gei olduu grlmtr. Ancak bu almada sinterleme evriminin soutma aamas kontroll olarak yava yapldndan; mikroyapda beynit oluumu az
gereklemi, martensit oluumuna ise rastlanmamtr. Gzenek orannn azalmasyla karbon katksnn mukavemet zerine etkisi daha da belirginlemektedir. Sonular yksek oranda gzenek ieren Distaloy AE numunelerinde yapda beynit ve martensit oluumlarnn artmasyla daha yksek mukavemet
deerleri elde edilebileceine iaret etmektedir.
Teekkr
Bu alma T-1431 proje numarasyla stanbul niversitesi Bilimsel Aratrma Projeleri Birimi tarafndan
desteklenmitir.
KAYNAKLAR
1. HGANS HANDBOOK-2, Production of Sintered Components, Sweden, 2004.
2. HGANS HANDBOOK-4, Compacting of Metal Powders, Sweden, 2004.
3. HGANS-A.B., Hgans Iron and Steel Powders for Sintered Components, Sweden, 1996.
4. HGANS A.B, Hgans Handbook for Sintered Component- Metallography, Sweden, 2007.
5. CHAGNON, F., TRUDEL, Y., Designing Low, Alloy Steel Powders for Sinterhardening Applications,
Metallurgy and Particulate Materials, 1-10, 1999.
6. KHORSAND, H., HABIBI, S.M., YOOZBASHIZADEA, H., JANGHORBAN K., REIHANI, S.M.S., SERAJI, H.R., ASHTARI, M., The Role of Heat Treatment on Wear Behaviors of Powder Metallurgy Low
Alloy Steels, Materials and Design, 23, 667-670, 2002.
7. CHAWLA, N., DENG, X., Microstructure and Mechanical Behavior of Porous
Sintered Steels, Materials Science and Engineering A, 390, 98-112, 2005.
8. MICHAILIDIS, N., STERGIOUDI, F., TSOUKNIDAS, A., PAVLIDOU, E., Compressive Response of
Al-foam Produced via a Powder Sintering Process Based on a Leachable Space-holder Material, Materials Science and Engineering, 528, 1662-1667, 2011.
9. BAKAN, H.I., A Novel Water Leaching and Sintering Process for Manufacturing Highly Porous Stainless Steel, Scripta Materialia, 55, 203-206, 2006.
10. KOTAN, G., BOR. A.S., Production and Characterization of High Porosity Ti- 6Al-4V Foam by Space
Holder Technique in Powder Metallurgy, Turkish J. Eng. Env. Sci, 31, 149-156, 2007.
11. GULSOY, H.O., GERMAN, R.M., Sintered Foams from Precipitation Hardened Stainless Steel
Powder, Powder Metallurgy, 51(4), 350-353, 2008.
12. KREMER, K., LISZKIEWICZ, A., ADKINS, J., Development of Steel Foam Material and Structures,
Technology Roadmap Program 9913 Final Report, The United States Department of Energy and
American Iron and Steel Institute, 2004.
13. ALY, S.M., High Temperature Mechanical Properties of Cast as well as Powder Metallurgical Manufactured Metallic Foams, Doctorate Thesis, Stipendiat am Institut fr Eisenhttenkunde, Aachen,
Deutschland, 2004.
328

YAKIT HCRELERNDE KULLANILACAK GZENEKL PASLANMAZ ELK

TOZ METAL PARALARIN RETM PARAMETRELERNN ARATIRILMASI
Adem KYL* ve Yusuf USTA**
**Arazi,naat ve Kamulatrma Daire Bakanl, Boru Hatlaryla Petrol Tama A.. Bilkent Plaza BOTA
Bilkent / Ankara, adamvillager@hotmail.com
*Makina Mhendislii Blm, Mhendislik Fakltesi Gazi niversitesi 06570 Maltepe / Ankara,
uyusuf@gazi.edu.tr
ZET
Bu almada yakt hcrelerindeki s deitiricilerinde de kullanlabilmesi dncesi ile SS316L kresel paslanmaz
elik tozlarndan, bir altlk zerinde tutundurulmu gzenekli yzeye sahip paralar retilmitir. Bunun iin minimum
basn-scaklk deerleri ile tozlar ve altlk arasndaki iliki incelenmitir. Ayrca; tozlarn altla balanmas iin,
altln yzey przlln arttrlmas yntemi uygulanmtr. Bu amala yzey andrma teknikleri aratrlm,
en dk yzey przll deeri belirlenmitir. almalar yaplrken prosesin endstrideki uygulanabilirlii gzetilmitir. Bunun yannda scaklk ve basncn, ak gzeneklilik zerindeki etkisi aratrlmtr. Yaplan deney ve
testler 200 MPa presleme basnc, 500C presleme scakl, Ra=1,7 m altlk yzey przll ile gzeneklilik
yzdesinin %29,6 deerlerinin yeterli balang koullar olduunu gstermitir.
Anahtar Kelimeler: Yakt hcresi, gzenek, paslanmaz elik, sinterleme, przllk, toz metalurjisi.
INVESTIGATION OF PRODUCTION PARAMETERS OF POROUS STAINLESS

STEEL SURFACES USED ON FUEL CELLS
ABSTRACT
In this study, parts that have porous surface of SS316L spherical stainless steel powder have been produced to be
used for heat exchangers of the fuel cells by designing and producing die and special punches. Minimum pressures
and temperatures for compacting have been examined to have bonding between powders and a substrate. Moreover, surface roughness of the substrate has been increased in order to bond substrate and the powders. Surface
etching techniques have been investigated and minimum surface roughness has been defined. Besides, the effects
of temperature and pressure on open porosity have been investigated. The experiments and the tests showed that
200 MPa compacting pressure, 500C temperature and Ra=1,7 m roughness, on the substrate are enough as the
initial conditions. Under these circumstances 29,6% porosity has been obtained.
Keywords: Fuel cell, pore, stainless steel, sintering, surface roughness, powder metallurgy
1.GR
Is deitiricilerde yzey alannn artrlmas, aktarlacak s miktarn dorudan etkilediinden, dar hacimler nedeni
ile daha byk yzeyli s deitiricisi kullanm zorunluluu giderek artmaktadr. Is deitiricisinde gzenekli yzeyler kullanmak veya yzeyinde kntlar oluturmak yzey alann arttrmak iin balca yntemlerdir. Hem kntl
hem de gzenekli yzeyin ayn anda imalat ise iki baarl uygulamann birletirilmesidir. Bu yzey alann nemli
llerde artrmakla birlikte klcal etki (capillary effect) yardm ile iki fazl soutma (nucleate boiling) da mmkn
olmakta ve s deitiricisinin verimi %300 mertebelerinde artmaktadr. Bu tr bir uygulama bakr tozlar kullanlarak
yaplm, teorik snrlarn yannda bu snrlarn endstrideki uygulanabilirlii aratrlmtr. Bugn, gelien yakt
329

hcreleri ve membran teknolojileri kk hacimde daha byk s aa karmaktadrlar. Yksek scaklk ve yaktn
oluturduu korozif ortam bu alandaki nitelikli malzeme ihtiyacn aka gstermektedir.
Mhendislik uygulamalarnn en nemli ve en ok karlalan ilemlerinden birisi, farkl scaklklardaki iki veya
daha fazla akkan arasndaki s deiimidir. Is deitiricilerinin konstrksiyonunda yumuak elikler, alaml elikler, zellikle bakr gibi dier alamlar, seramikler veya zel maksatlar iin de grafit gibi malzemeler kullanlr. Bu
malzemelerin seiminde korozif, scak, basnl, asitli veya bazik ortam alma koullarna dayanakllnn yan
sra, zellikle metal malzemelerde imalat kolaylnn (bilhassa kaynak kabiliyeti), s iletim katsays, younluk, s
yaynm katsays gibi fiziksel zellikler, pratikte standart ap ve boyutlarda imal edilebilme ve fiyat gibi etkenler gz
nnde tutulmaldr [1].
Paslanmaz elik endstriyel tesislerde, korozyon dayanm gereken yerlerde ska kullanlr. Paslanmaz elikten
mamul s deitiricileri yakt hcreleri alanndaki malzeme gereksinimini, zellikle korozyona olan direnci nedeniyle
karlamaktadr. Bilindii gibi yakt hcrelerinde (yakt pillerinde); elektrokimyasal tepkime sonucu aa kan sy
uzaklatrmak, bu teknolojinin verimli olarak kullanlabilirliini etkilemektedir. Yakt hcreleri yaplar gerei kk ve
karmak geometriye sahip olduundan oluan sy atabilmek iin gerekli mekanizmann boyutlar snrlanmaktadr.
Buna karn, yakt hcresinin gc arttka aa kan s da doal olarak artacak ve daha byk kapasiteli s
deitirici kullanm zorunlu hale gelecektir. Liter ve Kaviany [2] yaptklar almalarnda, gzenekli yzeylere sahip
s deitiricileri ile klcal etkisiyle (capillary effect) ift fazl s transferi (sv ve gaz) ve ayn zamanda artrlm yzey
alan elde etmiler ve bylece dz bir plakaya gre %300 gibi bir artla s transferi kapasitesine ulalabileceini
gstermilerdir. Ulalan bu sonu, yakt hcresi ve elektronik cihazlarn soutucularnda gzenekli yzeylere sahip
s deitiricilerinin kullanlabilecei ynnde bir motivasyon oluturmutur.
Literatr incelendiinde, gzenekli yzeylerin oluturulabilmesi iin zellikle bata kimyasal olmak zere eitli
yntemler olduu grlmektedir [3-6]. Ancak, kontrol edilebilir ve ak gzeneklilie sahip paralar iin toz metalurjisi yntemi nemli bir zmdr. Bunun yan sra iki farkl sv arasnda szdrmazl salamak amacyla bir plaka
zerinde gzenekli yapy oluturmak iin de yine T/M yntemi nemli bir alternatif olacaktr. Tipik T/M paralarn
yapsal teorik younluu %85-%99,9 aralnda deiirken, gzenekli yap iin kullanlan teknik ve sinterlemeyle
%25 ile %85 aras teorik younluklu paralar retilebilmektedir. Filtreler, kendi kendini yalayabilen yataklar, bataryalarn elektrotlar, ak kontrol cihazlar, ak snrlandrclar, darbe emiciler ile kpks yaplar bu paralara
rnek olarak verilebilir [7].
Gzeneklilik basn altnda dmekte younluk st snrna yaklamaktadr. Yksek gzeneklilie sahip olabilmek
iin dk basnta presleme gerekirken, tozlarn bir altla tutunabilmesi iin sktrma basncnn artrlmas gerekmektedir. Bakr ile yaplan almalarda; minimum basn seviyesinin 15MPa civarnda olabilecei, ancak tutunma iin scaklk altnda preslemenin yaplmas gerektii ve bunun da minimum 350C olmas gerektii belirtilmektedir [8]. Bakr tozlarndan baar ile retilen gzenekli yzeylerin [8], yakt hcrelerinin s deitiricilerinde anlan
zellikleri nedeniyle paslanmaz elikten retilmesi fikri bu almann kaynan oluturmaktadr. Tozlar ve yzey
arasnda gl bir ba salamak amacyla, lk, hatta scak presleme zorunluluu vardr. Ko, M. arkadalar yaptklar almada, sinterlemenin gerekli olaca, oksidasyonu engellemek iin sktrmann ve sinterlemenin korumal
atmosferde yaplmasnn gerekecei, yksek basn ve scaklk deerleri her ne kadar gl ve kompakt bir yap
iin gerekse de gzeneklilii snrlad, tutarl gzeneklilik seviyeleri iin uygun toz boyutunun salanmas gerektii
sonucuna varmlardr [9]. Is deitiricisi olarak kullanabilmek iin, sv ile ekillendirme (hydroforming) yntemi
kullanlarak, 0,05 mm kalnlndaki SS304 levha ile 0,5x0,5 mm ok ince ak kanall bipolar levhalar retilmitir.
Bu kanallar ile s transferi svs iin ak yollar oluturulmutur [10].
Benzer bir almada, dorudan metal lazer sinterleme kullanlarak, sinterlenmi gzenekli 316L paslanmaz elik
bileenlerin ileme koullar ve mikro yapsal zellikler incelenmitir. Sinterlenmi rneklerde genellikle %2155
gzeneklilik elde edilmitir [11].
Yakt hcreleri oluan kimyasal olaylar nedeniyle korozif bir ortam oluturmaktadr. stenitik 316L malzeme ile
500C scaklkta iletilen bir hcrede deneyler yaplarak, hava oksidasyonunun yksek olduu 500C st scaklklarda paslanmaz elik kullanmann uygun olmayaca belirlemitir [12]. 300 saat sonra 800Cdeki yakt hcresinde
hava oksidasyonundan dolay paslanmaz elik balang ktlesinin %5 orannda azald grlmtr [12].
Yakt hcrelerinin; dk emisyon ve grlt seviyeleri ile H2nin temel enerji kayna olmas durumundaki yksek
verimlilikleri nedeniyle yakn gelecekte nemli rol oynayaca tahmin edilmektedir [13]. Zamanla fosil yaktlarn
azalmasndan duyulan endie sonras iten yanmal motorlara gre pahal bir yntem olan yakt hcreleriyle elektrik
retme, yksek verimlilii ve emisyonsuz olmas sayesinde tekrar aratrlmaya ve gelitirilmeye balamtr [14].
330

Bugne kadar olan yakt hcrelerinin ksaca karlatrlmas Tablo 1de verilmitir [15].
ekil 1de yaps verilen yakt pilinde katot tarafndaki ak kanalndan hava geerken, anot tarafndaki ak kanalndan hidrojen (yakt) gemektedir. Anot tarafndaki gzenekli tabakadan katalizr tabakaya geen hidrojen, platin
katalizr sayesinde elektronlarn brakr [16].
ekil 1. Yakt hcresi (PEM) ve tabannda gzenekli tabaka bulunan kanaldaki ak.
Yakt Hcresi
Tr
alma
Scakl
Proton geirgen
zarl yakt hcresi
(PEMFC)
20-100C
Tablo 1. Yakt hcrelerinin ksaca karlatrlmas.

alma
Yakt
Avantajlar
Dezavantajlar
Aral
Dk scaklk yksek
<1W enerji younluu, hafif, ok saf H2, Pahal
H2
200kW
hzl ilk alma, Kat
katalizr
Elektrolit
Uygulama
Alanlar
Portatif Sistemler,
Jeneratr, Askeri
sistemler
Kat oksit yakt

hcresi (SOFC)
5001000C
1W 250kW
H2, CO2,
CH4
Yksek verim, yakt

eitlilii, ucuz katalizr,
hzl ilk alma, Kat
Elektrolit
Yksek Scaklk,
Korozyon, Hcre
retimi zor ve
pahal
Elektrik santralleri,
Orta lekli
iletmeler iin s
ve elektrik, Portatif
Sistemler
Alkaline (bazik)
yakt hcresi
(AFC)
50-100C
200W 10kW
H2
Katottaki aktivasyon
kayb dk, sv
elektrolit, yksek temas
ok saf H2, Pahal

katalizr
Uzay aralar
Fosforik Asit yakt

hcresi (PAFC)
190220C
10kW 1MW
H2
Safl dk hidrojen
kullanlabilir, sv
elektrolit, yksek temas
Elektrik santralleri,
Orta lekli
iletmeler iin s
ve elektrik
Eriyik Karbonat
yakt hcresi
(MCFC)
600650C
200kW 10MW
Yksek verim, yakt

eitlilii, ucuz katalizr, Yksek Scaklk,
Sv Elektrolit, yksek
Korozyon
temas
Elektrik santralleri
Dorudan
Metanol (veya
Etanol) yakt
hcresi (DMFC
veya DEFC)
50-100C
<1W 200W
Dk verim,
metanoln zehirli
bir yakt olmas
Portatif Sistemler
Dorudan Bor
hidrr yakt
hcresi (DBFC)
20-100C
1W 200W
BH4-1
Alternatif yakt, yksek

ak u gerilimi
Yaktn elde
edilmesi zor
Deneme
aamasnda
Dorudan Glikoz
yakt hcresi
(Biyolojik yakt
hcreleri) (DGFC)
10-50C
1W 20W
C6H12O6
Yakt vcutta bol

miktarda bulunmakta,
Glikozdan bakterisiz
olarak akm retimi
Dk g
younluu
Kalp pili, la
pompas, sensr
H2,CO
CH3OH, Ucuz Yakt, Kolay

(C2H5OH) depolanan sv yakt
331

almada 55 mm apl metal toz sktrma kalbnn tm paralarnn imalat yaplm, imalatlar tamamlanarak
montajlar yaplan sktrma kalbnn mekanik ksmlarnn yan sra elektriksel ksmlarnn hesap ve analizleri yaplmtr. Modellemede PHONEICS yazlm kullanlm, kalbn oda scaklndan 500Clik bir scakla ulamas
iin gereken zaman 2250 saniye (~37,5 dk) olarak bulunmutur (ekil 2).
ekil 2. Toz sktrma kalbnn kat modeli ve stma sresi sonunda kalpta oluan scaklk dalm.
Temin edilen 150 m apnda kresel paslanmaz elik tozu ierisinde bulunan daha kk apta tozlar ortamdan
ak gzeneklilii etkileyeceinden, 75 m alt tozlar birbirinden ayrlmtr. Deneylerde 100 m kalnlnda SS316L
paslanmaz elik levhalar altlk olarak kullanlmtr.
2.1. Toz Presleme Deney Dzenei ve Deneyinin Yapl
Tozlarn preslenmesi iin, mekanik laboratuarnda bulunan DARTEC marka niversal ekme-basma cihaz kullanlmtr (ekil 3). Cihazn kontrol nitesi kullanlarak basma yk profili oluturulmutur.
ekil 3. Metal toz presleme deney dzenei.

ncelikle, dz yzeyli numuneler oluturulmaya allmtr. Bu maksatla 55 mm apnda kesilen altlklarn, tozlara
dorudan temas edecek yzeyleri zmparalanarak hazrlanmtr.75 m elek alt tozlar, yaklak 2 mm kalnlkta
bir katman oluturacak ekilde alt kalba koyulmutur. Bu tozlarn zerine altlklar yerletirilmitir. Daha sonra st
zmba yerletirilerek izolasyonlar sarlm ve kalp stlmtr. nceden ayarlanm basn deerine 10 saniyede
ulalacak ekilde rampa girii uygulanm ve bu basn altnda 60 s beklenmitir. Bu sre bitiminde pres st enesi
332

kalp st zmbasndan ayrlm, izolasyon ceketleri karlarak kalbn soumas beklenmitir. ekil 4te kalptan
kan numuneler grlmektedir.
ekil 4. a) Presleme, b) Numunenin karlmas, c) 450C scaklk ve 100 MPa basn altnda tozlarn altla
tutunmam ancak kendi aralarnda tutunmu hali, d) 490C presleme scakl ve 150 MPa basn altnda altla
blgesel tutunmu bir numune.
Tozlarn kendi aralarnda tutunmas ancak altla tutunmamalar, altlklara ait przllk deerlerinin yeterli olmadn ortaya koymutur. Yzey przll artrma ilemi ncelikle kaba zmparalarla gereklemi, ancak yine
sonu alnamamtr. Bu durumda daha etkin bir yntem kullanlarak daha yksek yzey przllk deerlerine
ulalmas gerekmektedir.
2.2. Kimyasal Yntemle Yzey Przllnn Artrlmas
Elektrolitik bir ortam ierisinde bekleyen metal ierisinde aktiflikleri farkl blgeler ve mikro yaplar arasnda reaksiyon balar. Bu reaksiyon neticesinde kimyasal korozyon balar. Kimyasal korozyon metalin ierisinde bulunduu
ortamdaki dier bir elementle dorudan elektron alveriinin sz konusu olduu bir reaksiyondur.
Elektrokimyasal korozyonda konum olarak ounlukla farkl yerlerde oluan iki ksmi reaksiyon vardr. Genel btn
metallerde ve zellikle paslanmaz eliklerde elektrokimyasal korozyon hasarlarna daha ok rastlanmaktadr.
almada altlk olarak kullanlan SS316L levha (100 m kalnlnda) anot olarak kullanlmtr. Katot olarak yine
ayn levhadan oluturulmu levha kullanlmtr. Elektrolitik sv ierisinde elektrot balants olmayacak ekilde
katot balant ucu karlmtr Anot levhasnn tek taraf (pitting korozyonunun istendii yzey) 80 mesh zmpara ile
przlendirilmitir. Anodun bu przlendirilmi yzeyi katot tarafna doru konumlandrlmtr. Przllk deneyleri
nce farkl zeltilerde oda scaklnda yaplm ancak belirgin bir przllk art gzlenmemitir. Gzlemlenen
NaCl ierisinde scaklk art olduunda korozyonun hzla arttdr. Bu gzlem, zelti kab ierisindeki FeCl2 floklar oluumunun hzlanmas ve belirginlemesidir (ekil 5).
333

ekil 5. Farkl scaklklardaki denemeler ve NaCl zeltisinde FeCl2 bloklar.

Bunun zerine, 70C zerinde bir scakla sahip %(w/w)20 NaCl zeltisi (ktlece %20 NaCl zeltisi: 1000g NaCl
zeltisinde 200 g kat NaCl bulunduunu ifade etmektedir), ekil 6da grld gibi akm verilip, zeltide reaksiyon balatlmtr.
ekil 6. Altlklar iin hazrlanan hzlandrlm deney dzenei.
334

Deney dzenei iin kullanlan g kayna, 32V-2A DC g kaynadr. Bekleme sresi 8 dakika olarak belirlenmitir. lk yksek przllk deerine sahip yzeyler elde edilip, olumlu sonular alnmasndan sonra artlar birbiriyle ayn sekiz adet altlk hazrlanmtr. Bu artlara uygun olarak balayan elektro-kimyasal reaksiyonda; zelti
ierisindeki klor iyonlar, anottan gelen demir katyonlar ile birleerek, belirli bir sre ierisinde oyuklanma korozyonu gereklemektedir. Deney srasnda zaman ilerledike g kaynandan okunan besleme geriliminde bir art
gzlemlenmitir (balangtaki gerilim 3,8V-4V arasndadr). Gerilimdeki artn nedeni zeltinin iletkenliindeki
azalmadr. zelti iletkenliinin azalmas, serbest Cl- iyonlarnn azalmasn gstermektedir. Bu durum, reaksiyonunun gereklemekte olduunun gstergesidir. letkenliin azalmasyla meydana gelen zelti i direncinin art
gerilimde ykselme olarak kendini gstermektedir. Bu artn 8 dakika ierisindeki deiimi ekil 7de grlmektedir.
Scakln art reaksiyon hzn artrdndan sre ksalmtr. Deneyin oda scaklna yaplmas durumunda reaksiyon hz dm, pitting korozyonu sresi artmtr.
ekil 7. Elektrolitik zelti direnci.

Elde edilen sekiz adet altln przllk deerleri Taylor Hubson SURTRONIC 3+ przllk lm cihaz ile llmtr. lmler sonucunda elde edilen ortalama yzey przllk deeri (Ra) ve profildeki tepe-ukur ykseklikleri (Rz) przllk deerleri ekil 8deki grafikte verilmitir. Ra ortalama deeri 1,7 m civarnda iken Rz deerleri
8,5818,93 m arasnda deimektedir. Ortalama Rz deeri 14,4 m civarndadr. Bu fark uniform bir yzey dalm olmadn gstermektedir. Uniform kabul edilebilir bir yzeyin Rz/Ra=4 oranna sahip olmas gerekir [19, 20].
ekil 8. Altlk numunelerine ait Ra ve Rz deerleri.

Przllk deerlerinin llmesinden sonra, saysal ortama grnt aktarabilen OLYMPUS GX71 optik mikroskopta numunelerin yzey morfolojileri incelenmitir. Elde edilen en dk ve en yksek przl yzeyler ekil 9da
grlmektedir.
335

Ra=0,77 m, Rz=8,58 m
(Dk Przllk deerine sahip altlk)
Ra=2,30 m, Rz=17,48 m
(Yksek Przllk deerine sahip altlk)
ekil 9. En dk ve en yksek przl numunelere ait yzey grntleri (50x).

Bu artlarda; przllk deerleri Ra=0,77 m, Rz=8,58 m olarak llm olan dk przlk deerine sahip
altlk kullanlarak T=500C ve P=150 MPa artlarnda preslenmi, ancak altla tutunma gereklememitir. Tozlar
geri kalan przlendirilmi altlklara T=500C ve P=200 MPa artlarnda preslenmi, hepsinde hem tozlar hem de
altlk arasnda tutunma salanmtr. Altla tutunan bu numuneler, 1150C scaklkta 30 dakika beklenmek suretiyle
korumal atmosferde sinterlenmitir. Koruyucu gaz olarak %95 Argon %5 Hidrojen karm kullanlmtr. Sinterleme ilemi PROTHERM marka PTF 12/38/250 model tp frnda gerekletirilmitir (ekil 10).
ekil 10. Sinterleme frn ve uygulanan scaklk profili.

Bu artlarda sinterlenen malzeme zerinde grnr renk deiimleri meydana gelmitir. Yani numunede sinterleme srasnda oksijenle reaksiyon gereklemitir. Buna gereke olarak koruyucu gaz atmosferinin yetersiz kald
dnlebilir. Bu durum koruyucu gaz karm oranndan veya frna giren koruyucu gaz karmnn debisinden olabilecei gibi, tp frnn giriinde ve knda dardan havann girii tamamen engellenememi de olabilir. Bunun
yannda, disk eklinde giren malzemede ekil deiiklikleri meydana gelmitir. Altln tutunduu yzeyde meydana
gelen bombenin derinlii 3mm civarndadr (ekil 11).
ekil 11.Sinterleme frnndan kan numunelerin geometrilerindeki deiim.
336

Gzeneklilik deerlerinin belirlenmesi iin numuneler incelemeye alnacak ekilde yzeyleri parlatlarak OLYMPUS
GX71 optik mikroskopta incelenmitir. Grntler dzenlendikten sonra Image-JTM grnt analiz yazlm yardmyla binary modunda (ikili renk modu) gzeneklilik lm yaplmtr (ekil 12). Her numunenin farkl blgelerinden 7
adet grnt analiz edilmi ve numunelerin gzeneklilik oran %29,6 olarak tespit edilmitir.
ekil 12. Gzeneklilik analizi iin alnan resim ve siyah-beyaza dntrlm grnts.
Gzeneklilik deerleri ierisinde en byk deer %35,6 en kk gzeneklilik deeri ise %23,3tr.
3. SONULAR VE NERLER
almada; farkl geometrilere sahip zmbalarla scaklk, basn ve toz boyutu parametrelerinin aratrlmas hedeflenmitir. Ancak; 500C scaklk ve 50 MPa basn altnda tozlar birbiri arasnda tutunurken altla yapma
salanamamtr. Basn deeri 200 MPa deerine kadar testler yaplmtr. Bu nedenle gzeneklilik testlerinden
nce altlk przllnn artrlmas konusuna younlalmtr. Bylece, farkl yzey geometrileri (farkl zmba
kullanm) yerine sadece dz yzeyli numuneler elde edilmitir (tek tip zmba kullanlmtr).
Gerek kalptaki olumsuz deformasyonu nlemek ve gerekse uygulanabilirlik bakmndan maksimum deerler olarak, 200 MPa basn ve 530C scaklk kullanlm ancak, numunelerde snrl ve blgesel olarak altla tutunma
gzlenmitir.
Altlk malzemesinin yzeyine herhangi bir ilem yaplmakszn, tozlarla altlk arasnda tutunma salanamamtr.
Bunun zerine 80, 150 ve 240 meshlik zmparalar ile altlk yzeyi przlendirilmi ancak yeterli bir tutunma yine
salanamamtr. Altln tutunmasn glendirecek kimyasal bir przllk artrma almas yaplarak, mekanik
tutunma iin minimum przllk deerleri belirlenmeye allmtr. Kullanlan kimyasal zeltilerin farkl deriimlerinde przll artracak olan korozyon gzlemlenmitir. NaCl, HCl ve Fe3Cl zeltileri kullanlarak przlendirme almalar yaplm, en byk oyuklanma (przllk) NaCl zeltisi ierisinde gereklemitir. Bu durum
literatrdeki dier almalarla [3,17] paralellik gstermektedir. Elde edilen ortalama przllk deeri Ra=1,7 m,
ortalama Rz deeri ise 14,4 m civarndadr. Rz/Ra orannn yaklak 8 belirlenmesi, przlln uniform dalmadn gstermektedir. Altlklarda meydana gelen pitting korozyonu deliklerinin akm, zaman, konsantrasyon ve
levha kalnl parametreleri ile farkllatrlabilecei grlmektedir.
Altlk numunesi zerindeki korozyon, alt ve st blgede farkllk gstermektedir. Mikroskopta anot altln, akm
giri ve k taraflar incelendiinde, anot akm k tarafnda belirgin bir korozyon olduu grlmektedir. Kimyasal
yntemle przlendirme almas yaplrken, her taraftan eit ekilde przlenmi, daha uniform przl yzeyin
artlar aratrlmaldr.
Yaplan almalarda, zellikle sinterleme ileminde, artlarnn yeterince salanamad anlalmaktadr. Gelecekte yaplacak almalardan salkl sonularn alnabilmesi iin laboratuvar artlarnn (sinterleme ilemi) iyiletirilmesi nerilmektedir.
alma srasnda dz yzeylere sahip numuneler elde edilmitir. Altla tutunmann baar ile salanmasnn ardndan, yzey alann artrmak amacyla mikro kanallarn bulunduu numuneler elde edilmeli ve bunlarn gzeneklilikleri aratrlmaldr.
Kimyasal yntemden farkl olarak elektroerezyon yntemi, daha kontrol edilebilir yzey przlendirme imkan sunabilir. Bu sebeple, yzey przlendirmede elektroerezyonla przllk artrma ynteminin kullanlmas nerilmektedir.
Analiz neticesinde, minimum artlarda, tutunmay salayacak gzeneklilik oran %29,6 olarak tespit edilmitir. Przlln artrlmas ile tutunmay salayan snr gzeneklilik deerlerinin deiebilecei grlmtr.
337

TEEKKR
Bu alma Gazi niversitesi Bilimsel Aratrma Projeleri tarafndan 06/2010-56 kodlu proje olarak desteklenmitir.
Teekkr bir bor biliriz.
KAYNAKLAR
1. nternet: Trk Toz Metalurjisi Dernei Toz Metalurjisi retim Teknikleri http://www.turktoz.gazi.edu.tr/ttmd_
tr.htm (2009).
2. Liter S.G., Kaviany M., Pool-boiling CHF enhancement by modulated porous-layer coating: theory and experiment, International Journal of Heat and Mass Transfer, 44: 42874311 (2001).
3. Qiao, Y.X., Zheng, Y.G., Okafor, P.C., Ke, W., Electrochemical behaviour of high nitrogen bearing stainless
steelin acidic cloride solution: Effect of oxygen, acid concentration and surface roughness, Electrochimica
Acta., 54: 22982304 (2009).
4. Sato, S., Enoeda, M., Kuroda, T., Oharo, Y., Mohri, K., Cardella, A., Characteristic evaluation of HIP bonded
SS/DSCu joints for surface roughness, Fusion Engineering and Design, 58-59: 749754 (2001).
5. Torikai, Y., Penzhorn, R.D., Matsuyama, M., Watanabe, K., Tritium uptake by SS316 and its decontamination,
Journal of Nuclear Materials, 329-333: 16241628 (2004).
6. Wang, Y., Northwood, D.O., An investigation into polypyrrole-coated 316L stainless steel as a bipolar plate
material for PEM fuel cells, Journal of Power Sources., 163: 500508 (2006).
7. Neikov O., Naboychenko S., Mourachova I., Gopienko V.,Frishberg I., Handbook Nonferrous Metal Powders:
Technologies and Applications, Elsevier, Amsterdam, 212-213 (2009).
8. Cora . N., Usta Y., Ko Y., Micro-manufacturing of micro-scale porous surface structures for enhanced heat
transfer applications: an experimental process optimization study Journal Of Micromechanics And Microengineering, 1-19 (2009) .
9. Ko, M, Usta, Y., Karako, A., Investigations on thermo-mechanical fabrication of micro-scale porous surface
features, Journal of Power Sources., 179: 592602 (2008).
10. Mahabunphachai, S., Ko, M., Ni, J., Development of a novel process for manufacturing of fuel cell bipolar
plates: internal pressure assisted embossing of microchannels with in-die mechanical joining, 2006 ASME
International Conference on Manufacturing Science and Engineering, MSEC2006-21034, Ypsilanti, 1-5
(2006).
11. Gu, D., Shen, Y., Processing conditions and microstructural features of porous 316L stainless steel components by DMLS-mechanical fabrication of micro-scale porous surface features, Applied Surface Science,
255: 18801887 (2008).
12. Molin, S., Gazda, M., Kusz, B., Jasinski, P., Evaluation of 316 L porous stainless steel for SOFC support,
Journal of the European Ceramic Society, 29: 757762 (2009).
13. nternet: Hacettepe niversitesi Yakt Hcrelerinin Tarihesi http://yunus.hacettepe.edu.tr/~yilser/yakitpili.
htm (2010).
14. nternet: University of Denver The Telegraph Line: Batteries http://mysite.du.edu/~jcalvert/ (2010).
15. nternet: The Hebrew University of Jerusalem The Institute of Chemistry Origin of the Electric Current: Galvanic Batteries http://chem.ch.huji.ac.il/history/ grove.htm (2010).
16. F. Barbir, PEM Fuel Cells : Theory and Practice, Elsevier, (2005).
17. Dndar F. , PEM tipi yakt hcrelerinde kullanlan katalizrlerde farkl karbon destei kullanlarak yzey alannn arttrlmas ve kinetik zelliklerinin gelitirilmesi, Yksek Lisans Tezi, Gebze Yksek Teknoloji Enstits
Mhendislik ve Fen Bilimleri Enstits, Gebze, 4-10 (2006).
18. Berning, T., Djilali, N., Transport Phenomena in a PEM Fuel Cell: A Parametric Study Using a Three-Dimensional Computational Model Transport phenomena in a PEM fuel cell, 11th Canadian Hydrogen Conference,
Victoria, 699-707 (2001).
19. nternet: TMMOB naat Mhendisleri Odas imento Tipinin Donat Korozyonuna Etkisi http://www.e-kutuphane.imo.org.tr/pdf/3157.pdf (2010).
20. nternet: TMMOB Metalurji Mhendisleri Odas AISI 316L Tipi stenitik Paslanmaz eliklerin Taneler Aras Korozyona Duyarllnn Elektrokimyasal Polarizasyon Yntemiyle Belirlenmesi http://www.metalurji.org.tr/dergi/
dergi140/ d140_5061.pdf, (2010).
21. EN ISO 1302:2002, Geometrical Product Specifications (GPS) - Indication of surface texture in technical product documentation, International Standard ISO, 90-93 (2002).
22. TS 2040 EN ISO 1302, Geometrik mamul zellikleri (GM) Teknik mamul dokmantasyonunda yzey durumlarnn gsterilii, Trk Standard, (2005).
338

TOZ METAL Al MALZEMELERDE GZENEKLLK ORANININ ELEKTRK

LETKENLNE ETKS
Adem Kurt, Ahmet Ayata ve Fatih Iss
Gazi niversitesi, Teknik Eitim Fakltesi,06500 Ankara-Trkiye
ademkurt@gazi.edu.tr, ahmetayata42@gmail.com
ZET
Toz metal alminyum malzemelerin kullanm alan gn getike artmaktadr. Kullanm alanlarnn genilemesinde
toz metal malzemelerin zelliklerinin belirlenmesi byk neme sahiptir. Her belirlenen zellik yeni kullanm alanlar
oluturmaktadr. Bu amala bu almada toz metal Al malzemelerin gzeneklilik oranna bal elektrik iletkenlikleri
aratrlmtr. Bu amala 200, 250 ve 300 MPa sktrma basnlarnda toz metal numuneler preslenerek, ham
ve sinterlenmi younluklar belirlenmi, gzenek dalmlar ve gzenek ekilleri mikro yap incelemesi ile tespit
edilmitir. Sonrada bu numunelerin elektrik iletkenlikleri llerek gzeneklilik oranna gre iletkenlik deiimleri
belirlenmitir. alma sonunda artan gzeneklilik oranna bal olarak elektrik iletkenliinde azalma olduu grlmtr.
Anahtar kelimeler: Toz metal Al malzemeler, gzeneklilik, elektrik iletkenlii
THE EFFECT OF POROSITY RATE ON ELECTRICAL CONDUCTUVITY OF Al

POWDER MATERIALS
ABSTRACT
Use of Al powder materials increases recently. Defining of a property of the Al powder has an important role to
implement of the powder in another area. Every new property of a material defines a new application area. As the
purpose of this study, electrical conductivity of Al powder materials, were investigated in term of porosity. For this
purpose, 200, 250 and 300 MPa compression pressures were used and the green and sintered densities were determined, the pore distribution and pore shapes have been detected by micro-structural analysis. Then the electrical
conductivity of the samples were determined by measuring changes in conductivity according to the amount of the
porosity. Decrease in electrical conductivity was observed with the increasing porosity
1.GR
Toz metalurjisi; elementel veya alam tozlarn birbirleriyle kartrlarak retimi yaplacak para kalbnn ierisinde
sktrlp sonra da atmosfer kontroll bir frn ierisinde sinterlenerek partikller arasnda metalurjik bir ba oluuncaya kadar tutulmas sreleri ieren bir imalat yntemidir. Toz metalurjisi karmak ekilli paralarn son boyutta
retilmesinde ok ekonomik bir yntemdir. Bunun dnda u avantajlar da iermektedir [1] .
Karmak ekilli ve basit paralarn retiminde son derece uygun maliyetli bir yntemdir, hurda kayb yoktur ve daha
az ikincil ilemler gerektirir, bileenlerin fiziksel ve mekanik zelliklerine yakn paralar retilir, retilecek paralarn
younluk kontrol mmkndr, ikincil ilemler uygulayarak deiik zellikleri iyiletirilebilir.
Alminyum toz metalurjisi sreci drt temel admdan oluur bunlar;
Kontroll saflk ve boyuttaki Al tozlar alamlanacak metal tozlar ile kartrlrlar. Genellikle partikllerin birbirleriyle
ve kalp duvar ile souk kaynak yapmamalar iin toz yalayclar ilave edilir.
339

n kartrma yaplm tozlar zel yaplm metal kalp ierisinde ham mukavemet kazandrmak iin preslenirler.
n kartrlm Al tozlar dk basnlarda veya enjeksiyonla yksek younluklara karlrlar. 180 MPada %
90 ve 375 MPada % 95 younlua ulaabilirler. Ham younlukla, ham mukavemet 22 MPa ile 150 MPa arasna
kabilmektedir.
Ham mukavemet kazanm paralar atmosfer kontroll bir frnda ergime scaklnn altnda bir scaklkta sinterlenirler. Bu srete paracklar arasnda metalurjik ba geliir ve istenilen fiziksel ve mekanik zellikler bir araya
getirilmi olur. Alminyumda oksit olumas sinterlemeyi zorlatrr. Bunun iin sinterleme hidrojen, azot ieren ortamlarda yaplmaldr.
Birok Al alamlar 535585 oC scaklklarda 720 dakika srelerde sinterlenirler [2]. Azot atmosferi tavsiye edilir.
Al T/M malzemelerin zellikleri retim ekline gre deiebilmektedir. Mekanik zellikler younlua bal olarak 110
MPa ile 345 MPa arasnda deiebilmektedir. Sinterleme scakl, sresi ve atmosferi bunlar etkileyebilmektedir.
Toz metal Al malzemeler bu zelliklerinin dnda elektrik ve termal iletkenliin ve korozyon direncinin yksek olmas
gibi zellikleri nedeniyle bu alanlarda da kullanlmaktadr. Bu sebeple bu almada farkl gzeneklilie sahip Al toz
metal paralarn elektrik iletkenlikleri llerek gzenekliliin elektrik iletkenliine etkisi aratrlmtr.
Bu almada ortalama 51 m boyutunda elementsel Al tozlar kullanlmtr. Al tozlar 200, 250 ve 300 MPa sktrma basnlarnda preslenerek, 6,35 x 12,7 x 31,7 mm boyutlarnda toz metal Al numuneler retilmi, bu numunelerin ham ve sinterlenmi younluklar belirlenmitir. Ayrca younlua bal gzenek dalmlar ve gzenek ekilleri
mikro yap incelemesi ile tespit edilmitir. Sonrada bu numunelerin elektrik iletkenlikleri llerek gzeneklilik oranna gre iletkenlik deiimleri belirlenmitir.
Bu almada kullanlan Al tozlarn boyut analiz sonular aada ekil 1de verilmitir.
ekil1. Deneylerde kullanlan Al tozlarn boyut dalm
340

Farkl basnlarda preslenen numunelerin ham younluklar belirlenerek daha sonra 500, 540 ve 580oCde 45
dakika sreyle argon atmosferinde sinterlenmilerdir. Tablo 1de numunelere ait ham ve sinterlenmi younluklar
verilmitir.
Tablo 1. Toz metal Al numunelerin ham ve sinterlenmi younluklar
Sinterlenmi Younluk (%)
Basn
Ham Younluk (%)
500 C
540C
580 C
200 MPa
89
91
91,5
91,7
250 MPa
91,5
92,6
93
93,3
300 MPa
94
94,4
95,2
95,5
ekil 2. T/M Al numunelerin sinterleme scaklna bal younluk deiimleri

Sinterlenmi numunelere daha sonra elektrik iletkenlik testleri uygulanmtr.
3.SONULAR VE TARTIMA
3.1 Younlama
Bu almada farkl basnlarda preslenen ve farkl scaklkta sinterlenmi numunelerin basnca ve scakla
bal younluk deiimleri Tablo 1de verilmitir. Tablodan grlecei gibi 200, 250 ve 300 MPa presleme basnlarnda younluk deiimi % 89, % 91.5 ve % 94 olarak elde edilmitir. Artan presleme basncyla kalp iindeki tozlar
birbirleri zerinden kayarak younlama davran gstermilerdir. Artan presleme basncyla toz partikllerin bir
araya gelme oran artm bunun sonucu olarak younluk art elde edilmitir.
Presleme ile ham mukavemet kazandrlan numuneler sinterleme ilemi ile partikller ve toz taneleri arasnda
metalurjik bir ba oluturularak mukavemetlerinin art salanmtr. ekil 2 de verildii gibi sinterleme scakl
500oCde en dk presleme basnc olan 200 MPada younluk %89dan %91e, 540oCde %91.5 ve 580oCde
%91.7 younluklara ulalmtr. Artan sinterleme scakl ham younlua gre bir younluk artna sebep olmakla
birlikte sinterleme scaklnn sinterlenmi younluk artna etkisi artan presleme basncyla dt grlmektedir. rnein 200 MPa presleme basncnda %89 ham younluktan 580oC sinterleme scaklnda younluk %91.7
ye karak %2.7lik bir at gsterirken 250 MPada %1.8, 300 MPa da %1.5lik bir art gstermektedir. Ham younluk arttka partikller aras temasn artmas, bzlme orann drerek younlama orannn da azalmasna
sebep olduu dnlmektedir.
341

3.2 Elektriksel zellikler

Toz metal Al malzemelerin gzeneklilie bal olarak elektrik iletkenliklerinin belirlenmesi amacyla yaplan bu almada %8.3, %6.7 ve %4.5 orannda gzeneklilie sahip numuneler kullanlarak ve bunlara 10 Ae kadar akm
verilerek gzeneklilie bal gerilimleri llm ve gzenek miktarnn elektrik iletkenliine etkisi belirlenmitir.
ekil 3de presleme basncna bal oluan gzenek durumuna gre toz metal numunenin akm-gerilim ilikisi
verilmitir.
ekil 3. Presleme basncnn elektrik iletkenliine etkisi

ekil 3 de grld gibi 200 MPa dk presleme basncnda % 8.3 gzeneklilikte 1 volt gerilimde 8 A akm geerken %6.5 ve %4.5 gzenekli numunelerde 1 volt gerilimde 9.5 A akm gemektedir. Bilindii gibi tam youn bir
katya bir elektriksel alan uygulanrsa, serbest elektronlar hzlanrlar ve kafes atomlaryla arparak kinetik enerjilerini azaltr veya kaybederler. Meydana gelen akm, uygulanan elektriksel alann iddeti ve arpma frekans ile
belirlenen ortalama elektron hz ile orantldr. deal bir kristalde elektronlar direnle karlamadan hareket ederler.
Fakat gerek kristallerde elektronlar fononlar, dislokasyonlar, boluklar yabanc katk atomlar ve herhangi kafes
kusurlaryla arprlar [3]. Bunlarda elektronlarn hareketini snrlandrrlar. Toz metal malzemelerde gzenekler
boluklar oluturduundan elektronlar bu boluklara arparak kinetik enerjilerini azaltmaktalar ve dolaysyla boluklar elektronlarn hareketini snrlandrdndan iletkenlik deerlerinin dmesine neden olmaktadrlar. Ayrca toz
metal malzemelerde gerek sinterleme ncesi toz partikl yzeylerinde oluan oksitler, gerekse sinterleme srasnda
sinter atmosferine bal oluabilecek oksitlerin toz metal numunelerde elektrik iletkenliini drd yaplan almalarda belirtilmitir [4].
ekil 4. Sinterleme scaklnn elektrik iletkenliine etkisi
342

ekil 4de sinterleme scaklnn toz metal Al numunelerde elektrik iletkenliine etkisi grlmektedir.Burada da
gzeneklilie benzer bir iletkenlik davran grlmektedir. Dk sinterleme scaklnda gzenek kapanma oran
azaldndan baka bir ifadeyle daha fazla gzeneklili yap elde edildiinden dk basnlarda preslenmi numunenin elektrik iletkenliine benzer bir iletkenlik erisi elde edilmitir. 540 ve 580Clerde sinterlenmi numunelerde
gzenek oran azaldndan elektrik iletkenliinin artt grlmtr.
3.3 Mikroyaplar
ekil 5. Preslenme basncnn gzeneklilie etkisi, a) 200 MPa, b) 250 MPa, c) 300 MPa
Toz metal malzemelerde gzeneklilik oran presleme basncyla deimektedir. ekil 5te grlecei gibi presleme
basnc 200 MPa da %11 gzenekli bir yap olumutur. Gzenekler toz metal partikllerin presleme ile bir araya gelip oluturduklar tanelerin kelerinde boluklar halinde siyah noktalar olarak grlmektedir. Presleme basnc 250
MPaa karldnda gzenek miktarnn azald ekil 5bde grlmektedir ekil 5cde ise 300 MPada preslenmi
numunenin mikroyaps grlmektedir. 300 MPada gzenek miktar ve boyutunun iyice azald bariz bir ekilde
grlmektedir. Gzenek miktarnn ve boyutunun deimesinde ve azalmasnda presleme basnc etkili olduu gibi
sinterleme scakl da etkili olmaktadr.
ekil 5de mikroyaps verilen numuneler 500Cde sinterlenmilerdir. Sinterleme scaklnn gzenek deiimine
etkisi ekil 6da verilmitir.
ekil 6. Sinterleme scaklnn gzeneklilie etkisi a) 500 C, b) 540 C c) 580 C

ekil 6da 250 MPa presleme basncnda 500, 540 ve 580Cde sinterlenmi numunelerin mikro yap fotoraflar verilmitir. 500 ve 540Clerde sinterlenmi numunelerde gzenek miktar birbirine yakn gzkmekle birlikte 580Cde
gzenek miktarnn yok denecek kadar azald kalan gzeneklerin boyutlarnn kld grlmektedir. Sinterleme srasnda gzenek klmesinin nedeni partikller aras boyun blgesinin olumas, oluan boyun blgesinin
byyerek partikllerin eksenleri arasndaki mesafeyi azaltarak partikllerin bir btn tane ekline dnmeleridir.
Partikller taneye dnrken gzenekler yok olmakta, boyu byk olup da yok olamayan gzenekler de boyutlar
klerek tane kelerinde bulunmaktadrlar.
4.SONULAR
Toz metal Al malzemelerde gzenek miktarnn elektrik iletkenliine etkisinin belirlenmesi amacyla yaplan bu almada aadaki sonular elde edilmitir.
1. Toz metal malzemelerde younluk artnda presleme basnc nemli bir etken olup, presleme basncn artmas
ile ham numunelerin gzenek miktar da azalmaktadr.
2. Gzenek miktarnn azalmasn etkileyen bir dier faktr sinterleme scakldr. Bu almada kullanlan Al
malzeme iin 500, 540 ve 580C sinterleme scaklklar kullanlmtr. Artan sinterleme scakl younluu
artrrken gzenek miktarn azaltmaktadr.
3. Presleme basncyla artan younluk art toz metal numunelerin elektrik iletkenliinde de arta sebep olmaktadr. 1 volt gerilimde 200 MPa da preslenmi numunede 8 Amper akm geerken, 250 MPa da preslenmi
numune de 9.4, 300 MPada preslenmi numunede 9.6 Amper akm iletilmektedir.
343

4. Sinterleme scakl younluu artrdndan elektrik iletkenliinde de arta neden olmaktadr. 500Cde sinterlenmi numune yaklak 8 A akm iletirken, 540 ve 580Cde sinterlenmi numuneler 9.8 A akm iletmektedir.
KAYNAKLAR
1. Randall M.German Powder Metallurgy and Particulate Materials Processing Editrler. S.Sarta,M.Trker,N.
Durlu 2007 Ankara
2. http://www.aluminum.org/Content/NavigationMenu/TheIndustry/PowderandPaste/PowderMetallurgy.PDF
3. R.M.Rose, L.A.Shepard,J.Wulff, evirenler Kaif Onaran, Sabri Altnta, Malzemelerin Yap ve zellikleri Elekronik zellikler,1986
4. Ye.P. Mamunya, H. Zois, L. Apekis,, E.V. Lebedev, Influence of pressure on the electrical conductivity of metal
powders used as fillers in polymer composites, Powder Technology 140 (2004) 49 55
344

POWDER
COMPACTION AND
APPLICATIONS
www.turkishpm.org
345

New Press Type EP with Electrical servo drive system

Christian Mller,
DORST Technologies GmbH & Co. KG, Mittenwalder Str. 61,
82431 Kochel am See/Germany
Abstract
In this new press type the rigidness of a mechanical press meets the high precision and convenience of a closed
loop controlled hydraulic press. The flexibility is assured by easy programming, due to the powerful electronic
control system, proven with hydraulic presses since years. The well known IPG has been adapted to the new task
and guarantees quick setting of tools. The machine is designed to accept existing TPA die-sets, or optional quick
clamping system for new tool concepts. The positioning accuracy of the punches is within 0,001 mm, thus fulfilling
demand for minimized tolerances.
Also future environmental requirements, such as minimum energy consumption, low noise emission or absence
of hydraulic oil and lubricants are implemented in the new design. The paper presents the new type in detail and
compares the performance to existing press systems.
Keyworks: Powder Metallurgy, Compacting Press, Servo electrical press
1. Introduction
The standard drives for powder presses are nowadays mechanical drives, hydraulic drives or the so-called hybrid
drives. All these technologies have proven to be successful during many years of extensive use in the production
process and under various conditions.
The range of application of the different press types varies:
Mechanical presses are mainly used as standard machines with pressing forces of up to about 4500 kN for the production of simple parts in long production runs. These machines have a fixed sequence of operations, all individual
movements are interdependent of each other and the upper punch determines the pressing cycle.
This press type is especially characterized by reliability and low energy demand and combines a high production
rate with consistent part quality. Operation of the press requires well-trained and highly qualified technicians with
extensive knowledge of the functions and operational steps of the machines. The actual setting process and the
adjustment of the cycle are complex and time-consuming.
The application of hydraulic presses ranges from small pressing forces up to maximum pressing forces. All movements can be carried out independently of each other and that is the reason why this technology is predestinated
for multi- platen systems.
The machines are usually equipped with programmable control systems, which are complemented by measuring
systems on the machine axes. Thanks to this, it is possible to record and compensate deviations, which occur during the pressing process.
Hydraulic presses are used for the production of complex and multi-level parts with close tolerances. The closedloop control ensures stabilized results, even under varying external conditions. The setting process is reduced to a
minimum thanks to advanced electronic control systems, supporting software and technical experts. The hydraulic
drive requires high energy input and thorough maintenance to ensure reliability during continuous operation.
346

As a leading manufacturer of axial powder pressing technology, DORST Technologies is always striving for new
approaches and solutions to optimize the production step of shaping. The mentioned drive technologies are fully
developed nowadays.
For pressing forces of up to 1600kN there is now an alternative drive technology, which incorporates the various
advantages of both existing systems:
2. The Electrical Servo Drive System
2.1. Fundamental Principles Of The Electrical Servo Drive
With the new EP press series the movements of the punches are generated by means of servo-motors and a
backlash-free spindle drive. They provide for dynamic movements with accurate positioning and, as a result, for
high stroke rates and precise compacts.
In order to use all the positive characteristics of servo-motors to their full extent for the powder pressing technology,
DORST Technologies did not integrate the new drive type into an existing press type but has developed a new press
series for this purpose.
The motors are of compact design and do not require any intermediate elements such as a transmission or coupling, but activate the spindles directly. That is why this drive technology has an extremely high rigidity.
Each drive motor is equipped with its own measuring system the closed-loop control is carried out individually
and directly on the active axis. Thus, inaccuracies resulting from indirect measuring are eliminated. In addition, the
press is equipped with length measuring systems. Joint processing of both signals leads to a very high positioning
and repeat accuracy of the axes.
As a result there is a significant increase of speed, since the normal time-consuming adjustments, e.g. through
hydraulic lines and hydraulic valves, are eliminated and the correction is carried out directly on the axis!
All axes for compaction on a standard press, which are the upper punch, the die and the core rod, are driven by their
own servo-motor. All movements can be carried out independently of each other.
The maximum torque and thus the force are at disposal at any rotational speed and in any position. Thanks to this,
movements can be carried out at the highest speeds up to the pressing position.
2.2. Implementation Of The Technology In The Machine
The EP press type is equipped with a pre-stressed frame with four columns. The frame is of high rigidity and at the
same time ensures easy access to the press area, respectively the tool, from all sides.
The new press series comprises pressing forces from 150kN up to 1600kN and operates according to the die
withdrawal process. It is designed for the application of quick-action clamping systems as well as for the installation of die sets. Thanks to the resulting flexibility, tools from existing presses can easily be integrated into the new
machines.
The new development is based on the modular design of DORST Technologies: Besides the new frame, DORST
Technologies uses parts and complete subassemblies, which have been successfully used in production on other
press types for years and have proven their reliability.
For instance: Guidance of the axes is carried out in backlash-free linear guides, which provide a favorable length
to supporting difference ratio within the frame. These guides have been successfully used in powder presses of the
type TPA-HS for more than 10 years.
The EP press series is designed in compliance with well-proven and reliable technology, which fulfills all requirements for the operation in daily production.
The compact design of the drive motors allows for space-saving installation compared to conventional plants. The
floor space of an EP50 press requires for instance only about 70% of the floor space of a comparable mechanical
347

press for 500kN. Furthermore, there is the electrical installation, which requires a separate switch cabinet for the
drive motors. However, the switch cabinet can be installed independently of the press and thus further away and in
a space-saving manner, e.g. on a powder platform.
The operating level is not very high for the most types of the EP press series, so that a pit is usually not required.
The positioning and repeating accuracy of the press axes amount to 0,001 mm and therefore easily meet todays
requirements for tolerances of compacts.
These accuracies are achieved during each stroke by the extremely high consistency of the rotational speed, which
is higher by a factor of 10 compared to conventional plants as well as by the measuring systems installed in each
servo motor.
Closed-loop control is carried out by means of the sophisticated control system DVS/DCS, which has been used
worldwide in hydraulic presses for years and has been adapted to the specific requirements of the electrical drive.
Thanks to the quick reaction of the purely electrical closed-loop control system and the dynamics of the servomotors, all movements with consistently high precision can be carried out with maximum speed and thus be
used to increase the number of strokes. The time required by a motor to run up from standstill to the maximum
speed is approximately 100 ms.
Thus, the electrically driven EP presses achieve speeds of mechanical high speed presses. However, for the new
press type there is no need of taking early decisions during the investment regarding the press design. The flexibility of electrical presses allows for production optimization to be carried out only as a function of part geometry
and powder flow behavior. This means that when high parts or complex geometries are to be pressed, the press is
being operated with a lower number of strokes and auxiliary movements of the filler to ensure adequate filling, but
with pressing of flat parts the same press may be operated at a significantly higher speed optimized number of
strokes and thus maximum productivity in accordance with the pressing requirements are the result.
The maximum torque and thus the force are at disposal at any rotational speed and in any position. As a result, the
high efficiency factor of the servo motors is being transmitted to the machine as a whole. The energy required for
the operation of a powder press with a nominal pressing force of 500 kN amounts to an average amount of about 4
kW (operated at a pressing force of approx. 400 kN and 50 strokes/min). Even a mechanical press requires under
the same conditions approx. 6,5 kW and the energy demand of a hydraulic press is about three times as much.
For the purpose of meeting different requirements regarding press technology, all axes can be controlled according to position. The upper punch can alternatively be controlled according to the pressing force and can therefore
produce precise compacts with constant height or density.
2.3. Control System DVS/DCS and IPG
Complete monitoring and programming are carried out by means of the control system DVS/DCS, which has
proven to be successful for many years on hydraulic presses. With this control system all hardware-related and
software-related possibilities required for the control of the electrically driven EP press are available.
The control system DVS/DCS (Dorst Visualisation System/Dorst Control System) ensures completely free programming in due consideration of the technological requirements of the press. Depending on the individual part
to be pressed, its geometry and the desired tolerances, the technological optimum flow chart for the press will be
programmed. It is not a requirement to take into consideration any fixed operational sequences of the machine
(mechanical upper punch and/or die) nor it is necessary to adjust the speeds accordingly.
The software tool Intelligent Program Generator IPG is an integral part of the control system. On the basis of
some input data on geometry of the part to be pressed, the IPG calculates the complete pressing process and
generates the appropriate machine program. The machine program is exactly adapted to the respective press type
and, therefore, represents the perfect cycle. The required adaptations for the optimization of density, height and
weight can quickly and easily be carried out by means of the screen masks which were especially designed for this
purpose.
Due to the simple design and clear structure of the windows for programming, manual entries regarding operational
machine sequences can easily be carried out.
348

Access to all functions is as usually provided by the well-known user interface and each operator, who has already
experience with the control system of e.g. a hydraulic press, will be able to cope with it without any difficulties.
2.4. Advantages Compared To Previous Press Types
Due to the design and behavior of the servo motors, there are a number of advantages, which prove to be beneficial
for the press technology:
The compact design allows for little floor space of the press. This is a significant advantage of the EP press
series taking into account that it is not easy to enlarge the space in existing buildings.
The direct drive without intermediate components leads to a significant decrease of effort regarding maintenance and servicing, due to the fewer number of subassemblies. The provision of spare parts can be limited
to a minimum.
The machines of the EP press series do not require any auxiliary fluids and lubricants. Hydraulic oil is not required and therefore there is no need of oil change. In addition to resulting cost savings, this also means that
there are no environmental hazards due to leakage of such fluids. The installation place of the machine does
not have to be equipped with an oil pan or a leak proof pit.
The motors have a very low noise emission: Typically these emissions amount to less than 65 dB(A). This
means that, without taking any noise-absorbing measures, the noise level in the pressing plant falls significantly
below todays admissible values.
The low energy demand decreases the operating costs for a long term and for the entire lifetime of the machine.
Furthermore, there is the possibility of using the energy supply cabinet of the first electrically driven press for
further machines: Up to four powder presses can be operated simultaneously with only one supply cabinet. This
ensures a reduction in costs for the second and further machine investment!
3. Upshot
The introduction of the Servo Motor Drive Press EP represents a milestone in the development of compacting
presses for the PM industry. Environmental friendliness, low energy consumption and logistic advantages are combined with yet unknown opportunities for press movements and directly controlled adjustments.
349

MAGNESIUM BASED GRANULES AND POWDERS A TOOL FOR

SOLVING THE CHALLENGES OF OUR MODERN WORLD
Wolfgang GITTERLE
ALMAMET GmbH
ABSTRACT
Beside the typical use of magnesium in die casting there are manifold uses of magnesium in our modern world. To reach the requirements magnesium ingots are processed into granules, powders and
raspings. These products are then used for the production of chemical substances and metals, for
pyrotechnic applications and also for the refining of high quality steels. Other applications are the use
for increasing the performance of refractory materials in high temperature areas and for the production
of computer casings. Without magnesium based products some of our technical improvements would
not have been possible.
The presentation will show the chemical properties of the used magnesium, the mechanism of production and the chemical and metallurgical explications for the use of magnesium in these special application fields.
Keywords: Magnesium, raspings, granules, powders, chemicals, desulfurization
1. INTRODUCTION
Magnesium is a light metal with manifold applications. Beside the use for automotive parts,- one of the most famous
application was the use in engine parts of the Volkswagen Beetle-, magnesium is also a very important alloying
metal for aluminium alloys. According to figure 1 the world wide consumption of magnesium has become almost
800.000 tons per year [1]. The most important producer of magnesium is by far China with an yearly production of
more than 650.000 tons. The sales of magnesium raspings, granules and powders with chinese origin has reached
85.000 tons in 2010, which is a bit more than 10% of the world wide use of magnesium; this shows that the use of
magnesium for applications beside alloying and diecasting is still a niche market.
Figure 1. Worldwide use of magnesium [1].
350

Almamet as a producer of magnesium based raspings, granules and powders, is one of the most important players
in this market; although the quantities of material are not that high compared to the quantities in the steel industry,
nevertheless this is a field with a wide range of challenges and opportunities.
2. PROPERTIES OF MAGNESIUM
The atomic number of magnesium is 12, the atomic weight is 24,3050 g/mole. Magnesium has a density of 1,738
g/cm, a characteristic light metal with excellent properties for the use in automotive parts. The crystal lattice is
hexagonal which brings some difficulties in forging of magnesium parts. Aluminium- magnesium alloys with 50%
Mg and 50% Al are brittle and cannot be sawed with cutting machines.
Magnesium has a low melting point, it melts at 650C and has a vapour point of 1090C; the low melting point limits
the use of this light metal in some technical applications.
The normal potential of magnesium is -2,372 V, which indicates that magnesium has a high affinity to react with
oxygen. Especially for the use of magnesium based parts at higher temperature it is necessary to protect them
against oxidation. Therefore the use of coatings is a convenient way of protection.
3. PRODUCTION OF MAGNESIUM FINES
Magnesium is a very reactive material and a lot of safety issues have to be considered. Magnesium fines are
dangerous products which need to be transported and stored under consideration of strong safety regulations. The
problem of oxidation is always present during the production process of magnesium parts. Drilling can only be done
with special emulsions, based on oils or any other non- flammable liquids, which are able to reduce the process
temperature and avoid the oxidation and burning of magnesium.
The production of fine magnesium products can be done in two different ways. The conventional production route is
the sawing of ingots (figure 2), followed by the grinding of the produced rasping and, as last step, the classification
of the produced fines. According to the size of the products the materials are classified in raspings, granules and
powders. Typical granules of this production route are shown in figure 3.
Figure 2. Raw material for the production of magnesium fines
Figure 3. Magnesium granules Mg99,95, produced from ingots
351

Another possibility to produce magnesium fines is the spraying of liquid magnesium metal through a nozzle under
an inert atmosphere. This production route is cost intense and mainly preserved for the production of magnesium
powders for military applications.
While the output of the conventional route is approximately 50.000 tons per year, the production of atomized powders by spraying of magnesium metal is only a small part of this amount.
Especially for the use in hot metal desulfurization the use of magnesium granules made from secondary magnesium alloys has become an important production route. For this use the requirements are not so strong as for other
applications, this is why a significant amount of magnesium scrap is used for the production of desulfurizing reagent
[2].
4. APPLICATION OF MAGNESIUM FINES
The main application of ground magnesium is the use as desulfurizing agent for the production of steel. Magnesium
granules in a size of 0,2- 1,0 mm are injected into molten iron, react there with sulphur and form a slag which can
be rather easily removed. This is by far the most important application of magnesium fines. The raw material for
magnesium granules is mainly pure magnesium with 99,95% Mg content. Another source for magnesium granules
is secondary magnesium, consisting mainly of magnesium alloys AZ91 and AM50 and AM 60. These materials have
brought very good results when desulfurizing at temperatures above 1500C. The strength of these raw materials
limits the shape of the granules; it is much more difficult to get globular products compared to the results when
processing pure magnesium.
Magnesium granules are a very efficient reagent for removing the sulfur from hot metal. The efficiency is about
seven times higher than that of calcium carbide; a typical steelplant with initial sulfur contents of approx. 800ppm
in the hot metal before desulfurization and final sulfur contents of about 50ppm is using approximately 0,6-0,7 kg
magnesium granules per ton of hot metal [3]. Conventional steelplants using the typical route with blast furnace
and BOF converters are producing about 5 million tons of hot metal. This means that a mid sized steelplant has a
consumption of almost 3.500 tons of magnesium granules per year.
Another important application of magnesium granules is the use in semi- solid casting processes. Magnesium
granules are transported with a screw conveyor; friction leads to an increase of temperature and the granules start
to melt at the surface. This pulp of partly molten magnesium flows into the mould and fills it. With this process it is
possible to produce high quality computer casing boxes and automotive parts. Due to the high production costs of
the rasping this process is reserved only for high- end products. The advantages of this production route are low
thermal shrinkages and high quality surfaces of the products. With this production route it is possible to produce
thin- wall parts like notebook housings. The raw materials for this application are mainly magnesium alloys, based
on AZ91 or AM60 since it is necessary to reach high standards regarding the strength of the produced parts. Another advantage of this process is the short production schedule; the period from designing to mass production of
the consumer part is very short, compared to other production processes [4].
The production of cored wires filled with magnesium granules and ferroalloys is another special application in the
steel production. In this case magnesium helps to provide good conditions for alloying and helps to reach special
structures of inclusions in the casted steel, which is important to reach the high demands on modern steels.
A big quantity of magnesium raspings is used in chemical processes. Magnesium is filled into catalytic reactors;
together with organic substances chemical reactions will start and organometallic compounds are generated. These
so called Grignard- reactions, running at different temperature levels and with different organic reagents, are used
for the production of different intermediates for the production of plastics or vitamins. The magnesium raspings are
in a size of 1 50mm length, depending on the process; generally it can be said that all raspings used in Grignard
reactions, are tailor made according to the requirements of the customers. Due to the special application the used
magnesium has to be high purity material; even a small number of impurities can lead to outliers and wastage of the
whole charge. The yearly amount of magnesium used in this application is less than 10.000 tons.
Only a small amount of magnesium fines is used as powders. Magnesium powders are sensitive against oxidization
and have to be carefully protected against humidity and open fires.
The main use of magnesium powders is in processes where a high level of energy is required. Magnesium has a
high affinity to oxygen; in combination with the high specific surface of powders this type of magnesium product is a
proper reagent for the reduction of metallic oxydes, e.g. tungsten from WO3. For this applications the used magnesium has to be pure with a magnesium content of not less than 99,95% to avoid any impurities which might disturb
the properties of the produced metal.
352

Another important application of magnesium powders is the use in pyrotechnics as an energy source. The magnesium contains a lot of energy to start the specific reactions of the added metal oxydes with the result of sophisticated
colouring effects. The magnesium powders also burn with a bright flame, which is also used to bring a decorative
effect in fireworks. For the use in fireworks mainly magnesium-aluminium alloys with 50% Al and 50% Mg are used.
This material is brittle and can be crushed. The production of these powders is therefore done with crushers, it is
almost impossible to cut these alloys with saws. The powders are globular, which allows constant properties in all
dimensions; cutted magnesium powders have different dimensions in length and wideness, therefore these powders will have a different appearance when burning, they tend to make sparks in all directions.
Magnesium based powders are also used for military applications. In this field magnesium flares are in use to irritate thermal controlled weapons; In case if an airplane starts or lands in a dangerous area, in which it might be
attacked by thermal controlled weapons, a cloud of burning magnesium flares is generated which helps to irritate
any weapons which would have the engines of the plane as their target.
A very interesting application for magnesium based powders is the use in refractory bricks. Mainly powders based
on aluminium- magnesium- alloy 50/50 are used for increasing the performance of magnesia and carbon based,
resin bonded, refractory bricks. Additions of small amounts of Al-Mg- powders in a size of 0-500 microns have a
significant influence on the life time of the refractories. During the use of these bricks in converters or blast furnaces
the added alloy powder gets oxidized and forms Al2O3 and MgO. This phase has very good properties regarding
strength, supports the structure of the bricks and also prevents the carbon of the refractory bricks from oxygen.
Even as theses powders have an influence on the price of the refractory bricks, the use is justified by an increased
life time of the refractory material. For this special application Almamet is selling some hundred tons per year. All
powders are tailor made; every customer has his own special requirements. Beside the pure alloy powders some
customers need to be supplied with premixes of alloy powders with magnesia to decrease the hazardous potential
of these fine materials. It has been detected that the addition of 30% magnesia tremendously reduces the explosivity of these magnesium powders. In addition to this fact the dosage of the powder is much easier and helps the
producer of the refractory bricks to save time and brings big increases of the quality.
Some research activities were recently made with magnesium powders used for the storage of hydrogen [5]. The
hydrogen is stored as MgH2. The production of MgH2 is done with magnesium powder and pressurized hydrogen at
temperatures between 250C and 400C. The production parameters for the typical reaction can be seen in figure 4.
The MgH2 is a solid material which can be stored then in cartridges as a fuel for hydrogen driven cars. The hydrogen
is released then in the hydrolysis reaction between water and MgH2. This new application for magnesium powder
could be a solution for the storage of hydrogen for transport means in the future. The production process is patented
and the first commercial production should have been started [6].
Figure 4. Production parameters for MgH2 [4].

5. CONCLUSION
Magnesium raspings, granules and powders are positioned in a niche market. Although the materials are not known
well, they play an important role in our modern life. Magnesium fines are used in manifold production routes. The
modern production of steel, plastics and even nutritials would not be possible without magnesium fines. Since the
requirements of modern construction materials continue to increase, magnesium fines are getting even more important to fulfil the ambitious needs of our modern society.
353

6. REFERENCES
1. M. Shukun, W. Xiuming, X. Jinxiang, China Magnesium Development Report in 2010, 68th Annual World
Magnesium Conference, Prague, 2011, p.51ff
2. A. Ditze, C. Schrf, Utilising magnesium scrap in other sectors, Recycling of Magnesium, p. 141ff
3. R. Schwarzenbrunner, F. Landerl, R. Apfolterer, The Pig Iron Desulphurization as an Important Procedural Step
of the Steel Production, The X. International Symposium for Desulphurization of Hot Metal and Steel,
2008, Lisbon, p.40ff
4. I. Nakatsugawa, T. Tsukeda, K. Kitamura, Latest Developments in Magnesium Use for Thixomolding in Asia,
59th Annual World Magnesium Conference, Montreal, 2002, p. 11ff
5. H. Uesugi, T. Sugiyama, I. Nakatsugawa, T. Ito, Production of Hydrogen Storage Material MgH2 and its Applications, 67th Annual World Magnesium Conference, Hong Kong, 2010, p. 49ff
6. M. Jehan, Safe Clean and Efficient Solutions for Energy Storage, 66th Annual World Magnesium Conference, San Francisco, 2009, p. 171ff
354

APPLICATION OF CENTRAL COMPOSITE DESIGN TO INVESTIGATE

THE EFFECTS OF REINFORCEMENT VOLUME FRACTION AND
MATRIX-REINFORCEMENT PARTICLE SIZE RATIO ON WEAR
CHARACTERISTICS OF Al-SiCp METAL MATRIX COMPOSITES
1
Ege Anl Diler , Rasim pek and hret M. Erolu

1
Department of Mechanical Engineering, Ege University, 35100, Bornova, Izmir, Turkey, Ege.
anil.diler@ege.edu.tr, rasim.ipek@ege.edu.tr, sohret.eroglu@ege.edu.tr
ABSTRACT
In this study, the effects of reinforcement volume fraction, matrix-reinforcement particle size ratio and their interactions on the wear characteristics of Al-SiC metal matrix composites have been investigated by using central experimental composite design (CCD). To optimize the required number of experiments central composite design with
three factors and five levels was used. The fabricated composites were reinforced with SiC particles of 4.09, 7.5,
12.5, 17.5 and 20.91 volume fractions.
The particle sizes of 68, 86, 112, 138 and 156 m were selected for both matrix and reinforcement particles. All these
values were determined according to CCD. The wear behavior of these Al-SiCp metal matrix composites have been
investigated under dry adhesive wear condition. Main factors and their interactions were effective on wear behavior
of Al-SiCp composites. The best combination of factors to obtain the highest wear resistance was achieved when
matrix-reinforcement size ratio equaled to one or was a little higher than one for high volume fraction.
Keywords: Powder metallurgy; Al-SiCp; Metal matrix composites; Central composite design; wear.
1. Introduction
Metal matrix composites (MMCs) have been extensively used because of high strength, light weight, improved wear
resistance. These materials are preferred in several applications; for instance, brake pads which have been made
of Al-SiC composites have been used in railway or automotive applications [1,2].
Ceramic phases like SiC improve the wear resistance of materials. These phases are found as particle or whisker
forms in the Al-SiC composites. Although the study of Aiguo and Rack [3] showed that whisker reinforcement is
more influential than particle reinforcement in enhancing wear resistance of a composite, Miyajima and Iwai [4]
presented composite with particle was more beneficial than ones with whisker and fiber. There are many factors
affecting the wear behavior of Al-SiC composites. These factors are reinforcement size and volume fraction, abrasive size, load, speed, sliding distance, temperature, etc. The effect of matrix powder size hasnt been taken into
account in the studies which all other factors were investigated [3-13]. However, matrix powder size is one of the
important factors in Al-SiCp composites which are manufactured by powder metallurgy method.
Because, matrix-reinforcement size ratio determines the distribution of reinforcement particles in the microstructure.
In addition to matrix-reinforcement size ratio, reinforcement volume fraction also affects particle distribution. Due to
volume fraction and matrix-reinforcement size ratio, particle clustering may occur, which raises probability of particle clustering [14]. A reinforcement particle in a particle cluster can be easily pulled out from the material surface
contacting against the counterface material during the wear test. Hence, the wear resistance of the composites
355

reinforced with high reinforcement volume fraction can be lower than that of unreinforced materials. As a result of
aforementioned reasons, the matrix-reinforcement particle sizes and reinforcement particle volume fraction have a
strong impact on the wear behavior of the composites. As the number of the factors and their levels increases, the
number of experiment also increases. Therefore, many experimental design methods have been used to investigate the wear behavior of Al-SiCp composites. Most of the researchers used Taguchi method [15-18] while ahin
[19] applied factorial design method in his study.
Another experimental design method for statistical analysis is central composite design (CCD) method. CCD method has been preferred by some researchers [20-21] because the number of experiment is decreased with the help
of this method. Unfortunately, the effect of matrix powder size on the wear behavior of composites has not been
investigated in all the studies mentioned above.
The aim of this study is to investigate the effect of the matrix powder size besides reinforcement particle size and
volume fraction and their interactions on the wear behavior of Al-SiCp composites under adhesive wear condition
by using CCD statistical analysis.
2. ExperImental
2.1 Materials
SiC particle reinforced aluminum matrix composite specimens were manufactured from elemental powders by
powder metallurgy. According to CCD experimental method, the fabricated composites were reinforced with SiC
particles of 4.09, 7.5, 12.5, 17.5 and 20.91 volume fractions, and the particle sizes of 68, 86, 112, 138 and 156 m
were selected for both matrix and reinforcement particles.
The powders were blended for 1 h in triaxial mixer to provide homogeneous dispersion. Then powder mixture was
cold compacted under a pressure of 450MPa. The green compacts were then sintered at 600 C for 6 h.
2.2 Wear test
The wear tests were performed under dry sliding conditions using a ball-on-disc type testing machine. A hardness
of 62 HRC and 6 mm diameter bearing ball was loaded against the specimens. The track diameter was 10 mm.
Wear tests were applied under the normal load of 5 N and at a constant sliding velocity of 0.416 m/s and a sliding
distance of 500 m. Before and after the wear test all specimens were cleaned with alcohol to remove accumulated
debris on the wear track and weighed before and after the wear tests using an electronic balance with a resolution
of 0.0001 g.
2.3 Experimental design
The experiments were designed according to CCD method. Each variable was studied at two different levels (-1,
+1), two axial points (-1.68179, +1.68179) and a center point (0) which is the midpoint of each factor range. The
minimum and maximum range of variables investigated and the full experimental plan with respect to their actual
and coded values are listed in Table 1.
Table 1. Experimental range of the variables studied using CCD in the terms of actual and coded factors.
Experimental results were analyzed using the Minitab 15 software. The polynomial equations for the response were
validated by ANOVA (analysis of variance) to determine the significance of each term in the equations and also to
estimate the goodness of fit in each case. Response surfaces were drawn for the experimental results obtained for
the effect of the different variables on the wear loss of the MMCs after the wear test in order to determine the main,
interaction and quadratic effects of these variables.
356

Table 2. Central composite design plan and experimental results.

3. Results and discussion
The microstructures of Al-SiCp composites with different volume fraction, matrix and reinforcement size are shown
in Fig.1. Reinforcement particles were uniformly distributed in Al-SiCp composites with low volume fraction (Fig.1 a
and b) while they clustered in case high volume fraction of reinforcement was high level and matrix size was higher
than that of reinforcement particles (Fig.1 c and d).
Fig. 1. Optical micrographs of Al-SiCp composites at 100X magnification: (a) 7.5% Al(86m)-SiCp(138m);
(b) 7.5% Al(138m)-SiCp(86m); (c) 17.5% Al(86m)- SiCp(138m); (d) 17.5% Al(138m)-SiCp(86m).
357

Table 3, Analysis of variance (ANOVA) of CCD model.
Table 3 shows the ANOVA of CCD model. The coefficient determination (R2) was 0.9790. It means that the statistical model can explain 97.90 % variability in the response. When the value of P is less than 0.05, the terms (main
factors, interactions and quadratic effects of factors) of the model are significant. As seen from Table 3, P values of
the main factors were less than 0.05 values; therefore, volume fraction, matrix and reinforcement sizes had significant effects on the wear rate. Interactions of volume fraction*matrix size (A*B) and volume fraction*reinforcement
size (A*C) was also significant while interaction between matrix size and reinforcement size was insignificant on the
model. Except for volume fraction, quadratic terms of matrix and reinforcement size was insignificant.
To calculate the % contribution of the significant factors, the sum of squares of a factor divides the total sum of
squares. As seen from the Table 4, the factor of volume fraction of reinforcement particles had the highest contribution on the response of the model.
Table 4. Contribution of significant main factors, their interactions and quadratic effects of factors.
Table 4. Response surface regression including only significant terms.

Eq. (1), the regression equation including coefficients of significant terms and coded values of factors, is given below:
W = 0.003651 - 0.005698 (A) + 0.001244 (B) - 0.002316 (C) + 0.002881 (A2) - 0.000967 (AB) + 0.001750 (AC) (1)
where W is the response (wear loss) and A, B and C are the coded values of factors, volume fraction, matrix size
and reinforcement size, respectively.
358

Fig. 2. Main effects plot for wear of Al-SiC composites.

Fig. 2 shows the individual main effect of matrix size on wear. Total surface area of matrix powder increases as
their size decreases, which results in an increase in hardness of composite due to an increase in number of obstacles against movement of dislocations. Hence, wear loss of MMCs increased as matrix size increased in present
study.
Individual main effects plot of reinforcement particle size showed that wear loss decreased as reinforcement particle size increased (Fig. 2). The reason is that large sized particles have higher load bearing capacity than smaller
one [10]. Another reason is that matrix-reinforcement interfacial area is wider for MMCs reinforced with small sized
particles, which causes to reinforcement particles easily pull out from the matrix [21]. Large sized particles tightly
embedded in the matrix; therefore, they protect the matrix until they fracture into smaller particles. As a result of two
reasons mentioned above, wear resistance of MMCs increases as size of reinforcement particle increases.
As for individual main effect of volume fraction on wear, wear loss decreases as volume fraction increased. In
fact, an increase in volume fraction negatively affects the mechanical behavior of MMCs because particle clustering occurs as volume fraction increases. Particle clustering in MMCs weakens the mechanical strength such as
tensile strength [22]. From the point of view of wear, particle clustering depending on high volume fraction had
positive influence on wear resistance of MMCs in present study. This was only true when matrix- reinforcement size
ratio was high at high volume fractions. Because; for high volume fractions, wear resistance increased as matrixreinforcement size ratio increased. Reinforcement particles which are located in cluster region are not bonded to
each other due to low sintering temperature. These particles are more easily debonded from the cluster region
or pulled out from the matrix during wear. Debonded or pulled out particles cause three-body abrasive wear [23],
which results in an increase in wear due to the fact that hard reinforcement particles tend to abrade both MMC and
counterface surfaces. These particles form a hard and stable MML at a later stage of wear. Wear loss reduces in
these stages, called as mild wear, which is attributed to existence of a hard and stable MML resulting in better wear
resistance [24]. In this case, it is easy to form a thinner, harder and more stable MML for MMC reinforced with small
sized particle compared to big sized particle one. Although the individual main effect of reinforcement size increases
wear resistance, coarse particle size at high level of volume fraction has negative influence on wear resistance. It is
also important to note that since the stress on the debonded or pulled out particles is excessive and the probability
of having defects of coarse particles is high, these particles will begin to become smaller and smaller by fracturing.
This situation increases the wear resistance of MMCs in that the ability of these particles to plough or to scratch
decreases.
Actually, probability of particle clustering increases as matrix-reinforcement size ratio increases. Although particle
clustering has a strong effect on the mechanical properties of MMCs reinforced with particles, Table 3 shows that
interaction between matrix size (B) and reinforcement size (C) had insignificant effect on wear because its P value
is greater than 0.05.
359

Fig. 3. 3D response surface plot of the effect of volume fraction and matrix size and their interaction on wear.
Fig. 3 shows the interaction effect of volume fraction and matrix size on the wear of Al- SiCp composite while reinforcement size is constant kept at coded value of 0. This response surface plot indicates that wear loss increased
at low level of volume fraction and high level of matrix size and also that the volume fraction had a dominant effect
over the matrix size (Table 4).
Fig. 4. 3D response surface plot of the effect of volume fraction and reinforcement size and their interaction on wear.
The interaction effect of volume fraction and reinforcement size on the wear of Al-SiCp composite while matrix size
was constant kept at coded value of 0 is shown in Fig. 4. As aforementioned above, this response surface plot indicates that wear loss of Al-SiCp composites decreased at the high level of volume fraction and at the low level of
reinforcement size or at high matrix-reinforcement size ratio.
Consequently, for highest wear resistance the best combination of factors is achieved when matrix-reinforcement
size ratio equals to one or is a little higher than one for high volume fraction although both high volume fraction and
high matrix-reinforcement size ratio result in particle clustering.
4. Conclusions
In this study, the effect of reinforcement volume fraction, matrix and reinforcement size on wear of Al-SiCp composites was investigated using CCD, and the following results were obtained:
(1) Reinforcement volume fraction, matrix and reinforcement sizes as individual main factors and their interactions
except matrix size*reinforcement size interaction affect wear behavior of Al-SiCp composites.
(2) Individual main effect plots of volume fraction and reinforcement size indicate that wear loss decreases as
values of these factors increases while matrix size has contradictory effect. In interaction between volume fraction
and matrix size, the effect of volume fraction dominates that of matrix size.
360

(3) Although both volume fraction and reinforcement size as individual main factors decrease wear loss, interaction between volume fraction and reinforcement size plays a negative role on the wear resistance at high volume
fraction and reinforcement size.
(4) The best combination of factors to obtain the highest wear resistance can be achieved when matrix-reinforcement size ratio equals to one or is a little higher than one for high volume fraction.
References
[1] Laden K., Guerin J.D., Watremez M. and Bricout J.P., Frictional characteristics of AlSiC composite brake discs,
Tribology Letters, 8, 2000, 237-247.
[2] Vencl A., Rac A., Bobic I., Tribological behaviour of Al-based MMCs and their application in automotive industry,
Tribology in industry, 26, 3-4, 2004, 31-38.
[3] Wang Aiguo and Rack H.J., Abrasive wear of silicon carbide particulate-and whisker- reinforced 7091 aluminum
matrix composites, Wear, 146, 2, 1991, 337-348.
[4] Miyajima T. and Iwai Y., Effects of reinforcements on sliding wear behavior of aluminum matrix composites, Wear,
255, 2003, 606-616.
[5] Veeresh Kumar G.B., Rao C.S.P., Selvaraj N., Mechanical and tribological behavior of particulate reinforced
aluminum metal matrix composites - a review, Journal of Minerals & Materials Characterization & Engineering, 10, 1,
2011, 59-91.
[6] Daoud A., Abou El-khair M.T., Wear and friction behavior of sand cast brake rotor made of A359-20vol%SiC particle
composites sliding against automobile friction material, Tribology International, 43, 2010, 544-553.
[7] Deuis R.L., Subramanian C., Yellup J.M., Dry sliding wear of aluminium scomposites-a review, Composites Science
and Technology, 57, 1997, 415-435.
[8] Alpas A.T. and Zhang J., Effect of SiC particulate reinforcement on the dry sliding wear of aluminium-silicon alloys
(A356), Wear, 155, 1, 1991, 83-104.
[9] pek R., Adhesive wear behavior of B4C and SiC reinforced 4147Al matrix composites (Al/B4C-Al/SiC), Journal of
Materials Processing Technology, 162-163, 2005, 71-75.
[10] Bindumadhavan P.N., Heng Keng Wah, Prabhakar O., Dual particle size (DPS) composites: effect on wear and
mechanical properties of particulate metal matrix composites, Wear, 248, 2001, 112-120.
[11] Gl F. and Acilar M., Effect of the reinforcement volume fraction on the dry sliding wear behavior of Al10Si/SiCp
composites produced by vacuum infiltration technique, Composites Science and Technology, 64, 2004, 1959-1970.
[12] Sun Zhiqiang, Zhang Di, Li Guobin, Evaluation of dry sliding wear behavior of silicon particles reinforced aluminum
matrix composites, Materials and Design, 26, 2005, 454- 458.
[13] Mondal D.P., Das S., High stress abrasive wear behavior of aluminium hard particle composites: Effect of experimental parameters, particle size and volume fraction Tribology International, 39, 2006, 470-478.
[14] Bhanu Prasad V.V., Bhat B.V.R., Ramakrishnan P., Mahajan Y.R., Clustering probability maps for private metal
matrix composites, Scripta Materialia, 43, 2000, 835- 840.
[15] Basavarajappa S., Chandramohan G., Paulo Davim J., Application of Taguchi techniques to study dry sliding wear
behavior of metal matrix composites, Materials and Design, 28, 2007, 1393-1398.
[16] Kk M., Computational investigation of testing parameter effects on abrasive wear behavior of AL2O3 particlereinforced MMCs using statistical analysis, International Journal of Advanced Manufacturing Technology, 52, 2011,
207-215.
[17] Venkat Prasat S., Subramanian R., Radhika N., Anandavel B., Arun L., Praveen N., Influence of parameters on
the dry sliding wear behaviour of aluminium/fly ash/graphite hybrid metal matrix composites, European Journal of
Scientific Research, 53, 2, 2011, 280-290.
[18] Sahin Y., The prediction of wear resistance model for the metal matrix composites, Wear, 258, 2005, 1717-1722.
[19] Sahin Y., Wear behavior of aluminium alloy and its composites reinforced by SiN particles using statistical analysis, Materials and Design, 24, 2003, 95-103.
[20] Anoop S., Natarajan S., Kumaresh Babu S.P., Analysis of factors influencing dry sliding wear behaviour of Al/SiC
brake pad tribosystem, Materials and Design, 30, 2009, 3831-3838.
[21] Kumar S., Balasubramanian V., Developing a mathematical model to evaluate wear rate of AA7075/SiCp powder
metallurgy composites, Wear, 264, 2008, 1026-1034.
[22] Liu Z.Y., Wang Q.Z., Xiao B.L., Ma Z.Y., Clustering model on the tensile strength of PM processed SiCp/Al composites, Composites: PartA 41, 2010, 1686-1692.
[23] Bindumadhavan P.N., Chia T.K., Chandrasekaran M., Heng Keng Wah , Loh Nee Lam, Prabhakar O., Effect of
particle-porosity clusters on tribological behavior of cast aluminum alloy A356-SiCp metal matrix composites, Materials
Science and Engineering A 315, 2001, 217-226.
[24] Venkataraman B., Sundararajan G., Correlation between the characteristics of the mechanically mixed layer and
wear behavior of aluminium, Al-7075 alloy and Al- MMCs, Wear, 245, 2000, 22-38.
361

HGANAS NEW MACHINABILITY ENHANCING MATERIALS

Philippe SZABO*, Eda YILMAZTRK YKSEKDA**
*Hganas AB, France Office, 1117 Avenue Edouard Herriot, B.P. 117, F 69654, Villefranche sur Saone Cedex,
France, philippe.szabo@hoganas.com
ABSTRACT
This Hgans presentation is done in order to show how it can be find improvement for machining processes, through
material selection. A straightforward way to improve the process is to use a material with enhanced machinability.
By adding small portions of machinability enhancing materials to the powder mix for component production, it can
be got significantly increased tool life (or productivity) and improved surface finish of the components.
Hgans provides four different additives to choose from: totally new MnM and SM3, and the traditional MnX,
MnS. The optimal choice is dependent on the machinability process, indeed.
Main benefits to target are:
higher productivity
increased tool life
improved surface finish
Key Words: MnX, MnS, PM Enhancing Materials, Machinability of PM Parts.
1. INTRODUCTION
Powder Metallurgy (PM) is well known for producing complex parts to very close tolerance. Yet, machining is still
important for some applications:
- Further demands on tolerances
- Undercuts
- Further demands on surface quality
2. MACHINABILITY
Assumed that machining operation can be defined as a chip removing operation. Therefore, we can consider
machinability as a general property, strongly influenced by machining process.
When determination to do as questioning Is it easy to machine the material? or How to characterize
machinability? , we can summarize this topic through measurement of tool wear and life (the real action between tool edge and material) and then, surface quality of the machined part - cutting forces and torques shape of chip.
3. OBJECTIVE
Carry out Drilling & Turning tests on three different PM steels. Investigate how drill tool grades and additives will
influence machinability.
3.1 Experimental - Materials and Specimens for Machinability Experiments
Materials and Specimens:
362

Figure 1. Chemical composition of different powder mixes to be used in experimental application.

Additives: 0.3% MnS, 0.15% test additive MnM, SM3 in order to achieve variants in powder mix (Our new MnM &
SM3 are additives free from sulphur).
Compacted specimens: All specimens with GD = 7.0 g/cm
Sintering/Sinter Hardening:
Figure 2. Sintering and Sinter Hardening conditions of powder mixes to be used in experimental application.
Heat Treatment: After sinter hardening - tempering at 200C in air for 60 minutes.
Microstructures:
Figure 3. Microstructure of part produced by AHC

powder mix at the end of processes, resulted typically
with 83 HRB hardness level.
Figure 4. Microstructure of part produced by DAE

powder mix at the end of processes, resulted typically
with 92 HRB hardness level.
Figure 5. Microstructure of part produced by CRM powder mix at the end of processes, resulted typically with 35
HRC hardness level.
363

3.2 Experimental Drilling and Turning Process for Experiments

Figure 6. Drilling machine to be used in process Mazak Lathe Quick turn Nexus 200-II MY.
Figure 7. 100/42 mm ring specimen to be used in drilling process (full pattern is equal to 302 holes).
Test Method: To drill as many holes as possible before break down. (More than eight drill per test used to establish
statistic values).
Cutting Parameters & Drills:
Figure 8. Types and properties of drills to be used in experimental applications.

3.3 Experimental Results of Drilling and Turning Experiments
Drilling Machinability of AHC / DAE / CrM :
364

Figure 9. Affect of different type of enhancing materials on tool life and production efficiency.
(Test held on part produced by AHC based powder mix.)
(Test held on part produced by DAE based powder mix.)
Figure 11. Affect of different type of enhancing materials on tool life and production efficiency. (Test held on part
produced by CrM based powder mix.)
365

Turning Machinability of AHC / DAE / CrM :
(Test held on part produced by AHC based powder mix.)
Figure 13. Affect of different type of enhancing materials on tool life and production efficiency. (
Test held on part produced by DAE based powder mix.)
4. HGANAS SOURCING GRID
To facilitate the powder mix selection, Hgans has developed its internal Machinability Sourcing Grid.
The tool is based on a comprehensive range of tests under selected different process conditions with a representative selection of materials combined with Hgans four additives.
366

Figure 14. Illustration of the tool, by playing on the targeted results.

5. CONCLUSIONS
Hgans is proposing Machinability Enhancing Materials, in order to get main benefits at your production as ;
- higher productivity
- increased tool life
- improved surface finish
By improving your machining processes through material selection, you can get a straightforward way to improve
the process using a material with enhanced machinability. By adding small portions of machinability enhancing
materials to the powder mix for component production, you can increase tool life (or productivity) significantly and
improve the surface finish of the components.
For this aim, Hgans provides four different additives to choose from: MnM, MnX, MnS and SM3. The optimal
choice is dependent on the machinability process.
All results thank to Olof Andersson + Mats Larsson + Bo-Hu + Nandivana Nagarjuna and team / Hgans
AB
367

POWDER PROCESSES &

CHARACTERIZATION OF
METAL POWDER AND
PM PARTS
www.turkishpm.org
368

YAPAY YALANDIRMANIN SiC VE 7075 ALMNYUM ALAIMI EREN BR

LEVSEL DERECEL MALZEMENN SERTL ZERNE ETKS
Bertan SARIKAN*, M. Kemal ZTA**, Erhan BALCI*, Mustafa BEYL***,
Necip CAMUU*, mer KELE**
TOBB Ekonomi ve Teknoloji niversitesi, Makine Mhendislii Stz Caddesi No: 43
06530 Ankara TRKYE
**
Gazi niversitesi, Mhendislik Fakltesi, Makine Mhendislii 06570 Maltepe, Ankara TRKYE
***
Osmaniye Korkut Ata niversitesiMhendislik Fakltesi, Makine Mhendislii
Karacaolan Yerlekesi, 80000 Osmaniye TRKYE
e-posta: bsarikan@etu.edu.tr
*
ZET
Bu almada, scak presleme ve sv faz sinterleme yntemiyle, katmanl bir ilevsel dereceli malzeme (DM)
retilmitir. retilen malzemenin alt katman 7075 alminyum alam, orta katman %10 veya %20 SiC takviyeli
kompozit, st katman ise %20 veya %40 SiC takviyeli kompozitten olumaktadr. DMlere daha sonra yapay
yalandrma ilemi uygulanmtr. Bu ilem zeltiye alma ileminden sonra, 120C scaklkta ve 78 saate kadar
yaplmtr. Numuneler zerinde belirli zaman aralklarnda sertlik deerleri llmtr. Farkl yalandrma zamanlarnn numunelerin sertlik deerlerine etkisi aratrlmtr. almann sonunda, 65 saatlik yapay yalandrma
ilemi sonunda en yksek sertlik deerlerine ulald gzlemlenmitir.
Anahtar kelimeler: levsel dereceli malzeme, yalandrma, scak presleme.
EFFECT OF ARTIFICIAL AGING ON THE HARDNESS OF A FUNCTIONALLY

GRADED MATERIAL CONSISTING OF SiC AND ALUMINIUM 7075 ALLOY
ABSTRACT
In this study, a three-layer functionally graded material (FGM) was produced by hot pressing and liquid phase
sintering methods. The top, middle and bottom layers of this material consist of 20% or 40% SiC reinforced composite, 10% or 20% SiC reinforced composite and 7075 aluminum alloy, respectively. Then, artificial aging process
was applied to the materials. This was done at 120C and up to 78 hours. Hardness measurements were taken
at certain time intervals. The effect of duration of the artificial aging process on the hardness of the materials was
investigated. In conclusion, it was observed that the highest hardness values were obtained at the end of 65 hours
of artificial ageing process.
Keywords: Functionally graded material, aging process, hot pressing
1.GR
Her geen gn artan toplum ihtiyalarnn karlanmas gereklilii, tasarmclar yeni malzemeler gelitirmeye ynlendirmektedir. Bu kapsamda kompozit malzemeler geleneksel metal malzemelere gre daha dk younlua ve
369

istenilen mekanik zelliklere sahip olmalar nedeniyle tercih edilmektedir [1]. Kompozit malzemelerde anayapya
ilave edilen takviye malzemesi dk younluk, yksek sneklik ve toklua sahip olan sisteme, yksek dayanm,
rijitlik ve sertlik zellikleri kazandrarak stn mekanik zelliklere sahip bir malzemenin ortaya kmasn salamaktadr. Parack takviyeli kompozit sistemlerde takviye malzemesi olarak; silisyum karbr, bor karbr ve almina
yaygn olarak kullanlmaktadr [2].
Malzemede yne bal olarak istenen mekanik zelliklerin elde edilmesi amacyla kompozit malzemelerin bir tr
olan ilevsel dereceli malzemeler (DMler) ortaya kmtr. DMler heterojen bir yapya sahip olup, istenilen malzeme performansn salamak amacyla, kompozit malzeme ierisindeki yap, bileimi oluturan malzemelerin hacim
oranlarn ve mikroyapsal zelliklerini deitirerek ayarlanabilmektedir [3]. DMlerin retiminde; toz metalurjisi,
plazma pskrtme, kimyasal buhar keltme, lazer kaplama en yaygn kullanlan yntemlerdir. Bu yntemler arasnda toz metalurjisi, dk maliyet, dk enerji tketimi ve ilem sresinin ksa olmas gibi zellikleri nedeniyle
tercih edilen yntemler arasnda en nemlisi olarak gsterilebilir [4].
Farkl ekillerdeki takviye malzemelerine kyasla parack takviyeli kompozit malzemeler izotropik mekanik zellikler
elde edilmesi asndan daha elverilidir. Metal ve seramik toz paracklarnn sinterlenmesinde parack boyutu ve
dalm kompozit malzemelerin mekanik zelliklerini nemli lde etkilemektedir [5]. SiC takviyeli Al alamlaryla
ilgili literatrde yaplan almalarda; takviye paracklarn boyutu azaldka mekanik zelliklerin artt fakat bunun
yannda takviye boyutu azaldka ve anayap ierisindeki takviye miktar arttka, toz karm esnasnda takviye
paracklar arasnda topaklanmann daha fazla meydana geldii grlmtr [6]. stn mekanik zellikler elde
edilmesi asndan anayap ve takviye malzemesinin iyi ba yapabilme zelliine sahip olmas gerekmektedir [7].
Anayapdaki toz boyut dalmnn geni bir aralkta olmas yksek paketlenme younluklar salarken, sinterleme
ilemi sonucunda daha yksek mekanik zelliklerin elde edilmesine neden olmaktadr [7,8].
SiC parack takviyeli Al kompozitlerinin yalandrlmas ile ilgili yaplan almalarda, Mg atomlarnn Al ve SiC ara
yzeylerinde MgO paracklar eklinde bulunmas ve anayapda MgSi2 bileii olumasna bal olarak yalandrma ileminin yavalad grlmtr [9]. Bir baka almada ise Al ve SiCnin iyi ba yapt gzlemlenmitir
[10].
7xxx serisi alminyum alamlar yalandrlabilir alamlar olup, yalandrma scaklk ve sresine bal olarak
dayanmlarnn artrlabildii bilinmektedir [11].
AA 7075 iin kelti dizisi karmak olmasna ramen genel kabul gren kelti dizisi aadaki gibidir [12]:
Ar doymu kat zelti
GP blgeleri
-MgZn2
Yalandrma ilemi sonucu ulalan en yksek sertlik deerlerinin kararl faz yerine, yar kararl faznn oluumundan sonra elde edildii dnlmektedir. GP blgeleri ve yar kararl faz kelmenin ilk aamalarnda olumaktadr. Oluan zeltilerin boyutu ve younluu istenilen zelliklerin elde edilmesinde nemli bir ldr. Ayrca
oluan faznn tabakal yapsnn sertlii belirgin derecede artrd ve en yksek sertliin elde edilmesinde byk
miktarda rol oynad bilinmektedir [11,13].
Bu almada, SiC parack takviyesi ve alminyum alam (AA) 7075 (%5,1-6,1 Zn, %2,1-2,9 Mg, %1,2-2,0 Cu,
%0,5 Fe, %0,4 Si ve %0,18-0,28 Cr) ieren katmanl ilevsel dereceli malzemeler retilmitir. Daha sonra bu
malzemelere yapay yalandrma sl ilemi uygulanarak malzeme sertliinin zamanla deiimi aratrlmtr.
2. DENEYSEL YNTEM
Bu almada; %99.9 saflkta ve 45 m alt metal ve seramik tozlar kullanlarak iki farkl bileime sahip ve
katmandan oluan DMler retilmitir. Lazer parack boyutu lm yntemiyle almada kullanlan toz boyutlar
belirlenmitir. retilen kompozit malzemelerde anayap olarak AA 7075, takviye malzemesi olarak SiC seramik
paracklar kullanlmtr. ki farkl bileimdeki DMlerden ilkinde alt katman AA 7075, orta katman %10 ve st
katman %20 SiC takviyeli; dierinde alt katman AA 7075, orta katman %20 ve st katman %40 SiC takviyeli olmak
zere iki farkl bileimde DM retilmitir. Hacimce yzde bileimi hazrlanan tozlar deirmen tipi kartrcda 2 saat
sreyle kartrlmtr. Elde edilen karmlar, srasyla alt katmandan balanarak ortalama 13 MPa basn altnda
n sktrma ilemine tabi tutulmutur. Yaplan bu ilem sonras 70x70 mm boyutlarndaki malzemelere 13 MPa
basn altnda ve 575Cde 30 dakika sreyle sktrma ve sinterleme ilemleri e zamanl olarak uygulanmtr.
370

Daha sonra retilen iki farkl bileimdeki malzemenin k mikroskobu grntleri alnmtr. n sktrma ve ardndan gerekletirilen sinterleme ilemi 11 kW gcnde ve 15 ton sktrma kapasiteli scak presleme cihaznda
gerekletirilmitir. retilen DMlere 470Cde 1 saat sreyle zeltiye alma ve ardndan su verme ilemi uygulanmtr. Su verilmi malzeme, ya banyosunda 120C scaklkta 78 saate kadar farkl srelerde yapay yalandrma
ilemine tabi tutulmutur. Malzemelerin belli aralklarda sertlik lmleri gerekletirilmitir. Brinell sertlik lmleri
2,5 mm bilye ap ile 187,5 kg yk altnda gerekletirilmitir. lmler sonunda yalandrma sresinin DMlerin
sertlii zerine etkisi belirlenmitir.
3. DEERLENDRME
3.1 Yap ncelemeleri
retim sonras alnan kesit grntlerinde, 3 katmanl DMlerin baarl bir ekilde retilebildii grlmtr. ekil
1de %40 ve %20 hacimsel takviye oranlarna sahip DMnin kesit grnts rnek olarak verilmitir.
ekil 1. retilen DMlere ait kesit grnts.

Parack takviyeli kompozit malzemelerde toz boyut ve dalm sinterlenme davran zerinde nemli bir etkiye
sahiptir. Toz boyut lmleri sonucunda belirlenen ortalama toz boyutlar izelge 1de verilmitir.
izelge 1. almada kullanlan tozlarn ortalama boyutlar
Malzeme
Ortalama Toz Boyutu (m)
Al
10,22
Zn
6,66
Mg
45,08
Cu
19,17
Fe
6,66
Cr
33,42
Si
3,53
SiC
32,67
Takviye paracklarnn bykl, takviye malzemesinin anayap ierisinde homojen dalm asndan olduka
nemlidir. Takviye malzemesi olarak kullanlan SiC paracklar ve anayapnn nemli bir ksmn oluturan Al tozlar
arasndaki boyutsal oran, tozlarn nemli miktarda homojen dalmn salamtr. Elde edilen homojen dalm,
retilen DMnin hacimce %20 takviyeli blgesinden alnan ve ekil 2de verilmi olan k mikroskobu grntsnde
aka grlebilmektedir.
Homojen toz dalm 3 farkl katman ierisinde, malzeme zelliklerinin blgesel olarak farklln byk lde ortadan kaldrarak, izotropik mekanik zelliklerin elde edilmesini salamtr. Takviye miktarnn art ekil 3te verilen
ve hacimce %40 takviyeli katmana ait olan k mikroskobu grntsnde gzlemlendii gibi, takviye paracklarn
anayap ierisinde homojen dalm gsterdii fakat takviye miktarnn artna bal olarak yap iinde bir miktar
topaklanma meydana geldii gzlemlenmitir.
371

ekil 2. Hacimce %20 parack takviyeli katmana ait

k mikroskobu grnts.
ekil 3. %40 parack takviyeli katmana ait k

mikroskobu grnts.
ekil 3te grld gibi takviye miktarnn %40 olduu katmanda, takviye miktarnn nemli miktarda artmasna
ramen, anayap ierisinde mmkn olduunca homojen parack dalm elde edilebilmitir. Bu durum retilen
DMnin her katmannda izotropik mekanik zellik elde edilebildiinin bir gstergesidir. Anayapy oluturan Al 7075
alam ierisinde byk oranda bulunan Al, Zn ve Mg elementleri yap ierisinde MgZn2nin bulunmasn, yap ierisindeki MgO ve SiC paracklarnn bulunmas ise MgSi2 bileiklerinin bulunma ihtimalini glendirmektedir [8-9].
3.2 Sertlik Davran
ki farkl bileimde retilen DMlere 120Cde yapay yalandrma ilemi uygulanm, numunelerin belirli sre aralklarnda sertlik deiimleri belirlenmi ve ulalan en yksek sertlik deerleri tespit edilmitir. %20-10 takviye oranna
sahip DMye 120Cde uygulanan yapay yalandrma ilemi sonucunda DMyi oluturan katmana ait sertlik
deiimleri ekil 4de verilmitir.
ekil 4. Hacimce %20 ve %10 takviyeli katmanlara sahip DMnin yapay yalanma davran
Hacimce %20 ve %10 takviyeli katmanlara sahip DMye uygulanan ve 120Cde 78 saate kadar gerekletirilen
yalandrma ilemi sonucunda, beklendii gibi en yksek sertlik deeri en fazla takviye miktarna sahip katmanda
elde edilmitir. zeltiye alma ve su verme ilemlerinden sonra gerekletirilen yalandrma ileminin ilk saatlerinde sertlik deerlerinde belirgin biimde art grlrken, ilerleyen yalandrma srelerinde farkl katman iin
sertlik deerlerinde bir miktar d olduu ve daha sonra belirgin bir deiimin olmad gzlemlenmitir. Her
372

katmanda sertlik deiiminin genel olarak ayn ynelime sahip olduu grlmektedir. Anayapya ilave edilen takviye
malzemesinin, anayapnn yalanma karakteristiine etkisi olmad anlalmaktadr.
Hacimce %40 ve %20 takviyeli katmanlara sahip DMnin 120Cde 78 saat boyunca gerekletirilen yalandrma
ilemi sonucu elde edilen sertlik deiimi ekil 5te verilmitir.
ekil 5. Hacimce %40 ve %20 takviyeli katmanlara sahip DMnin yapay yalanma davran.
Uygulanan yapay yalandrma ilemi sonucunda hacimce %40 takviye oranna sahip katmanda en yksek sertlik
deeri elde edilmitir. Artan takviye oranlarnn sertlik deiim eiliminde genel olarak bir deiime yol amad,
takviyesiz alt katman ve takviyeli katmanlar arasnda sertlik deiiminin ayn ynelime sahip olduu grlmtr.
retilen her iki eit DMde de 65 saatlik bir yalandrma sonunda en yksek sertlik deerine eriildii gzlemlenmitir. GP blgelerinden sonra yar badak keltilerinin oluumu bu sre boyunca gereklemektedir. 65 saatlik srenin devamnda ise sertlik deerlerinde dme balamaktadr. SiC ilavesinin anayapnn sertlik deiimi eilimine etki etmedii, sadece takviyenin hacimsel oranna bal olarak sertlikte arta neden olduu tespit edilmitir.
4. SONULAR
En yksek sertlik deeri 120Cde 65 saate kadar yaplan yapay yalandrma ilemi sonucu %40 SiC parack
takviyeli katmanda elde edilmitir. Daha yksek yalandrma srelerinde sertlik deerlerinin azalmaya balad
gzlemlenmitir.
Anayapya ilave edilen takviye malzemesi orannn ulalan sertlik seviyesini etkiledii fakat ana yapnn yalanma karakteristiini deitirmedii belirlenmitir.
TEEKKR
Bu alma, TBTAK 110M034 projesi kapsamnda gerekletirilmitir. Verdii destekten dolay TBTAKa teekkr ederiz.
5. KAYNAKA
[1]. Kainer, K. U., Metal Matrix Composites: Custom-made Materials for Automotive and Aerospace Engineering, Wiley, Weinheim, 2006.
[2]. Kalkanl, A., Ylmaz, S., Synthesis and characterization of aluminum alloy 7075 reinforced with silicon carbide
particulates, Materials and Design, 29, 775-780, 2008.
[3]. Goupee, A. J., Vel, S. S., Transient multiscale thermoelastic analysis of functionally graded materials, Composite Structures, 92, 1372-1390, 2010.
[4]. Ruiz-Navas, E. S., Gordo, E., Garcia, R., Development and Characterization of 430L Matrix Composites
Gradient Materials, Materials Research, Vol. 8, No. 1, 1-4, 2005.
373

[5]. Chao, S., Song, M., Wang, Z., He, Y., Effect of Particle Size on the Microstructures and Mechanical Properties of SiC-Reinforced Pure Aluminum Composites, JMEPEG_ASM International, DOI: 10.1007/s11665010-9801-3, 2011.
[6]. Wang, Z., Song, M., Sun, C., He, Y., Effects of particle size and distribution on the mechanical properties of
SiC reinforced AlCu alloy composites, Material Science and Engineering, A 528, 1131-1137, 2011.
[7]. German, R. M., Toz Metalurjisi ve Parackl Malzeme lemleri, Tercme: Sarta, S.,Trker, M., Durlu,
N.,Trk Toz Metalurjisi Dernei Yaynlar: 05, Ankara, 15-500, 2007.
[8]. Aycan, M.F., Yalandrma ileminin Al2O3 ve SiC takviyeli aluminyum alam esasl kompozitlerin mekanik
zelliklerine etkisi, Yksek Lisans Tezi, TOBB ET F.B.E., 2010.
[9]. Wenchuan, M., Jialin, G., Yong, Z., Mingmei, W., Effect of SiC Particles on ageing behaviour of SiCp/7075
Composites, Journal of Materials Science Letters, 16, 1867-1869, 1997.
[10]. Dasgupta, R., Meenai, H., SiC particulate dispersed composites of an AlZnMgCu alloy: Property comparison with parent alloy, Materials Characterization, 54, 438-445, 2005.
[11]. Chen, J., Zhen, L., Yang, S., Shao, W., D, S., Investigation of precipitation behavior and related hardening in
AA 7075 aluminium alloy, Materials Science and Engineering, A 500, 34-42, 2009.
[12]. Lloyd, D. J., Chatuverdi, M. C., A calorimetric study of aluminum alloy AA-7075, Journal of Materials Science, 17, 1819-1824, 1982.
[13]. Sha, G., Cerezo, A., Early-stage precipitation in Al-Zn-Mg-Cu alloy (7050), Acta Materialia 52, 4503-4516,
2004.
374

SICAK PRES YNTEM LE ATOMZE Al-SiC KOMPOZT TOZLARININ

YOUNLATIRILMASI
Rdvan YAMANOLU, Erdem KARAKULAK, Muzaffer ZEREN
Kocaeli niversitesi, Mhendislik Fakltesi, Metalurji ve Malzeme Mhendislii Blm, 41380, Kocaeli, ryamanoglu@kocaeli.edu.tr, mzeren@kocaeli.edu.tr
ZET
Bu almada, Kocaeli niversitesi Metalurji ve Malzeme Mhendislii Blmnde retimi gerekletirilen Al-SiC
kompozit tozlarnn sinterleme davranlar incelenmitir. Sinterleme iin vakum destekli scak presleme teknii
seilmitir. retilen tozlar farkl scaklk, sre ve basn altnda sinterlenmi ve proses parametrelerinin sinterleme
karakteristii zerine etkileri saptanmtr. Elde edilen kompaktlarn younluklar, mikroyapsal karakteristikleri ve
sertlikleri incelenerek sonular deerlendirilmitir. Sinterlenmi numuneler dendritik yap sergilemi ve sertlikleri 79
ile 117 kg/mm2 arasnda deiim gstermitir.
Anahtar Kelimeler: Al-SiC, Dnel Elektrot Yntemi, Vakum Destekli Scak Presleme
CONSOLIDATION OF ATOMIZED Al-SiC COMPOSITE POWDERS

BY HOT PRESSING
ABSTRACT
In this study, sintering behaviour of Al-SiC composite powders fabricated at Kocaeli University Department of Metallurgical and Materials Engineering was investigated. A vacuum hot pressing technique was selected for sintering of
produced powders. The powders were consolidated under various temperature, holding time and pressure conditions. The effect of process parameters on the sintering characteristic was revealed. Hot pressed samples were
examined in terms of relative density, microstructure and hardness. Sintered samples showed dendritic structure
and their vickers hardnesses are in the range of 79-117 kg/mm2.
Keywords: Al-SiC, Rotating Electrode Process, Vacuum Hot Pressing
1. GR
zellikle otomotiv, uzay, denizcilik ve spor malzemeleri gibi endstriyel alanlarn ounda kompozit malzemeler
sahip olduklar stn zelliklerinden dolay geleneksel malzemelerin yerine tercih edilmektedirler [1-2]. Sz konusu
metal matrisli kompozit olduunda en yaygn kullanlan takviye malzemelerinden biri olan SiC, yksek scaklk mukavemeti ve modlne, dk younlua, iyi oksidasyon direncine ve yksek sertlie sahiptir [3-4]. Matris malzemesi olarak ise hafiflikleri, stn korozyon direnleri ve uygun mekanik zelliklerinden dolay aluminyum alamlar
dikkati ekmektedir. Matris ile takviye malzemesi arasndaki arayzeyin doas kompozitin zellikleri asndan
olduka nemlidir [5]. Dolaysyla SiC partiklleri ve aluminyum matris arasndaki fiziksel ve kimyasal uyum SiC/Al
kompozitlerin hazrlanmas srasnda kritik unsurlardr [6,7].
375

Al-SiC MMK (Metal Matrisli Kompozit) malzeme retimi iin farkl metodlar uygulanmaktadr. Bunlardan yaygn
olarak kullanlanlardan bazlar, dkm, infiltrasyon, sprey teknii ve toz metalurjisidir. Standart dkm tekniinde
SiC takviye faz ile matris alam ergitme srasnda kartrlarak homojenlik salanr ve katlatrlr. nfiltrasyon
tekniinde gzenekli yap olarak elde edilen SiC ktle iine sv halde matris malzeme infiltre edilir. Sprey teknii
ise atomize edilen matris malzemesi ierisine katlama tamamlanmadan partikllerin enjekte edilmesine dayanr.
Alternatif olarak kullanlan toz metalurjisi ile Al-SiC MMK retimi, aluminyum tozlar ile SiC partikllerinin kartrlmas, preslenmesi ve sinterlenmesine dayanr [8].
Bu almada da farkl olarak kompozit tozlar santrifuj atomizasyonu ile retilmi ve ardndan scak pres ile sinterlenmitir. Scak preslemede ilk younlama paracklarn yeniden dzenlenmesi ve partikllerin temas noktalarndaki plastik ak ile gerekleir. Dier basnl yntemlere nazaran scak presleme dngs daha yavatr. Sinterlenecek ktle arttka sreler ok uzayabilir. Maksimum basn deeri 50 MPadr. Kirlenmeleri ve oksidasyonu
nlemek iin genellikle vakum ortamnda allr. Pahal bir yntem olmasna ramen sert ve youn malzemelerin
zellikle de elmas kesici takmlarn retiminde yaygn bir ekilde kullanlmaktadr [9].
2. DENEYSEL ALIMA
Deneysel almada matris malzemesi olarak Etial-24 (DIN AlCu4Mg1) normunda Al-Cu alam kullanlmtr. Kullanlan alamn kimyasal bileimi izelge 1de verilmitir. Bu alama dkm srasnda yaklak 650 nm (ekil 1)
boyuta sahip, ktlece % 4 SiC partiklleri ilave edilmitir. Ergiyen alam silindirik kalplara dklerek katlamaya
braklmtr. Dkm yntemiyle retilen MMK malzeme scak ekstrzyon yntemiyle ekillendirilmitir. Scak ekstrzyon ilemi SiC partikllerinin yap iinde homojen dalm salamak ve uygulanacak atomizayon ilemine
uygun boyutlu ubuk elde etmek iin gerekletirilmitir. ekil 2de SiC partikllerinin homojen dalmlarnn salanmas iin kartrld srada ekilmi bir grnt sunulmutur.
izelge 1. Bu almada kullanlan matriks alamnn kimyasal bileimi.
Etial-24
% Si
0,5
% Fe
0,5
% Cu
4,3
% Mn
0,6
% Mg
1,5
% Cr
0,1
ekil 1. almada kullanlan SiC partikllerinin SEM grntleri
ekil 2. Pota ierisindeki dkm alam
376
% Zn
0,25
% Ti
0,15

Dkm ubuklar daha sonra plazma destekli dnel elektrot yntemi ile toz haline getirilmitir. Farkl boyutlarda toz
eldesi iin deiik devir saylarnda allmtr. Toz boyut dalmlarnn belirlenmesinin ardndan iki farkl grup toz
(150-250 ve 300-500 m) Diex marka vakum destekli scak pres (ekil 3) ile sinterlenmitir. Grafit kalplar arasna
konan tozlar farkl scaklk, basn ve srede younlatrlmtr.
ekil 3. Diex marka scak pres cihaz

Sinterlenen kompaktlarn younluklar arimet yntemi ile, sertlikleri Fisherskop marka Vikers sertlik cihaz ile belirlenmitir. Numunelerin mikroyapsal karakterizasyonlar iin Zeiss Axiotech k mikroskobu ve Jeol 6060 tarama
elektron mikroskobu kullanlmtr.
3. SONULAR
ekil 4de Kocaeli niversitesi Metalurji ve Malzeme Mhendislii Blmnde retilen ve bu almada kullanlan
kompozit partikllerin grntleri verilmitir. Devir saysna bal olarak elde edilen partikllerin morfolojileri deimektedir. Artan devir says ile tozlar kresellemektedir. Ayn ekilde dk devir saysnda ise kreselleme iin
yeterli zamann bulunmamas nedeniyle karmak ekilli partikller olumaktadr.
ekil 4. Al-SiC kompozit tozlarnn tarama elektron mikroskobu grntleri

150-250 ve 300-500 m boyut aralna sahip tozlar scak preste younlatrlmtr. izelge 2de plazma destekli
dnel elektrot yntemi ile retilen Al-SiC MMK tozlarnn vakum destekli scak pres ile sinterlenmesi srasnda kullanlan parametreler ve sonular sunulmutur.
377

izelge 2. Al-SiC MMK tozlarnn scak presleme parametreleri

Numune
kodu
Scaklk (oC)
Basn
(MPa)
Sre
(Dakika)
Younluk
(%)
Toz boyutu
(m)
A1
A8
A9
530
530
530
20
20
20
10
25
25
88,80
93,60
96,00
150-250
150-250
300-500
A2
A3
A6
A10
A11
550
550
550
550
550
20
20
23
20
20
5
10
7
25
25
95,50
96,20
98,20
97,00
98,60
150-250
150-250
150-250
150-250
300-500
A4
A5
A7
A12
560
560
560
560
20
20
25
20
15
30
20
25
97,80
97,90
99,00
99,20
150-250
150-250
150-250
300-500
10 dakika bekleme sresi ve 20 MPa basn altnda elde edilen (A1) % 88,8lik gibi nispeten dk younluk deerinden sonra ilk olarak scaklk 20 oC arttrlm sre ise 5 dakikaya drlmtr. Sredeki azalmaya ramen
scaklktaki 20 oClik art ile yaklak % 7lik bir ykselme salanarak (A2) % 95,5 younluk elde edilmitir. Tam
younlua ulamak iin bu aamadan sonra scaklk deitirilmeden sre tekrar 10 dakikaya karlmtr. Scaklk
etkisinin aksine bekleme sresi ok az da olsa younlua % 0,7lik (A3) bir katk salamtr. ok uzun bekleme
sresinden kanmak iin scaklk bir 10 oC daha arttrlm ve ilave olarak bekleme sresi 15 dakikaya ykseltilmitir. Bu iki katk ile younluk (A4) % 1,60 artmtr. Ayn scaklkta bekleme sresi iki kat arttrlarak 30 dakikaya
karlm (A5) ve daha nceki sonulardan da grld gibi bekleme sresinin etkisinin ok az olduu sonucuna
varlmtr. Tm bu denemelerden sonra sinterleme davranna etki eden en nemli parametrelerden olan basn
etkisini grmek asndan yine ok ksa bir bekleme sresi ve 550 oC de sadece 3 MPalk bir basn art ile (A6)
% 98,2 gibi olduka yksek bir younluk elde edilmitir. Bu aamada grlen etkili basn desteinin ardndan
scaklk tekrar 560 oC ye, basn deeri 25 MPaa ve bekleme sreside 20 dakikaya karldnda (A7) % 99luk
bir younlua ulalmtr. Tm bu parametrelere ilave olarak toz boyutu arttrldnda malzemelerin younluunda
art grlmtr.
A1 (% 88) ve A7 (% 99) numunelerine ait k mikroskop grntleri ekil 5a ve 5bde verilmitir. En yksek gzeneklilie sahip bu numunede tozlarn temas blgelerinde byk boyutlu boluklar grlmektedir. Yksek younlua
sahip numunede ise gzenekler neredeyse tamamen kapanmtr.
ekil 5. Sinterlenen numunelerin parlatlm konumda k mikroskobu grntleri,

a) % 88 younluklu, b) % 99 younluklu numune
378

ekil 6da bu kez A1 ve A7 numunelerinin dalanm konumdaki k mikroskobu grntleri sunulmutur. Dendritik katlama sergileyen bu numunelerde kimyasal kompozisyona bal olarak yer yer tektik blgelerde dikkati
ekmektedir.
ekil 6. Sinterlenen numunelerde dalanm konumda k mikroskobu grntleri

Optik incelemelerin yannda krlma yzeyleri de incelenerek yine ayn ekilde en dk ve en yksek younluklu
numuneler iin grntler ekil 7de verilmitir. Dk younluklu numunede partikller aras balant zayfken
yksek younluklu numunenin sahip olduu kuvvetli balant net bir ekilde grlmektedir. Yksek younlua sahip
numunede artan basnca bal olarak youn deformasyon grlmektedir.
a)
b)
ekil 7. Krlma yzeylerinin SEM grntleri, a) % 88, b) % 99 younluklu numune
379

Mikroyapsal karakterizasyonlarn ardndan karlatrma amacyla farkl yntemler ile retilen malzemelerin sertlikleri llmtr. izelge 3de SiC iermeyen dkm alam, SiC katkl dkm alam ve scak preslenmi numuneler iin sertlik deerleri verilmitir. SiC ierii ve yalanma ile sertlikte art meydana gelmitir.
izelge 3. Farkl yntemlerle retilen alamlarn sertlik deerleri
Malzeme
Sertlik (HV10) kg/mm2
AlCuMg (Dkm)
90
AlCuMg (Dkm, yalanm; 220 Cde 6 saat)
129
Al-SiC (Dkm)
110
Al-SiC (Dkm, yalanm; 220 oCde 6 saat)
139
Al-SiC (Scak pres)
117
Al-SiC (Scak pres yalanm: 220 Cde 6 saat)

o
141
Farkl parametrelere bal olarak elde edilen deiik younluk deerleri iin sertlik lldnde ise ekil 8deki
diyagram elde edilmitir. Artan younluk ile sertlikteki art net bir ekilde grlebilmektedir.
ekil 8. Sertlik ile younluk arasndaki iliki

Bu alma ilk olarak kompozit tozu retimi temeline oturtulmutur. Kompozit tozlar baarl bir ekilde retildikten
sonra sinterleme davranlarnn belirlenmesi iin scak pres ile younlatrlmlardr. Farkl parametrelerin sinterleme zerine etkileri saptanarak % 99 terorik younlua ulalmtr. Elde edilen malzemelerin mikroyapsal karakterizasyonlarnn ardndan sertlikleri llm ve dier yntemlerden daha yksek deerler elde edilmitir.
TEEKKR
Bu almaya Atomizasyon Teknikleri ile Toz retimi isimli proje kapsamnda verdii destekten dolay Kocaeli
niversitesi, Bilimsel Aratrma Projeleri Komisyon Bakanlna teekkrlerimizi sunarz.
KAYNAKLAR
[1] Thnemann, M., Beffort, O., Kleiner, S., Vogt, U., Aluminum matrix composites based on preceramic-polymerbonded SiC preforms, Composites Sciences and Technology, 67, 2377-2383, 2007.
380

[2] Mondal, D. P., Das, S., Suresh, K. S., Ramakrishnan, N., Compressive deformation behaviour of coarse SiC
particle reinforced composite: effect of age-hardening and SiC content, Materials Science and Engineering
A, 460-461, 550-560, 2007.
[3] He, X., Hang, X., Zhang, C., Zhou, X., Zhou, A., Microstryuctures and mechanical properties of Cf/SiC composites by precursor pyrollysis-hot pressing, Materials Science and Engineering A, 284, 211-218, 2000.
[4] Niklas, A., Froyen, I., Delaey, I., Comparative evaluation of extrusion and hot isostatic pressing as fabrication
techniques for Al-SiC composites, Materials Science and Engineering A, 135, 225-229, 1991.
[5] algl, U., Dikba, H. ve Takn, M., Scak presleme yntemiyle imal edilmi SiCp takviyeli aluminyum esasl
kompozitlerin dfuzyon kaynanda srenin birleme zerindeki etkisinin incelenmesi, Frat niv., Fen ve Mh.
Bil. Dergisi, 18 (3), 437-443, 2006.
[6] Wang, R. M., Surappa, M. K., Tao, C. H., Li, C. Z. and Yan, M. G., Microstructure and interface structure studies
of SiCp-reinforced Al (6061) metal-matrix composites, Materials Science and Engineering: A, Volume 254,
Number 1, 219-226, 1998.
[7] Ma, T., Yamaura, H., Koss, A. D. and Voigt R. C., Dry sliding wear behavior of cast SiC-reinforced Al MMCs,
Materials Science and Engineering: A 360, 116-125, 2003.
[8] Eslamian, M., Rak, J., Ashgriz, N., Preparation of aluminum/silicon carbide metal matrix composites using centrifugal atomization, Powder Technloogy, 184, 11-20, 2008.
[9] German, R. M., Toz Metalurjisi ve Parackl Malzeme lemleri, Trk Toz Metalurjisi Dernei Yaynlar,
2007.
381

WO3N H2CH4 GAZ KARIIMIYLA REAKSYONU YOLUYLA TEK ADIMDA

WC TOZ SENTEZ
enol ETNKAYA, erafettin EROLU
stanbul niversitesi, Mhendislik Fakltesi, Metalurji ve Malzeme Mh. Blm
Avclar Kamps, 34320 Avclar / stanbul
senol-c@istanbul.edu.tr seref@istanbul.edu.tr
ZET
Bu almada WO3 tozu Ar atmosferinde stlm ve akabinde H2CH4 (% 10) gaz karmlaryla 9001300 Kde
60 dk ve 120 dk srelerde reaksiyona sokulmutur. Deiik reaksiyon kademelerindeki rnlerin karakterizasyonu
iin XRD ve SEM teknikleri kullanlmtr. Partikl boyutu 0.21.5 m ve kristal boyutu ~50 nm olan tek faz WC
tozu, 1300 Kde 120 dk iinde elde edilmitir. Gibbs serbest enerji minimizasyon yntemiyle yaplan termodinamik
analiz sonular, WC oluumu iin deneysel artlar tahmin etmede ve sentez prosesini anlamada klavuz olarak
kullanlmtr. Termodinamik analiz, 1300 Kde WC oluumunun artan reaktan gazlar ile WO3 WO2 W WC
eklinde olduunu ngrmektedir.
Anahtar Kelimeler: WC toz sentezi, kat-gaz reaksiyonu, X-n difraksiyonu, morfoloji, termodinamik analiz.
ONE-STEP SYNTHESIS OF WC POWDERS BY REACTION OF WO3

WITH H2CH4 GAS MIXTURE
ABSTRACT
In this study, WO3 powder was heated in Ar atmosphere and were subsequently reacted with H2CH4 (% 10) gas
mixtures at 9001300 K for 60 min and 120 min. XRD and SEM techniques were used to characterize the products
at various stages of the reactions. It was found that single phase WC powders with particle size of 0.21.5 m
and crystallite size of ~50 nm were obtained at 1300 K within 120 min. Equilibrium thermodynamic analysis by the
method of minimization of Gibbs free energy was used as a guide to predict the experimental conditions for the
formation of WC and to understand the synthesis process. Thermodynamic analysis at 1300 K reveals that WC
formation follows the path WO3 WO2 W WC with increasing amount of reactant gases.
Keywords: WC powder synthesis, solid-gas reaction, X-ray diffraction, morphology, thermodynamic analysis.
1. GR
Tungsten karbr (WC), sertlik, elastisite modl, ergime scakl ve korozyon direnci gibi fiziksel ve kimyasal
zellikleri yksek olan refrakter bir malzemedir. Bu stn zelliklerinden dolay WC, anma direnli paralarda ana
bileen olarak kullanlmaktadr [13].
WC tozlar, deiik balang malzemeleri kullanlarak birok metotla retilmektedir. Klasik yntemle WC retimi,
W tozunun kat karbon siyah ile yksek scaklklarda (16002000 K) karbrizasyonu sonucu gerekletirilmektedir
382

[4]. Bu yntem, kat reaktanlar arasndaki reaksiyon hznn dk olmas nedeniyle uzun karbrizasyon sreleri
gerektirmektedir. Sentez sonras elde edilen kaba partikllerin boyutlar mekanik tme yoluyla drlmektedir.
Bu ilem, prosese ilave bir zaman ve klfet getirmektedir. Ayrca nihai rn, kat karbondan ve tcden kaynaklanan Ca, Si, Fe, S, P gibi empriteler ile kirlenmektedir [5].
Mikronalt WC partiklleri sentezlemek iin, hzl karbotermal indirgeme [5], yksek enerjili tme [6], kimyasal
buhar biriktirme [7], termokimyasal proses [810], kat-gaz reaksiyonlar [1114] gibi eitli yntemler gelitirilmitir.
Bu yntemlerde karbrizasyon scakl ve/veya sresi klasik ynteme gre daha dktr.
Kat-gaz reaksiyonu (gaz faz karbrizasyonu), gaz fazndaki karbon molekllerinin tungsten ieren partikllerle
yakn temas sonucu dk scaklklarda bile karbrizasyon hzn arttrmaktadr. Bu nedenle bahsi geen yntem
byk ilgi grmtr.
Giraudon ve dierleri [14], WO3in H2 / CH4 gaz karm ile e zamanl indirgenmesi ve karbrizasyonunu incelemilerdir. Oksit esasl balang malzemesi kullanldnda, W2C, W ve C gibi dier fazlar olmadan WC sentezlemek
iin indirgeme ve karbrizasyon arasnda hassas bir denge olduunu ifade etmilerdir.
Davidson ve dierleri [15], mikrokristal W tozlarnn H2 / CH4 gaz karm ile karbrizasyonunun 1073 Kde baladn, fakat yksek scaklklarda (11731323 K) reaksiyonun ok daha etkili olduunu belirtmilerdir.
Bu almada, WC sentezi iin ncelikle Gibbs Serbest Enerji Minimizasyon yntemi kullanlarak WO3H2CH4 sisteminde 9001300 K aralnda termodinamik analiz yaplmtr. Deneysel almalarda ise WO3 tozunun 9001300
Kde H2CH4 (% 10) gaz karmlaryla reaksiyon davran incelenmitir. Sentezlenen rnlerin karakterizasyonu
iin XRD ve SEM teknikleri kullanlmtr. Ayrca prosesin termokimyasnn akla kavuturulmas amacyla 1300
Kde kat ve gaz fazndaki deiimler termodinamik analizler yardmyla hesaplanm ve olas reaksiyon mekanizmas ortaya konmutur.
2. TERMODNAMK ANALZ
Termodinamik analiz, istenilen fazlarn sentezlenmesi iin gerekli proses parametrelerini tahmin etmek ve prosesin
termokimyasn anlamak iin kullanlan yararl bir yntemdir [16]. Bu amala yaplan termodinamik analizlerde,
Gibbs Serbest Enerji Minimizasyon ynteminden [17] yararlanlmtr. Termodinamik hesaplar iin, Eriksson tarafndan hazrlanan Solgas-Mix adl bilgisayar programnn Besmann tarafndan gelitirilmi versiyonu kullanlmtr
[18]. Bu yntemle sabit scaklk ve basnta, verilen girdi kompozisyonu iin denge halindeki (sistemin enerjisinin
minimum olduu durumdaki) gaz ve youn faz bileimleri hesaplanmaktadr. Hesaplarn yaplabilmesi iin ilgili
scaklk aralndaki mevcut olan tm element ve bileiklerin termodinamik verilerinin (Gof, bileenlere ait standart
serbest oluum enerjilerinin) bilinmesi gerekmektedir. Bu almada kullanlan termodinamik veriler, termokimyasal
tablolardan [19, 20] temin edilmitir.
Hesaplamalarda reaktan (girdi) bileimi ve scaklk deitirilmi, basn (1 atm) ise sabit tutulmutur. Hesaplama
sonular, scaklk ve girdi bileimine bal olarak kararl durumdaki kat fazlar gsteren hal diyagramlar eklinde
gsterilmitir. Ayrca, proses termokimyasnn aklanmas amacyla kat faz ve gaz faz bileimlerindeki deiimler
de grafik halinde gsterilmitir.
Deney dzenei temel olarak Ar (% 99,999), H2 (% 99,99) ve CH4 (% 99,5) gazlarn ieren gaz silindirlerinden, bu
gazlarn ak hzlarn hassas bir ekilde belirlemek iin ak lerlerden (Dwyer) ve ierisinde sentez reaksiyonlarnn gerekletirilecei kuvars tp (i ap: 20 mm) bulunan frn sisteminden (Strhlein) olumaktadr.
Sentez almalar iin gerekletirilen her bir deneyde ~10-3 mol (~0,2319 g) WO3 tozu (SigmaAldrich) kullanlmtr. Tm deneyler ncesinde, oksit tozunun bnyesinde bulanabilecek olan nemin giderilmesi amacyla ~373
Kdeki etvde 10 dakikalk bekletme yaplm ve tartmlar 10-4 g hassasiyete sahip analitik terazide (Sartorius
BP110S) gerekletirilmitir. Tartlan WO3 tozu, almina kaykk ierisinde tp frnn merkezine yerletirilmi ve
~25 K/dk stma hzyla Ar atmosferinde (85 cm3/dk) 900, 1000, 1100, 1200 ve 1300 Ke stlmtr. stenilen s-
383

cakla ulaldktan sonra Ar gaz ak kesilerek 60 ve 120 dklk srelerde H2CH4 gaz karm ile reaksiyonlar
gerekletirilmitir. H2 ve CH4 gaz ak hzlar srasyla reaksiyon sresi 60 dk iin 370 cm3/dk ve 40 cm3/dk; 120
dk iin ise 185 cm3/dk ve 20 cm3/dk olacak ekilde sabit tutulmutur. Bu ekilde sisteme verilen toplam reaktif
gaz miktarnn ayn olmas salanmtr. Tm deneylerde frn oda scaklna soutuluncaya kadar 85 cm3/dk ak
hznda Ar gaz sistemden geirilmitir.
Sentezlenen rnlerinin faz analizleri, Rigaku D/Max2200/PC marka XInlar Difraksiyon (XRD) cihaznda; morfoloji incelemeleri ise, Jeol 6335 marka Taramal Elektron Mikroskoplarnda (SEM) gerekletirilmitir. Reaksiyon
rnlerinin kristal byklkleri, (1) nolu eitlikte verilen Scherrer forml kullanlarak hesaplanmtr.
(1)
Eitlik (1)de gsterilen , Cu K radyasyonunun dalga boyunu (0,15418 nm); , difraksiyon asn; t, kristal boyutunu ve , yar ykseklikteki pik geniliini (FWHM) ifade etmektedir. FWHM deerleri belirlenirken ~0,2lik cihazdan kaynaklanan pik genilemesi de dikkate alnmtr.
4.1. Termodinamik Analiz Sonular
WC sentezi amacyla WO3H2CH4 sisteminde 9001300 K aralnda yaplan termodinamik analizde, gaz faznda
9001000 K iin 76 bileen; 11001300 K iin 46 bileen dikkate alnmtr. Bunlar arasnda H2, CH4, CH3, C2H4,
C3H6, CH2O, H2O, CO, CO2 ve H2WO4 bulunmaktadr. Denge durumundaki youn fazlar ise WO3, WO2, H2WO4
(sadece 9001000 K iin), W, W2C, WC ve Cdan olumaktadr. Tm hesaplamalarda WO3 miktar 0.001 mol ve
H2/CH4 mol oran 9.25 olarak sabit tutulmutur. Hesaplama sonular, ekil 1de scaklk ve CH4 mol kesri [noCH4/
(noCH4+noWO3)] ile kararl kat faz alanlarndaki deiimi gsteren denge diyagram olarak gsterilmektedir.
ekil 1. WO3 H2 CH4 sistemi iin denge durumundaki kararl kat faz alanlarnn CH4 mol kesri ve scaklkla
deiimi (noWO3 = 0.001 mol; noH2 / noCH4 = 9.25)
ekil 1den 9001300 K aralnda kararl durumdaki kat faz alanlarnn WO3+WO2, WO2, WO2+WC, WO2+W+WC,
WO2+W, W, W+WC, WC ve WC+C olduu grlmektedir. Dk CH4 mol kesirlerinde (0.08) WO3ten WO2 olumakta daha sonra tek faz WO2 blgesi kararl faz alan olarak gze arpmaktadr. Dk scaklklarda (9001000
K), artan CH4 mol kesri ile WO2ten WC faz direkt olarak olumaktadr. Yksek scaklklarda (11001300 K), artan
CH4 mol kesri ile WO2 nce We indirgenmekte ve daha sonra Win karbrizasyonu sonucunda WC olumaktadr.
Daha da yksek CH4 mol kesirlerinde ise WC faznn yannda serbest C ortaya kmaktadr. Ara scaklk kademesinde (10001100 K) ise WC, hem WO2ten hem de Wden olumaktadr. Ayrca, tek faz WC blgesinin artan
scaklkla darald grlmektedir. rnein tek faz WC blgesi, 900 Kde 0.54 CH4 mol kesirlerinde, 1300 Kde
ise 0.780.81 CH4 mol kesri aralnda olumaktadr. Yaplan termodinamik analiz sonucunda WO3in H2CH4 gaz
karmyla reaksiyonu sonucu tek faz WC sentezinin mmkn olduu belirlenmitir.
384

4.2. XRD Analiz Sonular

ekil 2de 9001300 K aralnda yaplan 60 ve 120 dklk deneyler sonras elde edilen rnlerin XRD paternleri
grlmektedir. Reaksiyon sresi 60 dk (ekil 2a) iin
900 Kdeki rnde ana faz olarak W ve az miktarda W2C
saptanmtr. Scaklk
1000 Ke karldnda, rnn W, W2C ve WC fazlarndan olutuu anlalmtr. 1100
Kdeki rnde W2C pikleri gzkmezken 1000 Kdeki rne gre We ait pik iddetlerinin zayflad ve WC pik
iddetlerinin artt tespit edilmitir. 1200 ve 1300 Kdeki rnlerin ana faz WCn yannda ok dk miktarda W
ierdii saptanmtr. Bu sonular, 9001300 K scaklk aralnda kullanlan reaktif gaz bileiminde 60 dk reaksiyon
sresinde saf WC elde edilemedii anlamna gelmektedir. Sisteme verilen toplam reaktif gaz miktar ayn kalmak
artyla 120 dk srede yaplan deneyler sonras elde edilen rnlerin XRD paternleri de (ekil 2b) benzer davran
sergilemektedir. Fakat, 60 dklk deneylere kyasla 9001200 K aralnda 120 dkda sentezlenen rnlerde W pik
iddetlerinin dt (daha az miktarda W ierdii) ve 1300 Kde tek faz WC elde edildii ilgili paternlerden anlalmaktadr.
ekil 2. 9001300 K aralnda sentezlenen rnlerin XRD paternleri (a: 60 dk, b: 120 dk)
ekil 3te XRD paternlerindeki her fazn ana pik iddetinin, fazlarn ana pik iddetlerinin toplamna oranlanmas
sonucu hesaplanm faz bileimlerinden tespit edilen tahmini karbrizasyon oranlar (C/W) verilmektedir. Karbrizasyon oran grafikleri, deney sonularn genel olarak zetlemektedir. ekilden, her iki srede sentezlenen rnlerde, ykselen scaklkla karbrizasyonun artt anlalmaktadr. Toplam reaktif gaz miktar her iki srede yaplan
deneyler iin ayn olsa bile 60 dklk rnlerin karbrizasyon oranlarnn 120 dklk rnlerden her zaman daha
dk olduu ve tek faz WC sentezinin ancak 1300 Kde 120 dklk reaksiyon sonucu salanabildii belirlenmitir.
Karbrizasyonun uzun sreli deneylerde daha etkili olmas, reaktif gazlarn tp ierisinde kal sresinin daha fazla
olmas (daha yava gaz ak) nedeniyle daha fazla CH4 gaznn paralanmasna, dolaysyla daha fazla C oluumuna iaret etmektedir.
385

ekil 3. Scaklk ve sreye bal olarak tahmini karbrizasyon oranlarndaki (C / W) deiim

XRD paternlerindeki piklerin yar ykseklikteki genilikleri belirlenerek balang tozu WO3in ve reaksiyon rnlerinin kristal boyutlar (1) nolu eitlik yardmyla hesaplanmtr. Tm rnlerde mikrodeformasyon deerlerinin ihmal
edilebilir dzeyde olduu saptanmtr. WO3 tozunun kristal boyutu ~50 nm iken; 900 Kde 60 ve 120 dk srelerde
sentezlenen rnlerdeki Win kristal boyutlar srasyla 32 ve 40 nm olarak hesap edilmitir. 1000, 1100 ve 1200
Kde sentezlenen WCn kristal boyutlarnn ise 60 ve 120 dklk srelerde srasyla 2026 ve 3034 nm aralnda
olduu bulunmutur. 1300 Kde yaplan deneyler sonras her iki sre iin de sentezlenen rnlerin kristal boyutlarnn ~50 nm olduu belirlenmitir.
4.3. Morfoloji ncelemeleri
ekil 4te 9001300 K aralnda 60 ve 120 dklk srelerde sentezlenen rnlerin morfolojileri grlmektedir. SEM
grntlerinden, artan scaklk ve sre ile partikl boyutlarnda byme meydana geldii anlalmaktadr. Tek faz
WCn elde edildii 1300 K 120 dk deneysel arttaki rnde partikl boyutunun 0.21.5 m arasnda olduu saptanmtr. XRD piklerinden hesaplanm olan kristal boyutlarnn SEM lmlerinden elde edilmi olan boyutlardan
daha dk olmas yapnn polikristal olduuna iaret etmektedir.
ekil 4. H2CH4 gaz karmyla 9001300 Kde sentezlenen rnlerin SEM grntleri (a), (c), (e) iin H2 : 370
cm3/dk, CH4 : 40 cm3/dk (b), (d), (f) iin H2 : 185 cm3/dk, CH4 : 20 cm3/dk
386

4.4. WC Oluumu in Reaksiyon Mekanizmasnn Termodinamik Modellenmesi

WO3H2CH4 sisteminde yaplan termodinamik analiz (ekil 1), 9001300 Kde tek faz WC sentezinin mmkn olduunu gstermitir. Deneysel almalarda ise, WO3in sadece 1300 Kde H2CH4 gaz karm ile 120 dklk reaksiyonu sonrasnda saf WC sentezlendii tespit edilmitir. allan artlarda daha dk scaklklarda CH4 gaznn
paralanma kinetiinin ve C difzyonunun yava olmas nedeniyle tek faz WC sentezi mmkn olmamtr.
ekil 1den 1300 Kde artan CH4 mol kesriyle WO3+WO2, WO2, WO2+W, W, W+WC, WC ve WC+C faz alanlarnn
olutuu grlmtr. 1300 Kdeki WC sentezinin kimyasal reaksiyon mekanizmasnn anlalmas iin CH4 mol
kesri ile denge durumundaki kat ve gaz bileimlerinin deiimi incelenmi ve sonular ekil 5a-bde grafikler halinde verilmitir.
ekil 5. CH4 mol kesri ile (a) kat ve (b) gaz fazlarnn bileimlerindeki deiim
(T = 1300 K; noH2 / noCH4 = 9.25; noWO3 = 0.001 mol)
ekil 5adan artan mol kesriyle ikili faz alanlarnda ortaya kan yeni fazn miktarnn artt anlalmaktadr. rnein, W+WC faz alannda (0.7120.776 mol kesir aralnda) artan CH4 miktar ile W %si azalrken WC %si artmaktadr. 1300 Kde H2CH4 atmosferinde WO3ten WC sentezinin srasyla WO3 WO2 W WC admlarndan
getii ekil 5adan belirlenmitir. Bu sonular, WO3H2CH4 sisteminde WC sentezi zerine yaplan literatrdeki
deneysel almalar [14, 2123] ile de uyum ierisindedir.
ekil 5bden grlecei zere tm CH4 mol kesirlerinde gaz fazndaki rnlerin ana bileenlerinin H2O, CO ve CO2
olduu anlalmaktadr. Bu sonular da literatrdeki WC sentezi iin WO3H2CH4 sisteminde yaplm deneysel
almalarda tespit edilen gaz trleri [14, 2123] ile de uyumludur. Ayrca termodinamik analiz sonucunda gaz
faznda dk mol kesirlerinde az miktarda H2WO4, yksek mol kesirlerinde de dk miktarda C2H4, CH3 ve H
gazlar tespit edilmitir.
ekil 5bden WO3+WO2 faz blgesinde gaz fazndaki ana bileenlerin H2O, CO2, CO ve H2WO4 olduu ve bu gazlarn miktarlarnn WO3ten WO2e dnmn tamamland mol kesri olan 0.081 mol kesrine kadar artt anlalmaktadr. 0.081 mol kesrinin altnda H2 ve CH4 gazlarnn giren miktardan daha az kt grlmektedir. Bu da H2
ve CH4 gazlarnn reaksiyona girdiine iaret etmektedir. Bu sonular, (2) (7) nolu reaksiyonlar ile ifade edilebilir.
(G0R = 18 400 J)
(2)

WO3 (k) + H2 (g) WO2 (k) + H2O (g)
(3)

4WO3 (k) + CH4 (g) 4WO2 (k) + 2H2O (g) + CO2 (g) (G0R = 170 856 J)

5WO3 (k) + H2 (g) + CH4 (g) 5WO2 (k) + 3H2O (g) + CO2 (g)
(G0R = 189 256 J)
(4)
387

3WO3 (k) + CH4 (g) 3WO2 (k) + 2H2O (g) + CO (g)

(G0R = 158 561 J)
(5)
4WO3 (k) + H2 (g) + CH4 (g) 4WO2 (k) + 3H2O (g) + CO (g)
(G0R = 176 961 J)
(6)
(7)

5WO3 (k) + CH4 (g) 3WO2 (k) + 2H2WO4 (g) + CO (g) (G0R = 24 795 J)
Tek faz WO2 blgesinde H2O, CO2 ve H2WO4 miktarlarnda hafif bir azalma gzlenirken CO ieriinde ise belirgin bir
art gzlenmektedir. Sisteme verilen H2 ve CH4 miktarlarnn fazla olmas nedeniyle bu gazlarn miktarlar artan CH4
mol kesri ile birlikte art gstermektedir. Muhtemel CO oluum reaksiyonlar aadaki gibi olabilir.
(G0R = 103 361 J)
(8)

CH4 (g) + H2O (g) CO (g) + 3H2 (g)
(G0R = 109 466 J)
(9)

CH4 (g) + CO2 (g) 2CO (g) + 2H2 (g)
(G0R = 6 105 J)
(10)

H2 (g) + CO2 (g) CO (g) + H2O (g)
(11)

2CH4 (g) + H2WO4 (g) WO2 (k) + 2CO (g) + 5H2 (g) (G0R = 292 005 J)
WO2+W blgesinde ise H2O, CO, CO2 ve H2WO4 ieriklerinde art olduu grlmektedir. ekil 5adan artan CH4
mol kesri ile birlikte WO2 ierii azalrken W ieriinin artt anlalmaktadr. Bu sonular nda WO2ten W oluumu iin aadaki reaksiyonlar yazlabilir.

3WO2 (k) + CH4 (g) 2W (k) + H2WO4 (g) + H2O (g) + CO (g)
(12)
(G0R = 9 384 J)
0
(13)

2WO2 (k) + H2 (g) + CH4 (g) 2W(k) + 3H2O (g) + CO (g) (G R = 94 667 J)
(G0R = 88 562 J)
(14)

2WO2 (k) + CH4 (g) 2W (k) + 2H2O (g) + CO2 (g)
Tek faz W blgesinde gaz fazndaki rnlerden H2O, CO2 ve H2WO4 azalmakta iken CO miktar ise belirgin bir ekilde artmaktadr. Bu sonular ise (8), (9) ve (15) nolu reaksiyonlar ile ifade edilebilir.
(G0R = 184 297 J)
(15)

CH4 (g) + H2WO4 (g) W (k) + 3H2O (g) + CO (g)
W+WC blgesinde ise H2O ve CO deerlerinde belirgin bir deiim olmazken CO2 miktarnda ise azalma olduu
grlmektedir. ekil 5adan grlecei zere artan CH4 mol kesri ile birlikte W ierii azalrken WC ierii artmaktadr. Bu sonular nda Wden WC oluumu srasnda gereklemesi muhtemel reaksiyonlar, (9), (10), (16) ve
(17) nolu reaksiyonlardr.
(G0R = 87 686 J)
(16)

W (k) + CH4 (g) WC (k) + 2H2 (g)
(G0R = 49 214 J)
(17)

W (k) + 3CH4 (g) WC (k) + C2H4 (g) + 4H2 (g)
Tek faz WC blgesinde gaz fazndaki rnlerden H2O ve CO2 azalmakta iken CO miktar ise artmaktadr. Bu sonular ise (8) ve (9) nolu reaksiyonlar ile ifade edilebilir.
WC dnm tamamlandktan sonra serbest C aa kmaktadr. Bu blgedeki muhtemel reaksiyonlar ise (9) ve
(18) nolu reaksiyonlar ile gsterilebilir.
(G0R = 52 626 J) (18)

CH4 (g) C (k) + 2H2 (g)
Bu bilgiler nda WO3in H2CH4 gaz karm ile 1300 Kdeki karbrizasyonu temel kademe iermektedir.
Bunlar; (a) WO3in H2CH4 gaz karm ile WO2e indirgenmesi, (b) ksmi indirgenmi rnn H2CH4 gaz karm
ile redksiyonun devam neticesinde W eldesi ve (c) Wden WC sentezi eklindedir. Bu sonular, WO3ten WC oluumu iin birok toplam reaksiyona iaret etmektedir. nerilen net reaksiyonlar ise aada gsterilmektedir.
(G0R = 101 739 J)
(19)

WO3 (k) + H2 (g) + CH4 (g) WC (k) + 3H2O (g)

4WO3 (k) + H2 (g) + 5CH4 (g) 4WC (k) + 11H2O (g) + CO (g)
(G0R = 510 317 J)
(20)

7WO3 (k) + 3H2 (g) + 8CH4 (g) 7WC (k) + 19H2O (g) + CO2 (g)
(G0R = 809 429 J)
(21)

4WO3 (k) + 2H2 (g) + 6CH4 (g) 4WC (k) + 12H2O (g) + C2H4 (g)
(G0R = 368 484 J)
(22)

4WO3 (k) + 3H2 (g) + 6CH4 (g) 4WC (k) + 12H2O (g) + 2CH3 (g)
(23)
(G0R = 178 642 J)
5. SONULAR
WC sentezi amacyla WO3 tozunun Ar atmosferinde stlmas akabinde H2CH4 (% 10) gaz karmlaryla 9001300
Kde 60 dk ve 120 dk srelerde reaksiyonlar gerekletirilmitir. Tek faz WC allan artlarda ancak WO3in 1300
Ke Ar atmosferinde stlmas sonras H2CH4 gaz karm ile 120 dklk reaksiyonu sonucunda elde edilmitir. Bu
artta elde edilen WC tozunun 0.21.5 m partikl ve ~50 nm kristal boyutlarna sahip olduu belirlenmitir. Gibbs
serbest enerji minimizasyon yntemiyle yaplan termodinamik analiz, WC oluumunun artan reaktan gazlar ile
WO3 WO2 W WC eklinde olduunu ngrmektedir. Ayrca, bu dnmler iin muhtemel reaksiyonlar da
saptanmtr.
388

TEEKKR
Bu alma, stanbul niversitesi Bilimsel Aratrma Projeleri Koordinasyon Birimince desteklenmitir. Proje
numaras: 1453.
KAYNAKLAR
1. German, R.M., Liquid-Phase Sintering, Plenum Press, New York, USA, 1985.
2. Matejka, D., Benko, B., Plasma Spraying of Metallic and Ceramic Materials, John Wiley & Sons, New York,
USA, 1989.
3. Eroglu, S., Ekren, H., Baykara, T., Surface Hardening of Tungsten Heavy Alloys, Scripta Materialia, Vol. 38,
pp. 131136, 1998.
4. Schwarzkopf, P., Kieffer, R., Refractory Hard Metals, The Macmillan Company, New York, USA, 1953.
5. Lassner, E., Schubert, W.D., Tungsten: Properties, Chemistry, Technology of the Elements, Alloys and
Compounds, Kluwer Academic / Plenum Publishers, New York, USA, 1998.
6. Bolokang, S., Banganayi, C., Phasha, M., Effect of C and Milling Parameters on the Synthesis of WC Powders
by Mechanical Alloying, International Journal of Refractory Metals & Hard Materials, Vol. 28, pp. 211216,
2010.
7. Tang, X., Haubner, R., Lux, B., Kieffer, B., Preparation of Ultrafine CVD WC Powders Deposited from WCl6
Gas-Mixtures, Journal de Physique IV, Vol. 5, pp. 10131020, 1995.
8. Koc, R., Kodambaka, S.K., Tungsten Carbide (WC) Synthesis from Novel Precursors, Journal of the European Ceramic Society, Vol. 20, pp. 18591869, 2000.
9. Reddy, K.M., Rao, T.N., Radha, K., Joardar, J., Nanostructured Tungsten Carbides by Thermochemical Processing, Journal of Alloys and Compounds, Vol. 494, pp. 404409, 2010.
10. Lei, M., Zhao, H.Z., Yang, H., Song, B., Tang, W.H., Synthesis of Transition Metal Carbide Nanoparticles
through Melamine and Metal Oxides, Journal of the European Ceramic Society, Vol. 28, pp. 16711677,
2008.
11. De Medeiros, F.F.P., De Oliveira, S.A., De Souza, C.P., Da Silva, A.G.P., Gomes, U.U., De Souza, J.F., Synthesis of Tungsten Carbide through Gas-Solid Reaction at Low Temperatures, Materials Science and Engineering A, Vol. 315, pp. 5862, 2001.
12. De Medeiros, F.F.P., Da Silva, A.G.P., De Souza, C.P., Gomes, U.U., Carburization of Ammonium Paratungstate by Methane: the Influence of Reaction Parameters, International Journal of Refractory Metals & Hard
Materials, Vol. 27, pp. 4347, 2009.
13. McCandlish, L.E., Kear, B.H., Kim, B.K., Chemical Processing of Nanophase WC-Co Composite Powders,
Materials Science and Technology, Vol. 6,
pp. 953957, 1990.
14. Giraudon, J.M., Devassine, P., Lamonier, J.F., Delannoy, L., Leclercq, L., Leclercq, G., Synthesis of Tungsten
Carbides by Temperature-Programmed Reaction with CH4-H2 Mixtures: Influence of the CH4 and Hydrogen
Content in the Carburizing Mixture, Journal of Solid State Chemistry, Vol. 154, pp. 412426, 2000.
15. Davidson, C.F., Alexander, G.B., Wadsworth, M.E., Initial Kinetics of Tungsten Carburization by Methane,
Metallurgic Transactions B, Vol. 9, pp. 553557, 1978.
16. Eroglu, S., Zhang, S.C., Messing, G.L., Synthesis of Nanocrystalline Ni-Fe Alloy Powders by Spray Pyrolysis,
Journal of Materials Research, Vol. 11,
pp. 21312134, 1996.
17. Eriksson, G., Thermodynamic Studies of High Temperature Equilibria, Chemica Scripta, Vol. 8, pp. 100103,
1975.
18. Besmann, T.M., SOLGASMIX-PV, a computer program to calculate equilibrium relationships in complex chemical systems, Report No: ORNL/TM-5775,
Oak Ridge National Laboratory, 1977.
19. Chase, M.W., Davies, C.A., Downey, J.R., Frurip, D.J., Mcdonald, R.A., Syverud A.N., JANAF thermochemical tables, 3rd ed., J. Phys. Chem. Ref. Data 14 (Suppl. l), 1985.
20. Barin, I., Thermochemical Data of Pure Substances, VCH Verlagsgesellschaft, WeinHeim, Germany, 1993.
21. Lfberg, A., Frennet, A., Leclercq, G., Leclercq, L., Giraudon, J.M., Mechanism of WO3 Reduction and Carburization in CH4/H2 Mixtures Leading to Bulk Tungsten Carbide Powder Catalysts, Journal of Catalysis, Vol.
189, pp. 170183, 2000.
22. Leclercq, G., Kamal, M., Giraudon, J.M., Devassine, P., Feigenbaum, L., Leclercq, L., Frennet, A., Bastin, J.M.,
Lfberg, A., Decker, S., Dufour, M., Study of the Preparation of Bulk Powder Tungsten Carbides by Temperature Programmed Reaction With CH4 + H2 Mixtures, Journal of Catalysis, Vol. 158, pp. 142169, 1996.
23. Decker, S., Lfberg, A.,. Bastn, J.M., Frennet A., Study of the Preparation of Bulk Tungsten Carbide Catalysts
with C2H6/H2 and C2H4/H2 Carburizing Mixtures, Catalysis Letters, Vol. 44, pp. 229239, 1997.
389

2014 ALMNYUM - KARBON SSTEMNDE Al4C3 FAZININ SENTEZLENMES

VE SONRASI YALANMA LEMNE ETKS
Sinan AKSZ, A. Tamer ZDEMR
sinanaksoz@hotmail.com, tozdemir@gazi.edu.tr
ZET
2014 Al alam tozlar ve %2 grafit, koruyucu saf Ar atmosferi altnda 7 s mekanik alamlanma ilemine tbi tutulmulardr. Elde edilen karm, 800 MPa basn altnda souk preslenmi ve malzemeler 5500C de, ayn koruyucu
ortamda uzun sre sinterlenmitir. Yaplan analizler, beklenen Al4C3 faz paracklarnn ancak sinterleme srasnda
olutuklarn gstermektedir. Son olarak, 5200C de 2 saat zeltiye alma ileminden sonra su verilen malzemeler,
1500C de 36 saatte kadar belli srelerde yalandrma ilemine tbi tutulmulardr. Mekanik alamlama yaplmadan
preslenip, sinterlenen 2. grup numuneler, yine ayn artlarda yalandrlmlardr.
Bu iki farkl malzeme grubunun yalanma zamanna bal sertlik deiimleri karlatrldnda, mekanik alamlanm malzemelerin dayanmlarnn dikkat ekici biimde artt ve 1500C de ok uzun tavlanmalarna ramen ar
yalanma belirtileri gstermedikleri belirlenmitir.
Anahtar Szckler: 2014 Al alam, Mekanik Alamlama, Yalanma, Al4C3 faz.
SYNTHESIS OF Al4C3 PHASE IN 2014 ALUMINUM CARBON SYSTEM AND

ITS EFECT ON SUBSEQUENT AGEING TREATMENT
ABSTRACT
2014 aluminum alloy powders and 2% graphite dust by weight were mechanically alloyed under the protective atmosphere of purified argon gas for about 7 h. Blended powders were later cold pressed at 800 MPa and then long
term sintered at 5500C under the same gas tight conditions. The expected Al4C3 phase could only be formed during
the process of sintering. Later, samples were solution treated at 5200C for 2 h, then water quenched and finally aged
at 1500C for several time intervals up to 36 h.
Another batch without the preliminary process of mechanical alloying, were similarly pressed, sintered and finally
aged hardened. When the change in hardness with respect to ageing time for each group were compared, it was
found that mechanically alloyed samples substantially reach to high strength values. However, softening due to
over-ageing could not be detected during the period of prolonged annealing at 1500C.
Key words: 2014 Al alloy, Mechanical Alloying, Ageing, Al4C3 phase.
1. GR
Gnmzde, Toz Metalurjisi (TM) ileri malzeme retiminde yaygn olarak kullanlan yntemlerden biridir [1, 2].
Mekanik Alamlama (MA) ise, normalde termodinamik olarak birbirleriyle karm oluturmayan maddeleri kat
reaksiyon teknii ile hzl ve etkin bir ekilde bir araya getirerek, eitli kompozit malzemeleri oluturabilmede temel
yntemlerdendir.
390

MA ileminde, nce tozlar en doru oranlarda kartrlr ve sonra toz haznesinde tc bilyalarla uygun grlen
sre ierisinde hzl bir ekil birbirlerine yerdirilirler [3]. Bylece, birbirlerine adeta atomik boyutta kattrlm yeni
ve farkl kombinasyonlarda alam tozlar oluturulur [4]. MA ile, ana malzemeye parack takviyesi olarak eitli
karbrler ve dier kat paracklar yedirilerek stn zellikte ve yksek performansta eitli kompozit malzemeleri
tasarlayp, retebilmek mmkn olabilmektedir.
zellikle alminyumda, eitli karbr paracklar takviye elaman olarak kullanlmaktadr. Alminyum karbr (Al4C3)
ierii alminyum metal teknolojisinde nemli bir bileen ve elmas bal seramiklerin (Al2O3Al4C3AlN) retimi
balangcnda ilk kullanlan malzemelerden olup, bu yap oda scaklnda yksek termal iletkenlikle birlikte yksek
elektrik direncine sahiptir. Ayrca, Al4C3 ilavesi metal kompozit ve alamlarnn mukavemetlemesini arttrmaktadr
(AlAl4C3, AlSiCAl4C3, AlAl3TiAl4C3, v.b.) [5].
Bilindii gibi, 2xxx ve 7xxx serisi alminyum alamlar neredeyse havaclk tarihi kadar uzun bir sredir hava
aralarnda etkin olarak tercih edilmekte ve arlkl olarak uak kanatlarnda, gvde ve d yzey kaplamalarnda,
perinlerde vs kullanlmaktadrlar. Yeni nesil 2014 alminyum alam, bu sektrde geleneksel olarak tercih edilen
2024 alamnn yerini alm bir malzemedir. Bu alam zellikle scak ekstrzyon ve scak haddeleme ilemleriyle
retilmektedir.
Genellikle ieriinde bulunan bakr, magnezyum, manganez oranlar daha rafine edilmitir. Ayrca, retimden gelen
dier kalnt elementlerin azaltlm olmas, sonraki kat hal ilemleri ve buna bal yapsal tasarm kabiliyetini arttrmaktadr [6]. 2014 alminyum alamnn genel dayanm zellikleriyle korozyon davran 2024 alamna gre
daha gelikindir.
Bu almada, gaz atomizasyon yntemi ile retilmi 2014 tozlar, %2 karbon (C) tozlaryla beraber MA ilemine tbi
tutulmu, presleme ve sinterleme sonras elde edilen malzeme son olarak yalandrlmtr.
15 bar basnl saf argon gaz ile atomize edilen 2014 Al alam tozlarnn dalm aral 20-180 m, ortalama boyu
ise 95 m dir. Bu tozlar, %2 grafit ile harmanlanp, yksek enerjili dikey Atritrde saf Ar gaz atnda MA ilemine
tbi tutulmulardr.
Bir nceki almada olduu gibi ilem, 500 dev. / dak. ve 20: 1 bilye toz orannda gerekletirilmitir [7]. Ancak,
grafit tozuna ilave olarak % 0.5 inko stearat alam sistemine katlm ve en uygun MA sresi olarak tespit edilen
7 saat sre sonuna kadar ilem sorunsuz olarak tamamlanmtr. lem sonunda elde edilen kompozit tozlarnn
ortalama tane boyutu 54,50 m ve toz boyut aral 1,60-331 m arasnda deimektedir. Balangta yaklak 125
HV olan sertlik 7 saatin sonunda 228 HV ye kmaktadr.
MA sonras tozlar, 800 MPa basn altnda preslenmiler ve daha sonra, 550 Cde 4, 8 ve 24 saat sre ile sinterlenmilerdir. Son olarak, malzeme, 5200C de 2 saat zndrldkten sonra su verilmi ve srasyla 1500C de 4, 8,
12, 16, 20 ve 24 saat yalandrlmlardr. Yalanma ncesi mikro-yapda oluturulmu olan Al4C3 paracklarnn
yalanm malzemenin dayanmna olan etkilerini net olarak grebilmek iin; 2ci grup bir malzeme, 2014 tozlarnn MA yaplmadan dorudan benzeri koullarda preslenmesi, sinterlenmesi ve ardndan yalandrlmasyla elde
edilmitir.
Malzeme yapsndaki deiiklikleri tespit edebilmek iin srasyla: Malvern Mastersizer E toz boyutu analiz cihaz,
Cuk =1.5406 ve 2/dakika tarama hznda Bruker D8 XRD analiz cihaz kullanlmtr. Mikro yap incelemeleri
Joel JSM-5600 taramal elektron mikroskobunda, sertlik lmleri ise, Shimadzu Mikro Sertlik cihaznda 100g yk
kullanlarak gerekletirilmitir.
7 saat MA sonunda elde edilen tozlarn XRD analizi incelendiinde beklenen Al4C3 faznn halen olumad anlalmtr (ekil 1). Bu bulgu dier baz almalarda elde edilen sonulara benzerlik gstermektedir [8-11].
Buna karn, MA sonras elde edilen tozlar, preslendikten ve 550Cde uzun sreler tavlanarak, sinterlendikten
sonra XRD analizleri tekrarlandnda, yapda ok yava bir hzda Al4C3 faznn olumaya balad ve Al2Cu faz
krnm tepeleri arasnda zamana bal olarak yavaa ykseldii grlmtr (ekil 2).
391

ekil 1. 7 saat MA ileminden sonra tozlarn XRD

analizleri.
ekil.2. MA ve preslenme
sonras 550 Cde 24 saat
sinterlenmi malzemenin
XRD analizi.
Dier yandan, 5500C de yaplan l ilem sv faz sinterlemesi iin yeterli olduundan, ilem sonras yava souma
sonucu tane snrlarnda youn olarak Al2Cu faznn olutuu grlebilmektedir [12, 13]. ekil 3de, 4 saat sinterlenmi numune mikro-yaps ve element dalm analizi (EDS) grlmektedir. Buna gre, resimde bulunan parlak
blgeler bakrca zengin (Al2Cu) alanlardr ve tane snrlarnda toplanmlardr.
ekil 3. 550 Cde 4 saat sinterlenmi yapda blgelere gre EDS sonular.
Homojenletirme (zndrme) ilemi ile birlikte, tane snrlarndaki Al2Cu zamanla erimekte, su vermenin ardndan
yalandrma ilemiyle, Al2Cu faz mikro-yap ierisinde daha homojen dalmaktadr. te bu yzden, rnein, 550
Cde 24 saat sinterleme sonrasnda 46 saat yalandrlan numunenin Al2Cu oluumuna ait XRD krnmlarnn nispi
olarak alald ekil 4te rahatlkla grlebilmektedir. Ksaca, yalandrma ile birlikte belli blgelerde biriken Al2Cu
miktar azalmaktadr.
ekil 4. MA ve preslenme
sonras 550 Cde 24 saat
sinterlenmi malzemenin 46
saat yalandrma
sonras XRD analizi.
392

MAnn yalanma zerine olan etkisi ise ekil 5de aka grlmektedir. MA ilemi yaplmam malzemenin balangtan gelen sertlik deerleri dktr. Su verme ve tavlama sonras bilinen yalanma mekanizmalaryla belli bir
deere kan dayanm, ksa bir zaman sonra azalmaya balamaktadr. te yandan, MA ilemiyle zaten peklemi
olan alam tozlar, preslendikten sonra sinterleme srecinde youn bir yap olutururken, Al4C3 faznn oluumuyla
ile malzeme yaps kararl hale gelmektedir. Bu yzden, homojenletirme ve su verme sonras ara malzemenin sertlii, MA ilemi uygulanmam malzemenin yalanma ilemi ncesi sertliinden daha yksektir. Yalanma srecinde
ise, balangta MA yaplm malzemede, dayanm ciddi miktarda giderek daha da artmakta ve sertlik deerleri belli
bir platoya eritikten sonra, dayanmda herhangi bir azalma olumamaktadr.
ekil 5. MA sonras 550 Cde

24 saat sinterlenmi yapnn
yalanma sresine bal sertlik
deiimi ile MA yaplmam ve
ayn artlarda yalandrlm
yapnn sertlik deiimiyle
karlatrlmas.
4. SONULAR
Yapda Al4C3 paracklarnn youn olarak bulunmas malzemenin dayanmn artrrken, yalanma sresini de
nemli lde uzatmaktadr. Nano boyda, ok sk dalml ve kararl paracklar [7], MA ile elde edilen souk deformasyon alt yap oluumlarnn zerinde oturduu, onlar hareketsiz kld (veya kararl hale getirdii) ve bylece
toparlanma safhasn bastrd veya teledii bilinmektedir [14-16]. Yalanma ile mikro-yapya ilave edilen Al2Cu
paracklar mikro-yapy daha fazla takviye ederken, daha kararl ve sabit hale getirerek dayanm yksek seviyelere kartabilmektedir. yle ki, malzeme 5500C de uzun sre tavlanmasna ramen mikro-yapda sertlik dne
sebep olabilecek hibir deiim (toparlanma veya yeniden kristalleme) belirtisi grlmemektedir. Ksaca, retilen
bu yeni ve nc malzemenin yapsal zellikleri, yksek scaklk uygulamalarna olduka uygun bir malzeme olabileceini gstermektedir.
KAYNAKLAR
1. Suryanarayana C., Mechanical Alloying and Milling, Progress in Mater. Sci., 46 (2001) 1-184.
2. German R.M., ed. Sarta S., Trker M., Durlu N., Toz Metalurjisi ve Parackl Malzeme lemleri, Trk Toz
Metalurjisi Dernei , Ankara, (2007).
3. Suryanarayana C., Mechanical Alloying, Pergamon Mater. Series, 2 (1999) 49-85.
4. Ruiz-Navas E.M., Fogagnolo J.B., Vlasco F., Ruiz-Prieto J.M., Froyen L., One Step Production of Aluminium
Matrix Composite Powders by Mechanical Alloying, Progress in Composites, 37 (2006) 2114-2120.
5. Solozhenko V.L., Kurakevych O.O., Equation of State of Aluminum Carbide Al4C3, Progress in Solid State
Communications, 133 (2005) 385-388.
6. Kaar H., Atik E., Meri C., The Effect of Precipitation-Hardening Conditions on Wear Behaviours at 2024
Aluminium Wrought Alloy Progress in Mater. Processing Tech., 142 (2003) 762-766.
7. Bostan, B., zdemir A.T., Kalkanl A., Microstructure characteristics in Al-C system after mechanical alloying
and high temperature treatment, Powder Metallurgy, 47:1 (2004) 37-42.
8. Arslan G., Kara F., Turan S., Quantitative X-ray Diffraction Analysis of Reactive Infiltrated Boron CarbideAluminium Composites J. European Ceramic Society, 23 (2003) 12431255.
9. Wu, N. Q., Wu, J. M., Wang, G.X., Li, Z. Z., Amorphization in the Al-C System by Mechanical Alloying, J. of
All. And Comp. 260 (1997) 121-126.
10. Besterci, M., Preperation Microstructure and Properties of Al-Al4C3 System Produced by Mechanical Allying,
Materials and Design, 27 (2006) 416-421.
11. Zhou, Y., Li Z.Q., Structural Characterization of a Mechanical Alloyed Al-C Mixture, J. Alloys and Comp.,414
(2006) 107-122.
12. imir, M., Gngr, ., gel, B., Al-Cu ve Al-Cu-Mg Toz Karmlarnn Azot Atmosferi Altnda Scak Presleme
almalar, 10. Uluslararas Metalurji ve Malzeme Kongresi Bildiriler Kitab Cilt III, 24-28 Mays, stanbul,
1781-1788 (2000).
13. Zhou, J., Duszczyk, J., 1999. Liquid Phase Sintering of an AA2014-Based Composite Prepared from an Elemental Powder Mixture. J. Mater. Sci. 34, (2008) 545550.
14. Doherty R.D., The Deformed State and Nucleation of Recrystallization, Metal Sci., 8 (1974) 132-142.
15. Higgins G.T., Grain Boundary Migration and Grain Growth, Metal Sci., 8 (1974) 143-150.
16. Hoyt J.J., On the Coarsening of Precipitates Located on Grain Boundaries and Dislocations, Acta Metall.
Mater., 39 (1991) 2091-2098.
393

POWDER
PRODUCTION AND
NANO MATERIALS
www.turkishpm.org
394

EFFECT OF PROCESSING DURATION ON MECHANICAL

PROPERTIES OF MG-BASED NANOCOMPOSITES REINFORCED
BY MULTI WALLED CARBON NANO TUBES (MWCNT)
Sardar S Iqbal*, Mustafa Aydin**, Saikat Talapatra***, Peter Filip*, Rait Ko****
Center for Advanced Friction Studies, Mechanical Engineering & Energy Processes, Southern Illinois
University Carbondale, IL sarwatiq@yahoo.com, filip@siu.edu
**
Dumlupinar University, Department of Mechanical Engineering, Main campus, 43100, Kutahya, TURKEY, m_aydin@dpu.edu.tr
***
Department of Physics, Southern Illinois University Carbondale, IL stalapatra@physics.siu.edu
**** Mechanical Engineering & Energy Processes, Southern Illinois University Carbondale, IL, kocr@
siu.edu
*
ABSTRACT
Mechanical properties of Mg-based nanocomposites reinforced with non-heat treated virgin/pristine
multi walled carbon nanotubes (CNT) and prepared by powder metallurgy method, were investigated.
Microstructure was characterized by scanning electron microscopy. The flexural load, Youngs modulus
and failure strain were determined for processing time of 5, 30 and 60-minutes in comparison to pure
Mg. Mechanical strength was found to be dependent on processing time. The maximum load bearing
capability increased by 11% and 6% for nanocomposites prepared for 30 min and 60 min, respectively,
and Youngs modulus increased for 30-minutes processed nanocomposites in comparison to Pure Mg.
However, failure strain of pure Mg was the highest followed by nanocomposites processed for 60-min
due to apparent accommodation of dislocations in pure Mg. SEM of nanocomposites processed for
30-min showed a good bonding of CNT with the matrix, a better dispersion of CNT, with rest of the nanocomposites exhibiting poor bonding. Mechanical strength and microstructure development showed a
strong dependence on dispersion of CNT and processing time.
Keywords: Magnesium, Carbon Nano Tubes, Composite Materials, Mechanical Properties
1. INTRODUCTION
Magnesium (Mg) based composites are more interested due to their potential applications in aerospace,
automotive and sports equipment industries [1]. Mg and its alloys are increasingly used in engineering
structures due to their higher specific strength [2]. Carbon nanotubes (CNTs) have recently emerged as
materials with exceptional properties exceeding those of any conventional material [3-6]. Efforts are being made to incorporate CNT as reinforcement into Mg matrix. Mechanical properties make CNTs ideal
candidates as reinforcements in composite materials to increase both stiffness and strength while also
contributing to weight savings. Carbon nanotubes have emerged as new reinforcements for a number
of material systems including polymeric [7,8], metallic [911] and ceramic [12] matrices.
Numerous research groups have added carbon nanotubes to polymer matrices with the aim of producing conductive and high strength polymers. However, no significant improvement in mechanical properties has been reported. The challenges faced were many, including nanotube agglomeration, and the
lack of control over alignment. Few research groups have investigated either metal or ceramic matrices.
A successful procedure was recently reported MWCNT were incorporated in both aluminum (Al) and
magnesium (Mg) matrices by powder metallurgy (PM) techniques [10,13]. Low-energy ball milling in a
Turbula mixer is used to homogenize the mix followed by compaction into a disc shape, and sintered.
The samples tested exhibited a ductile behavior, but the expected improvement in Youngs modulus was
395

only slightly achieved. The powder metallurgy technique is promising over other techniques such as
pressureless infiltration technique, mechanical alloying and by a powder can rolling technique [2, 14].
Various inadequacies in mechanical properties can be attributed, among several factors such as on
the difficulty of dispersion of CNT and subsequent agglomeration, use of limited amount of CNT, poor
bonding between matrix and CNTs, and the difficulty in the alignment of CNTs in the desired direction
in the matrix [9-11, 14,].
Although such issues have not yet been resolved, extensive efforts are underway to overcome them.
Present study discusses the impact of mixing duration of CNTs in Mg matrix on the mechanical properties.
2. EXPERIMENTAL PROCEDURES
In the present study, powder metallurgy method was used for the preparation of a CNT within Mg powders by ball milling mixing machine. Pure magnesium powder (99.9% pure, -325 mesh in size) from Alfa
Aesar was used as metal matrix. The multi wall carbon nano tubes (MWCNTs) produced by chemical
vapor deposition (CVD) process were used as reinforcements for the fabrication of nanocomposites.
Mg-nanocomposites were prepared by mixing CNTs at ratio of 1 % by weight. The mixing was performed
by high energy ball milling machine (Turbola spex 8000). The mixing duration was 5, 30, and 60 minutes. The mixture of Mg and CNTs was cold pressed at 700 MPa. Mg-nanocomposites were sintered at
620 oC under argon atmosphere for 2 hours in tube furnace. The density was measured by mineral spirit
method using Archimedes principle by taking average of three readings. The flexural tests were carried
out in Instron 4202 Universal testing machine at cross head speed of 0.2mm/min. The microstructure
of fractured surfaces of the nanocomposites was studied and analyzed using scanning electron microscopy Hitachi S-570.
Figure 1 shows the density and porosity of pure Mg and Mg-nanocomposites. It is apparent that the density of pure Mg is the highest, and reduced significantly after incorporating 1% CNT by weight. On the
other hand, pure Mg shows minimum level of porosity, whereas Mg-nanocomposites show progressive
increase in the porosity with increasing CNTs. Since the steady decrease in density and an increase in
porosity is due to the increase in the ratio of CNTs. This indicates that although, the decrease in density has occurred due to CNT reinforcements, yet an appreciable increase in porosity is observed, and
indicates the less effective homogeneous distribution of the CNTs in Mg-matrix, as the clustering of the
CNTs is unavoidable due to the sheer size of the CNTs at the nano levels. Goh et al. [15] also reported
on the decrease in the density of nanocomposites with increasing CNTs. Goh et al. [16] reported a similar case, and attribute it to the addition of lighter weight CNTs or the increase in porosity in the Mg matrix.
Esawi et al. [14] attributed the lower densification to the CNT clustering present in the material.
Figure. 1 Density and porosity of Pure Mg and Mg-nanocomposites.

Goh et al. [16] reported a decrease in ductility with increasing CNT contents, and attributed it to agglomeration of CNT becoming cluster which prevent the bonding between Mg and CNTs. Ultimately,
the nanocomposites are inherently prone with pre-existing cracks. These cracks are nucleation sites for
396

instability, and leads to the failure of the material. Goh, Lee and Gupta [15] reported that the increase
in porosity affects the integrity of the material, and attributed the existence of porosity to the clustering
of CNTs.
Figure 2 shows specific mechanical strength of the Mg-nanocomposites mixed for 0, 5, 30, and 60 minutes. It is apparent that the Mg-nanocomposites mixed for 30-minutes exhibit highest modulus closely
followed by Mg-nanocomposites mixed for 5-minutes. The lowest modulus was exhibited by Mg-nanocomposites mixed for 60-minutes. The specific strength of Mg-nanocomposites mixed for 30-minutes
was the highest followed by Mg-nanocomposites mixed for 60-minutes. The specific strength of pure Mg
was the lowest. Pure Mg exhibited the highest failure than the Mg-nanocomposites, which was followed
by Mg-nanocomposites mixed for 60-minutes. The Mg-nanocomposites mixed for 5-minutes exhibited
the lowest failure, and was followed by Mg-nanocomposites mixed for 30-minutes. Pure Mg showed
highest fracture energy followed by Mg-nanocomposites mixed for 60-minutes, and could be attributed
to higher failure strain. The lowest fracture energy is exhibited by Mg-nanocomposites mixed for 5-minutes, and was followed by Mg-nanocomposites mixed for 30-minutes.
Figure.2 Specific strength of Mg-nanocomposites for different mixing duration.

Li et al. [17] reported that the compression mechanical properties of the MWNT/Mg composites. The
compression at failure, the compressive yield strength and ultimate compressive strength reportedly
improved significantly up to 36% by only adding 0.1wt% MWNTs to the Mg alloy. Multiwall carbon nanotube/pure magnesium composites by a powder metallurgical method were produced, and found out
that the Youngs modulus increased 9% in comparison to pure Mg by adding 2 wt% CNTs [13, 18].
Shimizi et al. [19] fabricated 1 wt% of short and straight carbon nanotubes reinforced Mg alloy composites by a vacuum hot pressure method followed by extrusion. The yield strength, the tensile strength and
the Youngs modulus of the CNT/Mg composites reportedly improved by 23%. It is known that the CNTs
have high aspect ratio, which makes it possible to acquire smaller interparticle spacing in the matrix at
very low concentrations compared to other traditional reinforcements in powder form. Therefore, CNTs
can act as obstacles to dislocation movement in metals. Plastic deformation occurs if the dislocations
circumvent the obstacle or shear the nanotube. Due to CNTs smaller diameter , shear appears to be
the most likely mechanism. It would mean that dislocations are held up at and around the CNT, and the
stress concentration at the head of the pile-up group of dislocations causes the CNT to yield by deformation or fracture. Additionally, CNT are able to bridge the crack opening and crack bridging at the submicron and nano levels. In the case of obstacles with high aspect ratio, dislocations cannot easily climb
to circumvent the obstacle, so an improvements of flow stress and toughness can be expected.
397

Figure. 3 Mechanical strength and

failure of nanocomposites mixed for
different time.
Figure 3 shows the strength and failure displacement of nanocomposites. It is apparent that the introduction of CNT increased the load bearing capability of Mg metal by incorporating 1% CNT by weight.
The load bearing capability progressively increased with increasing mixing time, and maximum load
bearing capability is shown by Mg-nanocomposites mixed for 30-minutes. Subsequently, further mixing
time reduced the load bearing capability of Mg-nanocomposites mixed for 60-minutes. On the other
hand, Pure Mg showed higher failure resistance than the nanocomposites. The failure resistance of nanocomposites, progressively increased with increasing mixing time, which shows that nanocompsoites
are losing characteristics of pseudo fiber reinforce composite and are readily becoming homogenized
mixture of comparative particle size of Mg and CNT due to extensive crushing of CNT into progressively
finer bits and particles.
Figure 4 shows the SEM micrographs of fracture surfaces of Mg-nanocomposites for 30, and 60 minutes
mixing. It is apparent that Mg-nanocomposites mixed for 30-minutes show CNTs (in insert of SEM image, a) which are longer. However, Mg-nanocomposites mixed for 60-minutes show negligible traces
of CNTs of longer lengths, which indicates that the crushing of the CNTs occurred extensively, and
changed the CNT into a finer particle form and, therefore, losing the characteristics of CNT as fiber
reinforcement when compared with the Mg-nanocomposites mixed for 30-minutes. This also explains
the ductile behavior of the Mg-nanocomposites mixed for 60-minutes as the dislocations are easily accommodated due to comparative sizes of the constituents. It can be seen that the nanocomposite mixed
for 30-minutes have more agglomerated areas whereas Mg-nancomposite mixed for 60-minutes shows
no such behavior. The, CNTs can act as obstacles to dislocation movement in metals, however, unlike
Shimizi et al. [19], no significant plastic deformation is observed in the current Mg-nanocomposites.
Figure.4. The SEM

images of the Mg-CNT
composites mixed at
different duration (a)
30 min; (b) 60min. The
micron bar in insert in
(a) is 800nm; and in (b)
micron bar is 100nm.
398

4. CONCLUSIONS
1) Mg nanocomposites exhibited a lower density after incorporating CNT in comparison to pure Mg. The
porosity increase could be attributed to clustering of CNTs. SEM images of nanocomposites mixed
for 30-minutes exhibited longer CNTs, whereas nanocomposites mixed for 60-minutes showed negligible CNTs.
2) Mg-nanocomposites mixed for 30-minutes exhibited higher mechanical strength and modulus
among Mg-nanocomposites and pure Mg. The lowest strength was shown by pure Mg.
3) Mg-nanocomposites prepared by powder metallurgy showed that mixing duration impacts the overall mechanical and microstructural properties of the composites.
ACKNOWLEDGEMENTS
The authors would like to TUBITAK (The Science and Technological Research Council of Turkey) for
financial support during the post doctoral programmed at the Southern Illinois University,USA.
References
1. C. S. Goh, J. Wei, L. C. Lee and M. Gupta1. Development of novel carbon nanotubes reinforced
magnesium nanocomposites using powder metallurgy technique SIMTech technical reports
(STR_V9_N3_04_JTG) Volume 9 Number 3 Jul-Sep 2008.
2. Naing Naing Aung, Wei Zhou, Chwee Sim Goh, Sharon Mui Ling Nai, Jun Wei. Effect of carbon
nanotubes on corrosion of MgCNT. Composites. Corrosion Science 52 (2010) 15511553.
3. De Heer W. Nanotubes and the pursuit of applications. MRS Bull 2004:281.
4 Demczyk BG, Wang YM, Cumings J, Hetman M, Han W, Zettl A, et al. Direct mechanical measurement of the tensile strength and elastic modulus of multiwalled carbon nanotubes. Mater Sci Eng A
2002;334:1738.
5. PJF Harris. Carbon nanotubes and related structures: new materials for the twenty-first century.
Cambridge University Press; 2001.
6. RS Ruoff, D Qian, WK Liu. Mechanical properties of carbon nanotubes: theoretical predictions and
experimental measurements. CR Phys 2003;4:9931008.].
7 ET Thostenson, C Li, Chou Tsu-Wei. Nanocomposites in context. Compos Sci Technol 2005;
65:491516.
8. Thostenson ET, Ren Z, Chou T. Advances in the science and technology of carbon nanotubes and
their composites: a review. Compos Sci Technol 2001;61:1899912.
9. Laha T, Agarwal A, McKechnie T, Seal S. Synthesis and Characterization of plasma spray formed
carbon nanotube reinforced aluminium composites. Mater Sci Eng A 2004;381:24958.
10. Carreno-Morelli E, Yang J, Schaller R, Bonjour C. Carbon nanotube reinforced metal matrix composites. In: Proceedings of EURO PM 2003, October 2022, 2003, Valence, Spain.
11. Zhong R, Cong H, Hou P. Fabrication of nano-Al based composites reinforced by single-walled
carbon nanotubes. Carbon 2003;41:CO1-851.
12 .
Peigney A, Laurent Ch, Flahaut E, Rousset A. Carbon nanotubes in novel ceramic matrix
composites. Ceramics Int 2000; 26: 67783.
13. Carreno-Morelli E, Yang J, Couteau E, Hernadi K, Seo JW, Bonjour C, et al. Carbon-nanotube/magnesium composites. Phys Stat Sol 2004; 201(8):R535.
14. Amal M.K. Esawi , Mostafa A. El Borady. Carbon nanotube-reinforced aluminium strips. Composites Sci. & Technology 68; 2008: 486-92.
15. C.S. Goh, J. Wei, L.C. Lee, M. Gupta. Simultaneous enhancement in strength and ductility by reinforcing magnesium with carbon nanotubes. Materials Science and Engineering A 423 (2006)
153156.
16. CS Goh, J Wei, LC Lee, M Gupta,. Development of novel carbon nanotube reinforced magnesium
nanocomposites using the powder metallurgy technique. 2006 Nanotechnology, doi:10.1088/09574484/17/1/002.
17. Qiangqian Li, Andreas Vierecki, Christian A Rottmair, Robert F. Singer. Improved processing of CNT/
Mg alloy composites, Composites Science & Technology 69(7-8); 2009: 1193-99.
18. Song Hai-Yang and Zha Xin-Wei,. The effects of boron doping and boron grafts on the mechanical properties of single-walled carbon nanotubes 2009 J. Phys. D: Appl. Phys.42 225402
doi:10.1088/0022-3727/42/22/225402
19. Shimizu Y. Multi-walled carbon nanotube-reinforced magnesium alloy composites Scripta. Mater.
2008: 58; 26770.
399

Production of In-situ Cu/TiO2 Nano-composites &

Evaluation of Physical and Mechanical Properties
Amir Hossein MOGHANIAN*,Kazem PURAZRANG* ,
Parvin ABACHI* and Fahimeh SHOJAEEPOUR*
Dept. of Materials Sci. and Eng., Sharif Uni. of Tech., Azadi Ave., Tehran, Iran,
abachi@sharif.edu, f.shojaeepour@gmail.com, abapar1390@yahoo.com, purazrang@sharif.edu
*
Abstract
Copper matrix composites reinforced with TiO2 particles, because of good electrical and thermal conductivity and
strength at high temperature, are suitable for contact materials. At present work, Cu/TiO2 nano-composites, containing different amounts of TiO2, were produced by in-situ oxidation of Cu-Ti pre alloyed powders. The morphology of
milled powders and microstructure of nano-composite specimens were studied using SEM. To evaluate mechanical alloying progress of Cu and Ti powders mixture and internal oxidation after Cu2O addition, XRD analysis were
carried out. Physical and mechanical properties results of nano-composite specimens indicate the density, specific
electrical resistivity, hardness and wear rate values alternation with amount of TiO2 in Cu matrix .
Keywords: Copper matrix nano-composite; TiO2 particles; Internal oxidation; Specific electrical resistivity, Wear
rate.
1. Introduction
Oxide dispersion strengthened (ODS) copper matrix composites are known as highly thermal and electrical conductive materials with high strength at room and elevated temperatures [1].It has been realised that the performance of
moving electrical contacts is greatly governed with friction and wear of the contact surfaces, so that, their motion in
operation leads to formation of wear particles and contamination on contact spots and current passage breakdown
[2]. Therefore, evaluation of tribological behaviour of contact materials and improvement of contact quality, reliability
and durability is necessary. Referring to other works, wear resistivity of copper base composites containing fine
particles as reinforcement is noticeably higher than pure copper [3].
Internal oxidation, as in-situ production route of ODS materials, has been the subject of numerous investigations
during the past decade. This process has two major benefits, firstly, it can prevent the formation of external oxide
scale and secondly, internal oxidation provides a method of introducing second phase particles into an alloy which
can affect the mechanical and other properties of alloys [4]. The Cu/Al2O3 as a representative of these composites
owing almost identical electrical and thermal conductivity like as copper, represent higher strength in comparison
to pure copper [5]. Cu/Al2O3 nano-composites are proper in use as contact materials but the duration of internal
oxidation, during internal oxidation of Cu (Al) solid solution is too long and the complete oxidation and therefore
perfect elimination of Al from Cu lattice is difficult to achieve [6]. The remained solute Al in Cu will lead to decrease
in electrical conductivity of the composite [7]. Referring to the equilibrium phase diagram of Cu-Ti, solubility of Ti in
Cu is limited and less than 6 weight percent at 1143K and very negligible at room temperature. Additionally; due to
solubility limitation curve, extraction of remained titanium from copper lattice with subsequent heat treatment is possible. Moreover, oxidation rate of Ti is more than Al. Due to limited works on Cu/TiO2 composite as materials used
in electrical contacts, the present work concentrates on this system. Cu/TiO2 nano-composites has been produced
by in-situ internal oxidation of Cu-Ti alloyed powder. In order to investigate the effect of various amounts of TiO2
particles on the density, electrical conductivity, hardness and wear rate of Cu/TiO2 nano-composites, the Ti values
was selected at the range of 1-3 wt.%.
400

The elemental Cu (ME-1.12097.0500), Ti (purity of 99%, d<10m) powders and Cu2O powder (AC-19742.0500)
served as starting materials. At the initial stage, elemental Cu and Ti powders were mechanically alloyed for 60h in
argon atmosphere in Fritsch6 planetary ball. The stainless steel balls to powder weight ratios (BPR) and mill rotation speed were selected as 20:1, 10:1 and 250 rpm, respectively. Considering the Ti content in the range of 1-3
wt.% in Cu-Ti powder composition, the amounts of reaction products and X values were calculated according to
stochiometric oxidation reaction of Ti according to following reaction:
The theoretical values of TiO2 are presented in table 1. To specify pressed and sintered specimens, in continue the
capitals P and S will be added, respectively. Referring to Murty and et.al [8], the large lattice strain generation due
to Ti solution in Cu, some amounts of Ti can remain insoluble. Apparently, the insoluble Ti in Cu lattice can lead to
formation of coarse TiO2 particles.
Table 1. Theoretical values of TiO2 in Cu/TiO2 nano-composites according to different quantity of Ti in Cu-Ti alloyed powders
1
2
TiO2, wt.%
(vol.%)
1.66 (3.45)
3.33 (6.80)
Ti, wt.%
(10.03)
Specimen
Designation
C1
C2
C3
Following mechanical alloying, the Cu-Ti alloyed powder and Cu2O were milled for 10h under Argon atmosphere. To
prevent oxidation of very fine powder particles, compacting was firstly conducted in a hot press under 30MPa applied pressure at 400C in glove box. For more densification of specimens, a cold press was performed at 400MPa.
Internal oxidation completion was carried out during sintering at 800C for 1h. The heating rate was considered as
5C/min. The specimens were cooled down in the furnace.
X-ray diffraction analysis was used to determine progress of mechanical alloying process during milling and to
detect TiO2 formation after sintering. The density value of specimens was specified by usual Archimedes method
using precise balance model CP324S-Sartorius with an accuracy of 0.1mg. The electrical resistivity was measured
by micro-ohmmeter LOM-D500 working based on Kelvin Bridge. The specific electrical resistance were then determined considering specimens dimensions. The Vickers hardness was measured under applied load of 5 N. Dry sliding wear tests were carried out according to ASTM G-99 standard using pin-on-disk equipment. The pins having
a diameter of 5 mm and a length of 10 mm slide against the steel counter-face with 67HRC hardness. The sliding
speed and normal load were 0.25 m/s and 20 N, respectively. The sliding distances were selected as 1000, 2000
and 3000 m. The weight loss was measured using a precise electronic balance and converted to volume loss knowing the density values of specimens. The wear rate was given as volume loss per unit sliding distance. To study the
wear mechanisms of the specimens, worn surfaces of the pins were investigated using SEM and EDS analysis.
In order to determine the proper mechanical alloying time and BPR values with less contamination and efficient
alloying, milling process were performed in different times. Finally, the work was concentrated on two milling times
of 40 and 60hrs and BPR of 10:1 and 20:1. Figure 1 shows SEM micrographs of Cu-2wt.% Ti powder milled at
different conditions. In fact, flat like powder particles in figure 1a and 1b, indicate that more time is required to reach
a proper state between cold welding and fracturing of powder particles. Milling in almost 60 hours with BPR 20:1
not only decreases average particle size but also makes particles morphology relatively equi-axed. A decrease in
powder particle size and formation of thin layers between different particles make the atoms diffusion path shorter
and therefore facilitates formation of alloys. As shown in figure 1c, particle size of powders milled for 60hr with BPR
20:1 is less than the others. Additionally, the particles morphology indicate that an equilibrium state between cold
welding and fracture of powder particles has been achieved. However, to confirm suitability of selected milling time
and ball to powder weight ratio (BPR) for mechanical alloying of Cu-Ti system, X-ray diffraction was also applied to
the Cu-Ti alloyed powders after 60 hours with BPR 20:1. The XRD results of Cu-2wt.% Ti powder after mechanical
milling in different conditions are shown in figure 2.
401

Figure 1. Morphology of Cu-2wt.%Ti powder after mechanical milling of (a) 60 hrs with BPR 10:1, (b) 40 hrs with
BPR 20:1, (c) 60 hrs with BPR 20:1.
Figure 2. XRD analysis of Cu-2wt.%Ti powder after mechanical milling of 60 hrs with BPR 10:1 and 20:1
The intensity of the peaks decreases with increasing of BPR. This can be related to grains refinement, increase of
lattice strain along with increasing of dissolved Ti in Cu. Determination of crystallite size and lattice strain from the
XRD data and using the Williamson-Hall equation [9], confirms this comment. During milling of elemental Cu and Ti
powders, Ti dissolves in Cu, progressively. Since, atomic radius of Ti (2.93A) is larger than Cu (2.56A), the lattice
parameter of Cu should be increased. Therefore, according to Braggs law and considering direct dependence of
lattice parameter to lattice planes distances, XRD peaks of alloyed Cu should be shifted to lower values. However,
due to low difference in atomic radius of Cu and Ti, the displacement of peaks is very negligible. In addition, dissolving of limited amounts of oxygen atoms and their placement on interstitial sites of copper lattice would lead to strong
decrease of lattice parameter due to large difference in the atomic radii [10]. It should be noted that, the solution of
Fe atoms originated from milling jar and balls has the same effect. Another possibility for unexpected values is
formation of stacking faults during intense milling of copper having low stacking fault energy. Consequently, these
faults may cause a peak shift opposite to that caused by the dissolved atoms with atomic size of more than that of
Cu [11]. Referring to XRD analysis, it can be concluded that following the particles refinement and formation of thin
layers of Cu and Ti, after milling 60 hrs with BPR 20:1, Cu-Ti solid solution can be mainly formed.
The XRD results of pressed and sintered specimens of C1P and C1S, are shown in figure 3. It seems that, after
sintering, due to extraction of Ti atoms from Cu lattice and internal oxidation, diffraction peaks move to that of pure
402

Cu peaks again. The intensity increment of the peaks is also sensible. However, due to very low amount of TiO2
(max. 3.45 vol.%) and small particle size, the diffraction peaks of TiO2 are not appeared for this specimen.
Referring to SEM micrograph of Cu/TiO2 nano-composite in figure 4, average grain size is near 50 nm. The TiO2
particles as light regions, are smaller than 100 nm. However, the insoluble Ti in Cu lattice can lead to formation of
coarser TiO2 particles, with a size which depends on Ti particle size.
Figure 3. XRD results of Cu-Ti -Cu2O powders after pressing and sintering (C1P and C1S specimens)
Figure 4. SEM micrograph of Cu/TiO2 nano-composite ( C1S)

The specified physical and mechanical properties values of pressed and sintered specimens are presented in tables 2 and 3. As it can be seen, due to presence of Ti in Cu lattice and formation of solid solution, remained porosity,
presence of Cu2O and probably some TiO2 particles, specific electrical resistivity of pressed specimens increases
with increasing Ti content. In general, the values are higher than that of the of pure Cu which is equal to 1.7241.
cm. The specific electrical resistivity of Cu/TiO2 composites increases also with increasing the amount of TiO2 particles. Two important strengthening and hardening mechanisms can be considered in the Cu/TiO2 nano-composite
produced by in-situ oxidation: the oxide dispersion strengthening according to Orowan mechanism and refined
grains strengthening according to Hall-Petch relation [12].
Table 2. Properties of pressed specimens
Density
(g/cm3)
Specimen Designation
Specific electrical resistivity

(.cm)
C1P
C2P
7.2
7.05
3.34
5.92
C3P
6.83
7.22
Table 3. Properties of sintered specimens

Specimen Designation
C1S
C2S
C3S
Density
(g/cm3)
7.74
7.31
7.11
Specific electrical resistivity

(.cm)
1.95
2.79
7.19
403
Hardness
(HV)
75.3
87.8
96.5

To investigate wear behaviour of Cu/TiO2 nano-composites dry sliding wear tests were carried out according to
ASTM G-99 standard using pin-on-disk equipment. As shown in figure 5 a, by increasing the sliding distance, the
amount of the specimens volume loss increases. As the reinforcement particles, TiO2, increases, the volume loss
decreases. Figure 5 b shows the wear rate of Cu/TiO2 nano-composite versus TiO2 particles. The lowest wear rate
belongs to C3S specimen.

(a)
(b)
Figure 5. (a) Wear volume loss dependence to sliding distance and (b) Wear rate of sintered specimens
containing different amounts of TiO2 particles
Figure 6 shows worn surfaces of C2S nano-composite after sliding of different distances. Sliding speed and normal
load are constant and equal to 0.25 m/s and 20 N, respectively. Grooves and channels parallel to the wear direction
in figure 6a indicate an abrasive wear. Increasing the sliding distance causes the formation of some cracks perpendicular to the wear direction in the specimen surface which is indicative of the delamination dominance in high
distances. In addition, as the sliding distance increases to 2000 m, the depth and width of the grooves increases.
The EDS results in table 4 confirm an increase in oxygen content in the wear surfaces with increasing the sliding
distance from 1000 to 3000m. Due to friction between composite pin and counter-face disk surfaces, the temperature of surfaces increases to the level in which an oxide phase forms. As indicated in table 4c, the oxidation wear
mechanism can be more effective after 3000 m sliding.
Figure 6. SEM images of worn surfaces

of C2S specimen after sliding distances
of (a) 1000, (b) 2000, (c) 3000 m,
404

Table. 4. EDS analysis of worn surface of C2S specimen after sliding of (a) 1000, (b) 2000, (c) 3000 m
4. Conclusions
A study on the effect of milling condition and Ti content on the formation of in-situ TiO2 particles in Cu matrix composites and evaluation of some physical and mechanical properties reveal the followings :
1- Formation of TiO2 particles can be proceed by mechanical milling and subsequent sintering of Cu(Ti)-Cu2O
powders mixture.
2- The density of Cu/TiO2 nano-composites decreases with increasing TiO2 particles content having lower density
in comparison to Cu matrix.
3- Specific electrical resistivity and hardness of Cu/TiO2 nano-composites increases with increasing oxide particles content.
4- Increasing the sliding distance causes an increase in the rate of wear volume loss, especially in the case of
specimens with low content of particles correspoding lower wear resistance.
5- At low sliding distance, the dominant wear mechanism is abrasive, whereas, at higher sliding distance the delamination and oxidation mechanisms can perform greater role.
405

REFERENCES
[1] J.Y. Cheng, M.P. Wang, Nano scale Al2O3 dispersion-strengthened copper alloy produced by internal oxidation,
China-EU Forum on Nanosized Technology, pp. 93-101, 2002.
[2] M. Braunovic, V.V. Kochits and N.K. Myshkin, , Electrical contacts : fundamental, applications and technology,
pp. 373-376, 2007, NY., CRC Press.
[3] P.K. Deshpande, R.Y. Lin, Wear resistance of WC particle reinforced copper matrix composite and the effect of
porosity, Material Science and Engineering A, Vol. 418, pp. 137-145, 2006.
[4] S.Wood, D. Adamonos,Internal oxidation of dilute Cu-Ti alloys, Metallurgical Transaction, Vol. 6, pp. 17931794, 1975.
[5] Z. Shi, M. Yan, The preparation of Al2O3- Cu composite by internal oxidation, Applied Surface Science, Vol.
134, pp. 103106, 1999.
[6] S. H. Liang, L. Fang, Z. K. Fan., Effect of powder characteristics on Cr internal oxidation for preparation of Cr2O3/
Cu composite, Materials Science and Technology, Vol. 20,pp. 800-803, 2004.
[7] S.H. Liang, L. Fang, Internal oxidation of Cr in Cu-Cr/Cu2O composite powder prepared by mechanical activation Material Science and Engineering A, Vol. 437, pp. 27-33, 2004.
[8] B.S. Murty, M. Mohan Rao and S. Ranganthan,Nanocrystalline phase formation of solid solubility by mechanical
alloying Nanostrutured materials, Vol.3. pp.459-467, 1993.
[9] G.K. Williamson, W.H. Hall, Acta Metall, vol. 1, pp. 2231, 1953.
[10] E. Botcharova, M. Heilmaier, J. Freudenberger, G. Drew, D. Kudashow, U. Martin, Supersaturated solid solution of niobium in copper by mechanical alloying, jourmal of Alloys and Compounds, Vol. 351.pp. 119-125,
2003.
[11] C. Suryanaryana., Mechanical alloying and milling, Prog. Mater. Sci., Vol. 46, pp. 1-184, 2001.
[12] S.J. Hwang, J.H. Lee, Mechanochemical synthesis of Cu-Al2O3 nano-composites, Material Science and
Engineering A, Vol. 405, pp. 140-146, 2005.
406

Researches regarding the obtaining of cermet type

mixtures from TiC-WC-(Ni,Co)-Al2O3 and TiC-(Ni,Co)-Al2O3 systems
Emilia Maria Coman (Ciovica)*, Irina CARCEANU**
*
VALAHIA University of Targoviste, 2nd Carol I Street, code 130024, Targoviste, Dambovita Romania,
emilia_ciovica@yahoo.com
**
Metallurgical Research Institute of Bucharest, 39 Mehadia Street, code 060543,
6 County, Bucharest Romania, irina_carceanu@yahoo.co.uk,
ABSTRACT
The paper presents the results of experiments effectuated to obtain some intimate mixtures based on cermets
with a high level of TiC, special alumina Al2O3 and different concentrations of metal binder Ni/Co. We present the
physical-chemical characteristics of sinterized benchmarks made of hard composites of Cermet type.
Keywords: cermets; intimate mixtures, cutting plates.
1. INTRODUCTION
The technological evolution in the field of powder metallurgy is related in the last decade by the appearance and
development of some new methods to obtain composite materials with hi-tech characteristics, methods allowing the
creation of new materials with superior mechanical properties to the existing ones obtained either by modifications
of the chemical composition or by modifications in terms of the obtaining method.
The use stresses specific to the more and more complex mechanical processing by chip removal as well as the
emphasis on the increase of productivity have led to the elaboration of new materials obtained by the application
and development of some advanced technologies that may allow the obtaining of some products with hi tech characteristics; they must simultaneously have high values of the triplet hardness (wear resistance) tenacity (bending
resistance) chip removing speed as well as properties of mechanical shock resistance, corrosion and oxidization
at high temperatures appearing during their use. Regardless of the appearance, development and implementation
in industry of some advanced technological processes, the mechanical processing, especially the chip removal, still
occupies a dominating position.
The variety of processed materials and the processing conditions on plants in full diversification, the complexity of
the tribo-technical processes during chip removal as well as the numerous factors influencing the operation characteristics of the cutting tool have triggered worldwide, among the famous manufacturers in the field of processing
the hard alloy powders, preoccupations focusing on a series of aspects such as:
Obtaining the optimal geometry of the cutting plates depending on the characteristics of the cutting process;
Extending their field of use while restraining the range of powders used;
Design of some materials that might make possible the mechanical processing at higher and higher speeds
in absence of vibrations.
Cermet is a term used for a wide range of materials and, in accordance with the definition from Metals Handbook
cermet is a product of powder metallurgy made of ceramic particles bound in a metal matrix (see [1]).
Cermets are materials made of heterogeneous compositions of one of several ceramic phases wit metals or alloys
having a set of properties resulted from the combination of qualitative characteristics of the initial constituents and
also new properties that may no be encountered in the latter ones. Cermets have a set of physical-mechanical properties allowing their use in different technical fields for heavy duty work as materials resistant to high temperatures,
materials with a special refractoriness, materials resistant to oxidization at high temperatures, materials resistant to
corrosion in acid environments, materials resistant to wear [2].
407

Depending on the basic component, cermets fall into: oxydic cermets (oxide-metal) and non-oxydic cermets such
as those based on carbides (carbide-metal), nitride-based cermets (nitride-metal) or boride-based cermets (boridemetal). Carbide-metal cermets represent the largest class of composite materials being discovered since 1922. This
important invention consisting in the making of a combination between a hard component, namely wolfram carbide
(WC hexagonally compactly crystallized) with a ductile phase as binder - cobalt (Co), was the reason for the setting up of WIDIA company in Germany [3]
After a couple of years, they started the development of the titanium and nickel carbide-based materials, (TiC-Ni)
under the clear denomination of cermets. In current practice for the composites used in the processing of metals by
chip removing, the term cermet is used to define the tool materials based on titanium carbonitride (TiCN) bound with
nickel (Ni) and/or cobalt (Co), with the possibility to add some different carbides [4]. This terminology will apparently
help to tell these types of materials for cutting tools from the conventional ones based on wolfram carbide (WC),
though titanium carbonitride is not at all more ceramic than wolfram carbide[5].
At the same time, the complexity of the increasing processing operations has led to the appearance of some problems in terms of chi removing after the processing by chip removing of very small depth and high speed; the cutting
tools executed from such materials need sharp cutting edges that may be executed at a high qualitative level from
cermets as compared to those executed from conventional hard alloys with or without cover layers [6].
2. EXPERIMENTAL CONDITIONS
To execute the cutting plates, we tried to obtain some composition recipes of CERMET type CERMET with a high
content of TiC (superior to 25 %), different concentrations of metal binder Ni/Co and special alumina Al2O3.
The chemical composition of the powder mixtures was: TiC = 75 %; WC = 10 %; Co = 5 %; Ni = 5 %; Al2O3 = 5
% - for system (TiC - WC - (Ni, Co) - Al2O3) and: TiC =
75 %; Co = 5 %; Ni = 5 %; Al2O3 = 15 % - for system
(TiC - (Ni, Co) - Al2O3). The binder temporarily used to obtain some powder homogenous mixtures was transparent
A type paraffin [7].
The experimental works for the execution of the compositional systems of the type (TiC WC - (Ni, Co) - Al2O3 ) and
(TiC - (Ni, Co ) - Al2O3) consisted in:
choosing the raw materials;
characterization of the elementary powders and processed powders according to the standards in force;
obtaining the experimental powdery mixtures used to obtain cermets;
To obtain the basic mixtures based on cermets, we used the following powders:
wolfram carbide powder WC (from PLANSEE company AUSTRIA);
cobalt powder Co (from TIZIT company AUSTRIA);
nickel powder Ni (from TIZIT company AUSTRIA);
special calcinated alumina powder Al2O3 (ICEM Bucharest).
The properties of the powders used within the experimental works to obtain the mixtures used in the obtaining of
cermets are given in table 1a [4] and their supplementary characterization was made according to the international
standards in force being presented in table 1b.
Table 1a. Properties of powders used in the execution of the cermet-based mixtures
Material
Vickers
hardness
[HV50]
Crystallographic
structure
Melting
temperature [C]
Specific density Elasticity module

[g/cm3]
[Gpa]
WC
2200
hexagonal
2800
15.63
696
TiC
3000
cubic
3100
4.94
451
TaC
1800
cubic
3800
14.50
285
Co
< 100
Cubic /
hexagonal
1495
8.9
207
Ni
< 100
cubic
1455
8.9
207
408

Table 1b. Characteristics of the powders used in the execution of cermet-based mixtures
Powder type
WC
TiC
TaC
Co
Ni
Al2O3
Average particle diameter,

Fischer [m]
1.50
2.00
1.95
1.00
1.50
Initial: 4-5;
After : 2.0
Flow rate
[sec/100g]
37
33
31
it doesnt flow
35
Apparent freely poured density

[g/cm3]
7.83
2.28
6.55
3.46
2.30
it doesnt flow
3.70
In table 2, we present the physical-chemical characteristics of the special alumina used[7].

Special alumina used has a content of 1% Cr2O3 having the same role with that of Cr3C2 in case of metal carbide
powders, namely an inhibitor of granulation increase in sinterized structure.
Table 2. Physical-chemical characteristics of calcinated alumina powder
Material
Al2O3
[%]
Fe2O3
[%]
Alkalis
[%]
Humidity
[%]
SiO2
[%]
Al2O3
[%]
Specific density [g/

cm3]
Special alumina
cca. 99,5
max.
0,20
max.
0,15
max. 0,5
max.
0,15
cca. 98
3,70
The special alumina powder having an average diameter of particles of 4-5 m was subjected to grinding for 16
hours to obtain a granulation as close as possible to the metal carbide powders used. Thus, following the grinding
operation executed in Attritor, the average diameter of the alumina particles was 2 m.
Attritor mills are made of a cylindrical vertical tank where the grinding ball load is activated by means of a vertical
stem and a set of horizontal arms. These arms are arranged perpendicularly on the vertical stem and they carry
along the balls by the rotation movement. Balls will move at first together with the stem arms, then they will be carried along in a falling movement triggering the collision among them and with the processed material.
Collision may occur among balls, between balls and the tank walls and between balls, the stirring arm and arms.
Grinding occurs due to collisions and frictions. The mills of this type are produced in a wide range of capacities
(1-1000 dm3), they may have variable speeds, they may be cooled or may work in controlled atmospheres. The
Attritor type installations have a simple design, they are easy to operate and allow the continuous execution of the
process. Following fragmentation, we obtain a much more dimensionally uniform powder in a much shorter time as
compared to the time necessary for the ball mills.
For the experimental works, we prepared two mixtures having different compositions, according to table 3, so as
to obtain cermets.
Table 3. Compositions of experimental cermet-based mixtures
Material / Mixture coding
TiC
[%]
WC
[%]
Co
[%]
Ni
[%]
Al2O3
[%]
(TiC WC - (Ni, Co) - Al2O3) / A1

(TiC - (Ni, Co) - Al2O3) / A2
75
75
10
-
5
5
5
5
5
15
The execution of mixtures in reduced quantities (about 300 g) took place as follows:
the component powders were dosed by weighing on the analytic balance;
the powders were mechanically homogenized for 12 h, in cylindrical airtight containers 75 mm wide and 95
mm long, fitted on a rotating device with rotation n = 60 rpm.
The aspect of the mixtures obtained following this operation was uniform without inhomogeneities visible by the
naked eye. The powder mixtures were then bound with paraffin (4%), sieved in semidry state by a sieve having the
size of meshes of 0.4 mm and then dried finally obtaining an adequate granulation of the powder mixtures characteristic to the ready for pressing mixtures.
The binder used - A type paraffin has the following characteristics:

density: = 0.90 g/cm3;

melting type: Tt = 50 - 54 oC.
In table 4, we give the characteristics of the cermet type mixtures obtained - (TiC WC - (Ni, Co) - Al2O3) / A1; (TiC
- (Ni, Co) - Al2O3) / A2 [2].
409

Table 4. Physical-technological characteristics of experimental mixtures

Flow rate
Material / Mixture coding
[sec/100]
Powdery
mixture
obtained
(TiC-WC-(Ni, Co) - Al2O3)

/ A1
(TiC- Ni, Co ) - Al2O ) / A2
Physical-technological characteristics
Fischer average
Apparent freely poured
diameter FSSS
unsettled density [g/cm3]
[m]
55
4.56
1.95
62
4.23
1.80
The values obtained while determining the flow rate allow the use of these mixtures in making automatic presses
with volumetric filling. To know the compaction aptitude, it was necessary to determine the optimal specific pressing
pressure.
The specific pressure ranges between 200 - 300 MPa depending on the nature and composition of powders used,
the geometry and sizes of the part, the type and quality of matrix.
The pressing was executed bilaterally on a steel matrix with circular section having the surface of 1 cm2, and a steel
matrix having a rectangular section (6.26 x 43) mm2 to make the transversal rupture strength specimens, at specific
pressures of 2000 N/mm2 for the powdery mixtures of the type A1 and A2 (v.[7]).
From the cermet type powder mixtures obtained this way we pressed at least 15 cylindrical compressed items and
10 A type specimens from every composition, and we obtained the average densities of the compressed items
given in table 5.
Table 5. Average densities of the compressed items in uncured state from experimental cermet type mixtures
Density in uncured state [g/
cm3]
4.975
4.889
Powder class
TiC-WC-(Ni, Co) - Al2O3) / A1
(TiC- Ni, Co ) - Al2O ) / A2
All compressed items were measured (to subsequently determine the dimensional variation) and weighed (to determine the mass loss after the debinding pre-sinterization operation).
As we expected, the smallest density in uncured state may be noticed for mixture A2 where the alumina content
(having a smaller density as compared to the other constituents) is in a larger proportion (15 %) and does not contain wolfram carbide powder (with the highest density of all composing powders).
In the process for the obtaining of conventional hard sinterized alloys, especially of cermets, to facilitate the pressing operation, we frequently use paraffin, as we mentioned above. Once the pressing process ended, the lubricant
must be eliminated since its presence might cause certain drawbacks during the sinterization operation, such as:
- carburization or oxidization of parts;
- degradation of part surface (on the surface of parts might appear pinches caused by the exaggerated pressure
of the gases resulted from the cracking of the lubricant or its fast volatilization).
In general, lubricants melt at temperatures below 200oC and boil at temperatures below 350oC. Consequently, heating the parts must be slow by 30oC/min at most, up to 500-600oC, where they are kept for 30-45 minutes so as not to
appear physical-chemical modifications in the deparaffined parts. In case of paraffin, this must be extracted slowly
and controllably (depending on the size and surface specific to the parts) so as not to destroy the surface of the part
and paraffin should not decompose forming free carbon. Deparaffining shall be executed in depressurized hydrogen current, in a static oven, the determination of the optimal work temperature being obtained experimentally.
Thus, up to 400oC, the heating speed must be very slow, at 400oC paraffin cracks and forms inferior paraffinic hydrocarbons and free carbon. Its evaporation takes place depending on the surface of the compressed item exposed to
the thermal flow that must ensure the volatilization of the lubricant without restrictions, the volatilizing quantity being
replaced by another diffusing from the inside to the surface.
Once paraffin has been transferred to the gas current, this must be removed from the reaction area as soon as
possible; the parts must be put in such a manner that the maximum surface should be exposed in the atmosphere
of the oven without creating areas of agglomeration or areas from where paraffin may not be removed in order to
avoid its depositing on certain areas of the oven and its subsequent cracking.
The pressed benchmarks were submitted to debinding in Siemens-Plania oven, in hydrogen atmosphere, using as
a packing agent the alumina calcinated beforehand at 1450oC, for 5 hours, to ensure the thermal stability.
The parameters of the debinding pre-sinterization process were:
410

atmosphere- hydrogen;
pre-sinterization temperature was in the temperature interval (800-900)oC;
maintaining at pre-sinterization temperature: 30 min.;
total time of the debinding pre-sinterization cycle: 8h 30 min;
Following the debinding pre-sinterization operation, we noticed that the established parameters allowed a uniform
elimination of the binder without the appearance of cracks. The pressed benchmarks were submitted to the sinterization operation to obtain the complex of properties imposed to the material.
The sinterization operation was executed in a vacuum induction heating furnace of Balzers type, with currents of
average frequency and the parameters of the sinterization operation were the following:

values of the sinterization temperature were in the interval 1400oC 1450oC;

soaking time at sinterization temperature: 60 min.;

total time of the cycle: 8 h.
For the characterization of the sinterized benchmarks, we determined the following physical-mechanical properties:

Vickers hardness HV50;
density (g/cm3);

transversal rupture resistance (daN/cm2);

contraction to sinterization.
In table 6, we present the characteristics of sinterized benchmarks made of the analysed compositions. The structural compositions were analysed by electronic microscopy SEM by means of an electron scan microscope CX
100-JEOL-TEMSCAN, at 100 kV, the magnification being 300,000 times, equipped with an energy dispersive analysis system (EDS) and wave length (WDX);
Table 6. Characteristics of sinterized benchmarks
Number of batch
Density
[g/cm3]
Batch A1/ (TiC-WC)-(Ni,Co) - Al2O3)

Batch A2/(TiC- Ni, Co) - Al2O3 )
4.775
4.376
Rupture
resistance
[N/mm2 ]
525
350
HV50
1400
1450
Contraction on the direction of

application of the pressing force
Ch [ % ]
3.375
2.430
We may notice that the densities obtained have values typical to the cermet type hard alloys and fall in the interval
4.37-4.77 g/cm3, the smaller value of the density of mixture A 2 (4.376 g/cm3) as compared to the one corresponding
to the powdery mixture A1 (4.775 g/cm3) is due to the fact that WC powder is missing from the structure of one of
these mixtures (case of mixture A2) having the highest density among the carbides present in the four mixtures
and to the fact that this class - class TiC - (Ni, Co) - Al2O3 mostly containing titanium carbide.
The values of resistance to transversal rupture determined by parallelipipedic sinterized specimens indicate that
batch A1/ (TiC-WC-(Ni,Co) - Al2O3) registers a clearly superior value to class TiC - (Ni, Co) - Al2O3 due to the presence of wolfram carbide.
The value of the triplet density rupture resistance hardness obtained this way indicate that the sinterization
parameters established for these mixtures allowed a high level of densification of the sinterized structures.
The sinterized benchmarks were prepared for metallographic examination in order to determine microstructure.
Microstructural analysis was executed by gradually highlighting the phases by Murakami attack.
Murakami attack specific for the highlighting of the phases present in cermets and hard alloys is a mixture made of
10 gr K3Fe(CN)6, 10 gr. KOH and 100 ml distilled water.
The samples for analysis were analysed under the electronic microscope with a magnification of X 1000, in attacked
state (see figures no. 1-2).
Figure 1 presents the morphology of particles from the structure of class type A1/TiC-WC-( Ni, Co) - Al2O3; we may
notice fine granulation powders but also the fact that the phases existing in the sinterized structures are somehow
non-uniformly distributed; the structure presented is an angular structure characteristic to the sinterized hard alloys
(a possible explanation might be that this class of powder has the highest content of WC; structural non-homogeneity might be due to the insufficient humectation of the carbide phase WC by the binder phase Ni/Co).
411

Attack: Murakami
Attack: Murakami
X1000
X1000
Figure 2 Microstructural aspect of cermet type

mixture A1/ TiC-WC - (Ni,Co) - Al2O3)
Figure 1. Microstructural aspect of cermet type

mixture A1/ TiC-WC - (Ni, Co) - Al2O3)
In figure 2, we present the morphology of the particles from the structure of class type A2/(TiC-(Ni, Co) - Al2O3 ); we
may notice fine granulation powders, a relatively uniform distribution of components (relatively rounded shape of
particles allows a high level of enveloping of particles). The structure presented is a structure typical to a cermet
a structure of the type nucleus-cellular edge, the ceramic-metallic particles having rounded, annular shapes.
3. CONCLUSIONS
We may obtain cermet-based mixtures with a high content of TiC (superior to 25%), different concentration of
metal binder Ni/Co and special alumina Al2O3 by using techniques specific to the powder metallurgy;
The systems of ceramic-metallic materials selected were characterized from the physical-mechanical and structural viewpoint in accordance with the norms specific to the powder metallurgy;
The experiments effectuated allowed us to establish the factors with a significant influence on the characteristics
of the materials of Cermet type under study, namely formation parameters, composition of gaseous environments
as well as thermal and temporal parameters of the thermal treatment processes;
The cermet type powdery mixtures obtained experimentally are recommended to be used in the making of cutting
plates utilized on automatic machines, at very high chip removing speeds and in conditions of dry processing.
4. REFERENCES
1. C. Collin, 13-th International Plansee Seminar,Comparative study of the properties of WC-Co Cermet, vol. II,
Reute, 1993, 505-522;
2. C. Collin, 1993, Processing of composition gradient WC-Co Cermet, 13-th International Plansee Seminar, Vol
2, Reutte, 522-537
3. N. Cherradi, 1996, Matriaux a gradient: exploatation du concept et tecniques de production par mtallurgie du
poudres, La Revue de Mtallurgie CIT/Science et Genie des Matriaux, 185-196;
4. M. Sjostrand, 2001, Advances in coating technology for metal cutting tools, Metal Powder Report, No. 4, 2430;
5. A.F. Lisovsky, 1987 On the inhibition of metal melt by sintered carbides, Powder Metallurgy Intternational, No.
5, 18-21;
6. C. Ciocardia, E. Dragulanescu, I. Dragulanescu, 1985, Aliaje dure sinterizate din carburi metalice, Ed. Tehnic ,
Bucureti;
7. Raport de Cercetare ICEM-C156/2004, Faza II/2004; Researches regarding the obtaining of
cermet type mixtures from TiC-WC-(Ni,Co)-Al2O3 and TiC-(Ni,Co)-Al2O3 systems
412

SINTERING
AND SINTERING
ATMOSPHERES
www.turkishpm.org
413

atmosphere effect on Sintering behaviour of Astaloy

CrM and Astaloy Crl Hgans powders with manganese and
carbon additions
Tadeusz PIECZONKA*, Maciej SULOWSKI*, Andrzej CIAS*
*AGH University of Science and Technology, Faculty of Metals Engineering and Industrial Computer Science,
Physical and Powder Metallurgy Research Unit,
PL 30-059 Krakw, Poland, Al. Mickiewicza 30, pieczonk@agh.edu.pl
Abstract
Dilatometric data for Astaloy CrM (3% Cr-0.5% Mo) and Astaloy CrL (1.5% Cr-0.2% Mo) powders with additions
of 0.3% carbon and 3.0% manganese during sintering cycles up to 1120 and 1250C in different atmospheres are
reported. For comparison, also Astaloy CrM and Astaloy CrLpowders were investigated. Starting with green densities of approx. 6.8 g/cm3, the final density of sintered compacts was influenced mainly by the sintering temperature, while the results showed the only minor effect of the sintering atmosphere on the final dimensional changes.
However, the sintering atmosphere influences the sintering behaviour and a final chemical composition of sintered
compacts. In sintered and cooled in the dilatometer Mn-Cr-Mo-C steels predominantly bainitic structures were
obtained / observed.
Keywords: Pre-alloyed Iron Based Powders, Sintering, Dimensional Control, Dilatometry
1. INTRODUCTION
Chromium and manganese are potentially important alloying elements in sintered steels. When correctly employed,
they can improve mechanical properties, hardenability and nitridability [1-6]. For these reasons Cr and Mn are the
elements, which are widely used in many structural wrought steels. However, up to date, these elements have seen
little exploitation in the powder metallurgy (PM) industry due to their extremely high affinity for oxygen [7-16]. One
of the recent (1998) industrially available means of incorporating chromium into structural PM parts production is
use of the water atomised pre-alloyed Astaloy CrM (Fe-3%Cr-0.5%Mo) powder developed by Hgans AB [17].
This producer delivers also (since 2002) a modified powder grade AstaloyCrL (Fe-1.5%Cr-0.2%Mo) [18]. Sintered
compacts made of these powders alloyed with carbon indicate attractive mechanical properties, including sinter
hardening effect [19-24]. The limited use of both powders in PM industry is associated with the processing requirements of very low dew point/oxygen potential of the sintering atmosphere at normal link-belt sintering temperatures.
The atmosphere requirements are relaxed by the use of elevated sintering temperatures (above 1200C) [1]. There
has been, however, a reluctance on the part of manufacturers to use this technique in, for example, walking beam
or pusher furnaces on the grounds of cost and availability. This situation is changing with the introduction of modern,
more cost efficient furnaces.
Because high temperature sintering (HTS) promotes oxide reduction, it is an especially very useful PM route for
steels containing elements which have a high affinity for oxygen, particularly if they are added in elemental form.
HTS further promotes homogenisation of the microstructure and pore rounding, which can lead to the improvement
in the mechanical properties of PM steels [4]. Additionally, the hardenability of Astaloy CrM and Astaloy CrL steels
can be further increased by manganese addition to the starting powder, and e.g. Mitchell et al [1-4] have reported or
obtaining martensite, including by air hardening, and presented initial sinter hardening data. It is well known in PM
industry that the dimensional changes occurring during the whole PM cycle have to be carefully controlled to produce high precise parts and to keep required tolerances. There are many parameters influencing the dimensional
behaviour of the compact during sintering. Main of them is the sinterability of the material subjected to the specific
414

external conditions, which includes chemical homogenisation and material sintering atmosphere interactions.
Thus, in this paper a study of the temperature and atmosphere effect on dimensional changes of Mn and C containing compacts based on Astaloy CrM and Astaloy CrL Hgans grade powders is shown.
The following starting powders were used:
commercial pre-alloyed Fe-3%Cr-0.5%Mo Hgans Astaloy CrM grade powder,
commercial pre-alloyed Fe-1.5%Cr-0.2%Mo Hgans Astaloy CrL grade powder,
smaller than 40 m fraction (distribution centred around 10 m) of low carbon ELKEM ferromanganese powder
supplied by Elkem Ferromanganese Sauda, Norway, containing 77.0 wt% Mn, 1.3 wt% C, 0.2 wt% O2, 0.02 wt%
N2 and Fe bal.,
commercial C-UF Hgans fine graphite powder.
The lubricant was not added.
The starting powders were mixed in Turbula mixer for 30 minutes to prepare the following mixtures:
Astaloy CrM + 0.30 wt% C + 3.0 wt% Mn,
Astaloy CrM + 0.33 wt% C + 3.0 wt% Mn,
Astaloy CrL + 0.30 wt% C + 3.0 wt % Mn,
Astaloy CrL + 0.33 wt% C + 3.0 wt% Mn.

For comparison, the compacts based on as-received Astaloy CrM and Astaloy CrL powders were also used.
Mixtures were carefully handled to minimise any segregation of the constituents. The mixtures were compacted
into rectangular specimens of size 4x4x15 mm3, using uniaxial pressing at 600 MPa. This resulted in green densities of about 6.8 g/cm3. The sintering experiments were carried out in a horizontal push rod dilatometer NETZSCH
402E. The measuring direction (length of the specimen) was chosen perpendicular to the pressing direction of the
compacts.
The gases used as the sintering atmospheres were:
nitrogen, purity 5.0
95 vol.% nitrogen + 5 vol.% hydrogen mixture prepared from 5.0 purity gases, and
argon, purity 4.5.

The dew point measured at the inlet to the dilatometer was at least 55C. The flow rate was 50 ml/min at the
internal tube diameter of 38 mm.
Samples were heated at 10 C/min to the isothermal sintering temperature of either 1120C or 1250C. Isothermal
sintering was then carried out for 60 minutes. It should be noted that the dilatometer used could not maintain the
constant cooling rate during the whole cooling period. Thus, the cooling rate within the linear range (from isothermal
temperature down to about 380C) was 20C/min (0.33C/s). Below 380C the cooling rate was decreasing continuously as it is seen on T-curves (e.g. in Figure 1). The temperature control was accurate to 1C. The changes in
slope of the dilatometric traces were examined in detail.
Sintered compacts were used to prepare metallographic specimens. 2% nital was used for etching. The microstructures of sintered compacts were observed by light microscopy.
Figures 1-4 show the complete dilatometric plots obtained during the current investigations. In the case of unmodified Astaloy CrL and Astaloy CrM powders, used as standard materials, initially the thermal expansion is observed,
transformation begun at ~888C and ~878C, respectively, and finished at
then the shrinkage due to
~918C for both powders, being ~ 0.20% with minor effect of the atmosphere. The isothermal dimensional changes
of pure Astaloy CrL and Astaloy CrM compacts are strongly influenced by the temperature. During sintering at
1120C, the changes are negligible, irrespective of the sintering atmosphere, while at 1250C the effect of the
sintering atmosphere is significant: the ~0.45% shrinkage is observed for both powders but only in hydrogen containing atmosphere (95%N2/5%H2). This behaviour can be explained by the extending oxides reduction at higher
transformation starting earlier (i.e. at higher temtemperature [22]. Cooling period is characterised by the
perature) in argon than in other atmospheres. Astaloy CrL specimens cooled from 1120C began to expand due to
the transformation at ~870C in argon and at ~850C in nitrogen and nitrogen/hydrogen mixture. In case of Astaloy
CrM the respective temperatures are: ~880C and ~830C. Compacts cooled after sintering at 1250C start to
transform at ~880C in argon (irrespective of the powder grade) while at ~840C for Astaloy CrL and only at ~820C
for Astaloy CrM in other atmospheres.
415

Figure 1. Dilatometric
curves for sintering cycles
at 1120C under different
furnace atmospheres. The
details are given in individual figures.
Figure 2. Dilatometric
curves for sintering
cycles at 1250C under
different furnace
atmospheres. The
details are given in
individual figures.
416

Specimens containing manganese and graphite heated from room temperature initially expand thermally, till ~
transformation in other atmospheres, which are: ~
680C in argon atmosphere and till the beginning of
780C for Astaloy CrL-base composition and ~ 815C for Astaloy CrM-base one. Similarly to the not modified powders, the dimensional behaviour of Mn and C alloyed mixtures in argon differs from those in nitrogen and nitrogen/
hydrogen mixture. The expansion rate starts to decrease slightly only in argon at by ~ 130C (Astaloy CrL base
transformation,
powder) or even by ~ 160C (Astaloy CrM) lower temperature than that of the initiation of the
which is better visible in Figure 5. Generally, Mn and C lower the temperature at which this transformation starts.
This is important since it has been demonstrated by Mitchell et al [1, 4] that alpha phase sintering in Astaloy CrMbase alloys is to be avoided. Except argon, there were only minor effects due to the composition of the sintering
transformation. It is, however, worthy of note that the thermal conductivity of the sinteratmosphere on the
ing atmosphere was anticipated to be of more importance during cooling, especially when sinter hardening effects
were expected.
transformation the specimens expand until the sintering plateau, due to thermal
After completion of the
expansion and possibly also alloying and other sintering processes. The slopes of the dilatometric curves in this
increasing temperature region depend on composition of the mixtures, being steeper for those based on Astaloy CrL
powder, implying that homogenisation processes continue to take place. All the specimens sintered at 1120C expanded continuously during heating at almost constant rate, independently of the atmosphere (Figure 1), whereas
those heated to 1250C reached their maximal length admittedly at that temperature, but starting at about 1200C at
significantly lower expansion rate, which indicates that sintering shrinkage begins to dominate thermal expansion,
starting just at 1200C.
There was observed only a minor effect of the sintering atmosphere on isothermal shrinkage. At 1120C both
mixtures shrank by ~0.6%, while at 1250C by ~1.3% in case of Astaloy CrL based composition and by ~1.4% for
Astaloy CrM based one. The influence of sintering atmosphere on dimensional changes is more clearly illustrated
in Figures 3 and 4. Interestingly, the argon produces the highest final shrinkage.
Figure 3. The influence of the sintering atmosphere on dimensional changes for specimens sintered at 1120C.
Figure 4. The influence of the sintering atmosphere on dimensional changes for specimens sintered at 1250C.
417

Figure 5. Detailed dilatometric heating segments.

The addition of carbon and ferromanganese to the Astaloy CrL and Astaloy CrM powders, which enhances sinter
hardening effects, can be related to the cooling segments of the dilatometric curves (Figures 6 and 7). In the con transformation is not detected now. Because of the advanced
trary to the unmodified base powders the
homogenisation the sintered alloys show increased hardenability. Thus the approximate bainite start temperatures
appear to be ~470C for Astaloy CrL + 0.3% C + 3% Mn and ~460C for Astaloy CrM + 0.3% C +3% Mn, respectively for compacts sintered at 1120C. The sintering temperature of 1250C increases the bainite start temperature
(Bs) by about 40C. Independently of the composition and isothermal sintering temperature, Bs temperature is by
about 20C higher in argon than in other atmospheres.
Figure 6. Detailed dilatometric cooling segments for compacts sintered at 1120C.
Figure 7. Detailed dilatometric cooling segments for compacts sintered at 1250C.
418

The higher heat conductivity of the 95% N2 / 5% H2 atmosphere during cooling made only a negligible difference in
heat transfer when the non-linear region of cooling rate was reached, probably due to the small thermal mass of the
dilatometric sample. Thus sinter hardening was not significantly influenced by the high heat conductive hydrogen.
It is well known in PM steel that carbon not only changes the transformations behaviour but also acts as a reducing agent. The last role is connected with some lost of this element during sintering. Therefore, the LECO analysis
has been performed on the sintered compacts to control the final carbon content. The results showed the large
decrease of carbon concentration: from ~25% up to ~75% as compared with that in green compacts. At higher
sintering temperatures the higher carbon reduction was recorded. Thermodynamics indicates favourable conditions
for carbothermic reduction of Cr and Mn oxides at conventional sintering temperatures. For reduction of Cr2O3 and
MnO by solid carbon thermodynamic calculations for atmosphere predominantly of nitrogen were carried out by
Cias and Mitchell [24, 25]. Comparison of calculated ratio of partial pressures p(CO)/p(CO2) and maximum allowed
partial pressure of O2 and H2O in the 90% N2 / 10% H2 atmosphere with the experimentally obtained one, by continuous atmosphere monitoring during the sintering of Astaloy CrM + 0.5% C, clearly shows favourable conditions
for carbothermic reduction of the chromium oxides during isothermal sintering at 1120C or higher [26]. The effect
of the sintering atmosphere is not unambiguous. The relatively low carbon concentration in sintered steels seems
to be responsible for their rather limited sinter hardenability.
The examples of sintered microstructures are shown in Figures 8 and 9.
Figure 8. Microstructure of Astaloy CrL + 0.3 wt% C + 3 wt% Mn sintered at 1250C: left in N2/H2=95/5, right in
argon.
Figure 9. Microstructure of Astaloy CrM + 0.3 wt% C + 3 wt% Mn sintered at 1250C: left in N2/H2=95/5, right
in argon.
Generally for both base powders, sintering in nitrogen and in 95% N2 / 5% H2 gas mixture produces homogeneous
bainitic microstructure with rounded pores, whereas the microstructure of compacts sintered in argon is characterised by bainitic matrix containing one phase bright grains. The identification of the phase and the role of argon in its
appearance require further investigations.
419

4. CONCLUSION REMARKS
The relatively small shrinkages observed at the sintering temperatures probably resulted from solid state sintering
of the compacts with a relatively low green density of approx. 6.8 g/cm3. In accordance with the theoretical phase
diagrams, for the Fe-3%Cr-0.5%Mo-C and Fe-1%Cr-3%Mn-0.5%Mo-C systems [27], to obtain a liquid phase for the
alloys investigated temperatures of the order of 1400C are required. Therefore to increase densification at chosen
isothermal temperatures this sintering period should be elongated. Based on isothermal shrinkage rate shown in
Figures 1 and 2 it can be stated that there is still a potential for further shrinkage at these temperatures.
Why argon modifies the sintering behaviour and microstructure of materials investigated is not completely clear.
Probably it can be explained, at least partly, by the low heat conductivity of this gas. The further investigations in
this field, including mechanical properties of in argon sintered compacts, are under way.
ACKNOWLEDGEMENTS
The financial support of the Ministry of Science and Higher Education under the contract no N N507 477237 (AGH
no 18.18.110.961) is gratefully acknowledged.
REFERENCES
1. Mitchell, S.C, Wronski, A.S., Cias, A., Stoytchev, M., Microstructure and Mechanical Properties of Mn-Cr-Mo-C
Steels Sintered at >1140C, Advances in Powder Metallurgy and Particulate Materials, Vol .2, MPIF, pp.7129 to 7-144, 1999.
2. Wronski, A.S., Becker, B.S., Wright, C. S., Mitchell, S.C., Alloy Design for Improved Mechanical Properties and
Robust Processing, Proc. DFPM99, ed. L. Parilak and H. Danninger, Vol. 1, pp.1/155 to 1/166, 1999.
3. Mitchell, S.C., The Development of Powder Metallurgy Manganese Containing Low-Alloy Steels, Ph.D. thesis,
University of Bradford, 2000.
4. Wronski, A.S., Cias, A., Barczy, P., Stoytchev, M., et al, Tough Fatigue and Wear Resistant Sintered Gear
Wheels, Final Report on EU Copernicus Contract No. ERB CIPA CT-94-0108, European Commission, 1998.
5. Lindsley, B., James, B. PM Steels That Contain Manganese, Advances in Powder Metallurgy & Particulate
Materials, MPIF, Hollywood, Vol. 10, pp. 36-49, 2010.
6. Hryha, E., Dudrova, E., Nyborg, L., Critical Aspects of Alloying of Sintered Steels with Manganese, Metallurgical and Materials Transactions A-Physical Metallurgy and Materials Science, 41A (11), pp. 2880-2897.
7. Navara, E., Sintering of Iron Powder with an Addition of Ferromanganese, Sintering85, compiled by G.C.
Kuczynski et al., Plenum Press, pp. 343-356, 1985.
8. Klein, A.N., Oberacker, R., Thmmler, F., High Strength Si-Mn- Alloyed Sintered Steels. Microstructure and
Mechanical Properties, Powder Metallurgy International, Vol. 17, No. 1, pp. 13-16, 1985.
9. Klein, A.N., Oberacker, R., Thmmler, F., High Strength Si-Mn- Alloyed Sintered Steels. Sinterability and Homogenization, Powder Metallurgy International, Vol. 17, No. 2, pp. 71-74, 1985.
10. Salak, A., Effect of Extreme Sintering Condition upon Properties of Sintered Manganese Steels, Powder
Metallurgy International, Vol. 16, No. 6, pp. 260-263, 1984.
11. Salak, A., Manganese Sublimation and Carbon Ferromanganese Liquid Phase Formation During Sintering
of Premixed Manganese Steels, International Journal of Powder Metallurgy, Vol. 16, No. 4, pp. 369-379,
1980.
12. Danninger, H., Pttschacher, R., Jangg, G., Seyrkammer, J., Salak, A., Manganese Alloyed Sintered Steels
Prepared from Elemental Powders, Proc. PM94 World Congress, EPMA, Paris, Vol.1, pp. 879-882, 1994.
13. Danninger, H., Gierl, C., New Alloying Systems for Ferrous Powder Metallurgy Precision Parts, Science of
Sintering, 40, pp. 33-46, 2008.
14. Selecka, M., Salak, A., Pieczonka, T., Stoytchev, M., Solid Phase Sintering and Alloying of Powder Fe-Mn
Steels Observed by Dilatometry, Proc. Int. Powder Metallurgy Congress and Exhibition EURO PM2007,
Vol. 1, pp. 47-50, 2007.
15. Selecka, M., Salak, A., Pieczonka, T., Solid Phase - Gas Phase Sintering and Alloying of Powder Fe-Mn Steels
Analysed by Dilatometry, Steel Grips, Vol. 6, No. 5, pp. 355-358, 2008.
16. Hryha, E., Nyborg, L., Dudrova, E., Bengtsson, S., Microstructure Development During Sintering of Manganese Alloyed PM Steels, Proc. EURO PM2009 (CD), Copenhagen, Denmark, 2009.
17. Lindberg, C., Mechanical Properties of Water Atomised Fe-Cr-Mo Powder and How to Sinter It, Advances in
Powder Metallurgy and Particulate Materials, Vol. 2, MPIF, pp. 7-229 to 7-244, 1999.
18. Engstrom, U., Klekovkin, A., Berg, S., Edwards, B., Frayman, L., Hinzmann, G., Whitehouse, D., Efficient LowAlloy Steels for High Performance Structural Applications, Advances in Powder Metallurgy & Particulate
Materials, MPIF Las Vegas, USA, Vol. 7, pp. 68-79, 2003.
19. Molinari, A., Straffelini, G., Campestrini, P., Influence of Microstructure on Impact and Wear Behaviour of Sintered Cr and Mo Steel, Powder Metallurgy, Vol. 42, No. 3, pp. 235-241, 1999.
420

20. Engstrm, U., Evaluation of Sinter Hardening of Different PM Materials, Advances in Powder Metallurgy &
Particulate Materials, Vol. 5, MPIF, pp. 5147 to 5-157, 2000.
21. Lindberg, C., Johansson, B., Maroli, B., Mechanical Properties of Warm Compacted Astaloy CrM, Advances
in Powder Metallurgy & Particulate Materials, Vol. 6, MPIF, pp. 681 to 6-92, 2000.
22. Castro, F., Ortiz, P., Study of Gas Solid Interactions During Sintering of Cr-Containing PM Steels, Proc. of
EURO PM2003, Valencia, Spain, Vol. 1, pp. 243-249, 2003.
23. Bergman, O., Nyborg, L., Evaluation of Sintered Properties of PM Steels Based on Cr and Cr-Mn Prealloyed
Steel Powders, Powder Metallurgy Progress, Vol.10, No.1, pp. 1-19, 2010.
24. Cias A., Development and properties of Fe-Mn-(Mo)-(Cr)-C sintered steels, Ed. AGH UST, Krakw, 2004.
25. Mitchell S. C., Cias A., Carbothermic reduction of oxides during nitrogen sintering of manganese and chromium steels, Powder Metallurgy Progress, Vol. 4, No 3, pp. 132-142, 2004.
26. Hryha E., ajkova E., Dudrov E., Study of reduction/oxidation processes in Cr-Mo prealloyed steels during
sintering by continuous atmosphere monitoring, Powder Metallurgy Progress, Vol. 7, No 4, pp. 181-197,
2007.
27. Pieczonka, T., Mitchell, S.C., Stoytchev, M., Kowalczyk, M. Liquid Phase Sintering of Fe-3Cr-1Mn-0.5Mo High
Carbon Steels, Proc. of the 2002 Int. Conf. on Powder Metallurgy & Particulate Materials, Orlando, USA,
Vol. 11, pp. 1428, 2002.
421

CARBON, OXYGEN AND NITROGEN VARIATIONS DURING SINTERING OF

Mo PREALLOYED AND Ni-Cu-Mo DIFFUSION BONDED STEELS
Mohammad MOMENI*, Herbert DANNINGER** and Christian GIERL***
Institute of Chemical Technologies and Analytics, Vienna University of Technology, Getreidemarkt 9/164,
A-1060 Wien/Vienna, Austria
*mmomeni@mail.tuwien.ac.at, **hdanning@mail.tuwien.ac.at, ***cgierl@mail.tuwien.ac.at
ABSTRACT
In this research, Mo prealloyed and Ni-Cu-Mo diffusion bonded steels were produced, sintering was conducted
from 700 to 1300C temperature in nitrogen atmosphere, and interstitial elements; i.e. carbon, oxygen and nitrogen
contents were determined by carrier gas hot extraction method (Leco). In both steels, the major part of the oxides
are reduced up to 1000C, with resulting loss of carbon, but above this temperature only about 0.01% oxygen is
removed. Nitrogen pickup was measured in both materials by less than 0.03% up 1000C; this confirms once more
that nitrogen can be used as neutral atmosphere except for soft magnetic materials.
Keywords: Sintered steel, Interstitial contents, Mo prealloyed, Cu-Ni-Mo diffusion bonded, Powder metallurgy.
1. INTRODUCTION
Sintering not only means formation and growth of interparticle contacts and lowering or in some cases, eliminating
the porosity, but it also brings about changes of the specimen
chemistry [1]. Therefore, investigation of the reduction of surface oxides, carbon dissolution, formation of sintered
contacts and phase transformation during the thermal cycle is a necessity to understand the sintering procedure in
an appropriate manner.
Standard alloying elements for PM-steels such as Cu, Ni and Mo, having significantly less affinity to oxygen than Cr,
require O2 partial pressures better than 10-13 bar and thus can be easily sintered in standard atmospheres [2]. Thus
industrial sintering is feasible in N2/H2 atmospheres containing tolerably low fractions of oxygen and/or oxidizing
species including H2O and CO2.
During sintering in an inert atmosphere such as dry nitrogen, carbon acts as an agent for reduction of oxidic surfaces of metal powders. Thus, the transport via gas phase is a parallel process to the direct solid state diffusion of
carbon in the iron matrix [3], but Dautzenberg et al [4] stated that the solution of carbon into premixed sintered steel
during sintering is not depending as usually assumed - on a conversion of the graphite into CO but appears to be
a direct solid state diffusion.
Sintering atmospheres based on nitrogen/hydrogen combinations are widely used for processing high performance
and close dimensional tolerance steel components. In practice, a relatively low dew point is required which is of
no concern as the commercially available industrial gases of today are of good quality. The low dew point of the
nitrogen ( -70C) helps prevent decarburization and increase reducing potential [5,6]. Generally, nitrogen by itself
does an effective job of keeping oxygen out of the furnace [7], and sintering in nitrogen results in faster dissolution
of carbon relative to hydrogen [3,8].
Carbon can act as reducing agent both as element and in CO, the latter one is known as indirect carbothermic reaction and the former as direct oxide reduction [9]. For plain carbon steels, investigations showed that there are three
temperature ranges within which gas formation, associated with weight loss, preferentially takes place. The first
interval, ranging between 50 and about 500C, is mostly associated with desorption of water or decomposition of
hydroxides, mass 18-H2O being preferentially detected in two maxima at 150 and 450C, respectively. In the same
422

temperature range also mass 44-CO2 can be detected, with a pronounced maximum at 350-400C, which shows
carbothermic reduction reactions. The second temperature interval is rather narrow, between 680 and 750C, but
here a very pronounced mass loss occurs, indicates CO formation. The second peak occurs at slightly higher temperatures in Fe-Mo-C than for Fe-C at about 750C, i.e., apparently following the shifting of the ferrite to austenite
transformation [10,11].
A third, rather less pronounced peak which, however, in total results in larger mass loss than the other peaks is
found in the temperature range 950-1100C and also consists mostly of CO [12]. The only reasonable explanation
was that the oxygen originated from different sources, i.e., the reduction at about 700C involves the surface oxygen
and the process at higher temperatures the oxygen present within the powder particles.
In this work, two different alloyed steels, i.e. Mo prealloyed and Ni-Cu-Mo diffusion bonded steels, were produced.
They were compacted at 600 MPa and sintering was done between 700 and 1300C in N2 atmosphere. With
relatively wide range of sintering temperature, the sintering procedure can be studied from initial stages up to high
temperature levels. Oxygen, carbon and nitrogen contents were measured by carrier gas hot extraction method
(Leco). Oxygen content is helpful in order to evaluate reduction of oxides and estimate progress in sintering procedure. Carbon is consumed during carbothermic reduction; therefore the carbon loss should be compensated, and
the nitrogen pick up can also be evaluated by nitrogen measurement.
Mo prealloyed powder Fe-1.5% Mo (Hgans Astaloy Mo) and 4%Ni-1.5%Cu-0.5%Mo diffusion bonded grade (Hgans Distaloy AE) were used for this experiment. Natural graphite UF4 was used as an additive and 0.5% HWC
as a lubricant, and two chemical compositions were produced, i.e. Astaloy Mo- 0.5% C and Distaloy AE- 0.5% C.
Powders were mixed in a tumbling mixer for 60 min.
Charpy test bars (ISO 5754) were prepared by compacting at 600 MPa. The specimens were first dewaxed at
600C for 30 min in flowing high purity N2 in a small tube furnace. After that they were sintered in N2 at widely varying temperatures, between 700 and 1300C with 100C interval, in a large pusher furnace with gas tight superalloy
retort, isothermal sintering time was 60 minutes. The cooling rate was approx. 0.5C/s average.
Sintered densities were measured using the Archimedes method (DIN ISO 3369). Dimensions were measured with
precision of 0.01 mm for each sample, and the dimensional change during sintering was calculated. Then the oxygen and nitrogen contents of the specimens were measured using carrier gas hot extraction (Leco TC400). Carbon
content was measured after sintering using combustion analysis (Leco CS230). The measured carbon, oxygen and
nitrogen content of base powders is presented in Table 1. Mass change was calculated from difference of mass
between green and sintered parts.
Mass spectrometry investigations have been conducted in a Netzsch STA 402C pushrod
dilatometer with alumina measuring system. Before each test run, the system was evacuated and flooded with
high purity helium for 3 times. Then the runs were performed by heating at 10 K.min1 up to 1300 C, soaking for
1 h, and then cooling at 10 K.min1. N2 (99.999%) with flow rates of 10 ml.min1 was used as protective gas (only
running through the balance system) and with 50 ml. min1 as working atmosphere (in contact with the specimen).
For identifying the degassing processes occurring during sintering, recorded intensities of m44 (CO2), m12 (C) and
m16 (O) were evaluated.
3.1. Density and dimensional change
Sintered densities and dimensional changes of both steels as function of sintering temperature are presented in
Figure 1. The results show only marginal changes of sintered density for both diffusion bonded and prealloyed
steels below 900 and 1000C respectively; increasing by only about 0.02 g.cm-3 for the former and without any
significant increment for the latter. In diffusion bonded powder compacts, contacts between particles are originated
not only from compacting pressure but also from powder particles itself, therefore with slight oxide reduction and the
subsequently carbon dissolution at initial stages of sintering, sintered density slightly improved. The reason is due
to the characteristics of diffusion powder particles; on surfaces with highest content of metallic alloying elements
the sintering contacts can be formed and improved already by slight carbon dissolution, while for plain carbon steel
compacts higher carbon dissolution is necessary to enhance the Ac or load bearing cross section.
423

Dimensional changes of course show an opposite trend to sintered density. The observed expansion between 700
and 900C for prealloyed steel shows that sintering contacts is not formed properly at these temperature intervals,
the reason is due to the carbon dissolution and formation of austenite.
As already reported, sintering is in progress in both ferritic and austenitic areas and the sintering bridges are improved up to 900C but the significant sintering contacts are formed in Mo containing prealloyed material at higher
temperature levels [13].
Table 1. Measured carbon, oxygen and nitrogen content of different base powders.
Material
Astaloy Mo
Distaloy AE
Carbon
(wt%)
0,0082
0,0089
Oxygen
(wt%)
0,0842
0,1220
Nitrogen
(wt%)
0,00056
0,00081
Figure 1. Dimensional properties as a function of sintering temperature, compacted at

600 MPa, sintered 60 min in N2, A: sintered density, B: dimensional change.
3.2. Interstitial elements
Table 2 shows the measured carbon, oxygen and nitrogen contents for both steels sintered from 700 to 1300C
with an interval 100C, and the graphs of interstitial elements as function of sintering temperature are represented
in Figure 2 and Figure 3.
In order to eliminate the effect of different atomic weight, carbon and oxygen contents are presented in atomic
percentage in Table 3 with their accumulated reductions at different temperature intervals (for calculating the atomic
percent out of weight percent, only main alloying elements i.e. Fe, Mo, Ni, Cu, C, O and N were considered).
As stated in Table 1, the oxygen content in the diffusion bonded material is about 50% higher than in the prealloyed grade. Oxygen content in AstaloyMo and DistaloyAE was reduced from 0.08 to 0.006 wt% (0.28 to 0.02 at%)
and from 0.09 to 0.007 wt% (0.33 to 0.03 at%) respectively when the sintering temperature increased from 700 to
1300C.
Figure 2 shows that in both steels the major part of oxygen content was reduced up to 1000C, and above 1000C
only about 0.01% oxygen is removed. While below 1100C the diffusion bonded grade shows more oxygen content
than AstaloyMo, above 1000C the oxygen contents in both steels are relatively similar.
It is obvious that in a neutral atmosphere such as nitrogen, and in presence of admixed graphite in powder compacts, oxygen is reduced through carbothermic reaction which means by carbon consumption. Carbon decreased
from 0.64 to 0.55 wt% (2.9 to 2.5 at%) for Mo containing material while it decreased from 0.54 to 0.47 wt% (2.5 to
2.2 at%) for diffusion bonded grade. For Mo containing material terminating carbon consumption up to 1300C is
visible while for DistaloyAE oxide reduction yields relatively similar carbon level in the range of 1100 to 1300C.
Higher level of oxygen content in DistaloyAE compared with AstaloyMo below 1100C should be reduced with
higher level of carbon consumption at lower sintering temperatures. The relative ratio of carbon consumption to
424

oxygen reduction (as stated in Table 3) at 800C is about 1.5 and 2 for Mo containing and diffusion bonded material. The reason can be in part due to the slightly finer particles of the latter and also its bonded structure that yields
smaller diffusion path to reduce oxides especially at initial stages of sintering.
Table 2. Carbon, oxygen and nitrogen contents with their standard deviations for
both steels sintered in a wide temperature range.
Compaction
pressure
(MPa)
AstaloyMo-0.6%C (Mo)
Material
DistaloyAE-0.5%C (AE)
600
Sintering
Carbon
C
Oxygen
O
temperature content standard content standard
(C)
(Wt%) deviation (Wt%) deviation
Nitrogen
content
(Wt%)
N
standard
deviation
700
0,6382
0,0042
0,0815
0,0016
0,0059
0,0002
800
0,6212
0,0071
0,0670
0,0017
0,0104
0,0004
900
0,5971
0,0015
0,0422
0,0013
0,0231
0,0002
1000
0,5828
0,0050
0,0178
0,0004
0,0262
0,0002
1100
0,5731
0,0018
0,0088
0,0002
0,0239
0,0002
1200
0,5671
0,0113
0,0087
0,0003
0,0226
0,0002
1300
0,5504
0,0061
0,0058
0,0001
0,0217
0,0001
700
0,5433
0,0042
0,0948
0,0035
0,0098
0,0007
800
0,5125
0,0035
0,0756
0,0006
0,0077
0,0002
900
0,4995
0,0081
0,0513
0,0011
0,0119
0,0009
1000
0,4816
0,0043
0,0213
0,0004
0,0197
0,0001
1100
0,4739
0,0071
0,0118
0,0010
0,0189
0,0001
1200
0,4766
0,0021
0,0088
0,0012
0,0178
0,0001
1300
0,4726
0,0070
0,0073
0,0003
0,0175
0,0001
Figure 2. Interstitial elements as a function of the sintering temperature, compacted at 600 MPa, sintered in N2
atmosphere, A: Carbon and B: Oxygen.
Figure 3 shows the nitrogen uptake from the atmosphere during sintering. Sintering in N2 base atmosphere enhances the probability to pick up the nitrogen in the sintered part.
High purity N2 by itself is usually thought to be an inert gas in sintering of ferrous compacts, but the chemical analysis shows that there is a small amount of nitrogen pickup, less than 0.03% up to 1000C, and at higher sintering
temperatures nitrogen contents tend to level off. Therefore the amount of N introduced is rather low and, except for
soft magnetic materials, pure nitrogen can be used as neutral atmosphere.
It is also reported that even the higher N content in Cr-Mo prealloyed steel, present as nitrides, is not dangerous for
the mechanical properties of the material because the nitrides are distributed in the matrix and not concentrated at
the grain boundaries [14].
425

Table 3. Carbon and oxygen contents, their reductions (at %) and ratio carbon consumption to oxygen reduction
at different temperature intervals for both steels.
Compaction
pressure
(MPa)
AstaloyMo-0.6%C (Mo)
Material
DistaloyAE-0.5%C (AE)
600
Sintering
temperature
(C)
Carbon
content
(at %)
Oxygen
content
(at %)
Reduction
of carbon
(at %)*
Reduction
of oxygen
(at %)*
Ccons/Ored
ratio*
700
2,91
0,28
NA
NA
NA
800
2,84
0,23
0,07
0,05
1,46
900
2,73
0,14
0,18
0,14
1,34
1000
2,67
0,06
0,24
0,22
1,11
1100
2,62
0,03
0,29
0,25
1,15
1200
2,60
0,03
0,31
0,25
1,25
1300
2,52
0,02
0,39
0,26
1,49
700
2,49
0,33
NA
NA
NA
800
2,35
0,26
0,14
0,07
2,03
900
2,29
0,18
0,20
0,15
1,30
1000
2,21
0,07
0,28
0,26
1,08
1100
2,18
0,04
0,31
0,29
1,08
1200
2,19
0,03
0,30
0,30
1,00
1300
2,17
0,03
0,32
0,30
1,04
*Oxygen reduction and carbon consumption were calculated with respect to the sintered part at 700C.
Figure 3. Nitrogen content as a function of the sintering temperature, compacted at 600 MPa, sintered in N2 atmosphere.
3.3. Mass spectrometry
Comparative intensities for mass 44 (CO2), m12 (C) and m16 (O) recorded by mass spectrometry in the dilatometer
are shown in Figure 4 and Figure 5. Figure 4 shows carbothermic reduction by CO forming CO2 which is more
intense at lower temperature according to Boudouard equation. Mass 12 can be used to derive an indirect indication of the formed CO [11,15] as recording m28 during sintering in nitrogen atmosphere is not effective because
of interference of the m28 signals for the two chemical compounds with the same mass, i.e., CO and N2, and m16
shows the spectra for atomic oxygen.
426

Figure 4. Comparative gas intensities for mass 44 (CO2), compacted at 600 MPa, sintering at 1300C in N2
atmosphere, heating-cooling rate: 10K/min.
DistaloyAE shows the tallest and widest peak for all three mass intensities during reduction of surface and internal
oxides, therefore more surface and internal oxides are removed by formation of CO2 and CO. Observing almost the
same level of intensity for mass 16 or atomic oxygen above 1150C certifies that for both steels the same amount
of oxygen should be reduced above that temperature. While the oxygen contents were measured ex situ from the
specimens sintered at different temperatures for 60 min isothermally in a laboratory furnace, the mass intensity was
in situ recorded by mass spectrometry during the sintering procedure, but it seems that the results of these two different analytic methods can be reliably correlated.
Figure 5. Comparative gas intensities for mass 12 (C) and mass 16 (O), compacted at 600 MPa, sintering at
1300C in N2 atmosphere, heating-cooling rate: 10K/min.
Figure 6 shows the carbon consumption as a function of oxygen reduction. This graph is helpful to predict one of
them if the other has been measured. The relations between C consumption and O reduction show that the majority of oxygen removal in all alloys takes place by formation of CO and not CO2, i.e. by direct reduction.
427

Figure 6. Carbon consumption as a function of oxygen reduction for both sintered steels; compacted at 600 MPa,
sintering at 700-1300C in N2 atmosphere.
4. CONCLUSION
The chemical analysis shows that for both steels the major part of oxides is reduced up to 1000C; yielding an
oxygen content of about 0.02 wt%, and with using higher sintering temperatures oxygen is reduced to less than
0.01 wt% for both steels and then tends to level off. The content of carbon, as reducing agent, shows its continuous
decrease in Mo prealloyed steel from 700 to 1300C but for diffusion bonded material there is not any significant
reduction above 1100C. The higher ratio of carbon consumption to oxygen reduction at 800C for diffusion bonded
steel in comparison with Mo prealloyed grade indicates more carbon loss in the former material at initial stages of
sintering. Nitrogen pickup was measured in both materials to be less than 0.03% up to 1000C; this confirms once
more that nitrogen can be used as neutral atmosphere except for soft magnetic materials.
5. REFERENCES
1- Xu, C., Blanco, L., Campos, M., Torralba, J.M., Effect of High Density Levels on Degassing of High Strength PM Steel
Compacts, Euro PM2004, Vol.2, Sintering, Vienna, Austria, p.19-24, 2004.
2- Hatami, S., Hryha, E., Nyborg, L., Nilsson, D., Modelling of Sintering Atmosphere and Microstructure Development of
Chromium Alloyed Steel, Powder Metallurgy Progress, Vol.8, No.2, pp.115-120, 2008.
3- Simchi, A., Danninger, H., Gierl, C., Electrical Conductivity and Microstructure of Sintered Ferrous Materials: IronGraphite Compacts, Powder Metallurgy, vol.44, No.2, pp.148-156, 2001.
4- Dautzenberg, N., Hewing, J., Beitrag zur Kinetik der Graphitaufloesung beim Sintern von Kohlenstoffstaehlen, Proceedings Powder Metallurgy Symposium Grenoble 7 pages, 1974.
5- Wilyman, P.R., Sintering With Nitrogen Based Atmospheres, Powder Metallurgy, Vol.28, No.2, pp. 85- 89, 1985.
6- Lindqvist, B., Kanno, K., Considerations When Sintering Oxidation-Sensitive PM Steels, Powder Metallurgy and Particulate Materials, MPIF, Part 13, 16-21 June, Orlando, USA, pp.278-290, 2002.
7- Philips, T., Dwyer, J.J., Zurecki, Z., Controlling Properties of Sintered Steel Powder Metal Components Using Atmosphere Composition As a Variable, Air Products and Chemicals, Inc., 8 p., 2006.
8- Danninger, H., Wolfsgruber, E., Ratzi, R., Sintering of Different PM Ferrous Materials at Moderate Temperatures, 1998
PM World Congress, Sintering, Spain, File PDF No. 589, pp.290-295, 1998.
9- Ortiz, P., Castro, F., Thermodynamic and Experimental Study of Role of Sintering Atmospheres and Graphite Additions
on Oxide Reduction in Astaloy CrM Powder Compacts, Powder Metallurgy, Vol.47, No.3, pp.291-298, 2004.
10- Danninger, H., Gierl, C., New Alloying Systems for Ferrous Powder Metallurgy Precision Parts, Science of Sintering,
Vol.40, pp.33-46, 2008.
11- Danninger, H., Gierl, C., Kremel, S., Leitner, G., Roessler, K.J., Yu, Y., Degassing and Deoxidation Processes During
Sintering of Unalloyed and Alloyed PM Steels, Powder Metallurgy Progress, vol.2, No.3, pp.125- 140, 2002.
12- Danninger, H., Gierl, C., Processes In PM Steel Compacts During The Initial Stages of Sintering, Materials Chemistry
and Physics, Vol.67, pp.4955, 2001.
13- Momeni, M., Gierl, Ch., Danninger, H., Ratio Tensile Strength-Vickers Hardness in Sintered Steels as a Function of
The Sintering Temperatures, Powder Metallurgy Progress, Vol.8, No.3, pp.183-189, 2008.
14- Dlapka, M., Gierl, C., Danninger, H., Bengtsson, S., Dudrova, E., Nitrogen Pickup During Sintering and Subsequent
Cooling of Chromium Alloyed PM Steels, PM2010 Powder Metallurgy World Congress & Exhibition, Florence, 10-14
Oct, Florence, Italy, Vol.2, pp.13-20.
15- Momeni, M., Gierl, C., Danninger, H., Study of the Oxide Reduction and Interstitial Contents during Sintering of Different Plain Carbon Steels by In Situ Mass Spectrometry in Nitrogen Atmosphere, Materials Chemistry and Physics,
Vol.129, Issues 1-2, pp.209-216, 2011.
428

SINTER HARDENING A TIME / COST EFFICIENT PRODUCTION LINE

Peter JOHANSSON*, Eda YILMAZTRK YKSEKDA**
*Hganas AB, SE-263 83, Hganas, Sweden, peter.johansson@hoganas.com
ABSTRACT
In order to cut costs and increase production capacity; sinter hardening could be the process route to choose. By
implementation of the sinter hardening process in the production line, it will be possible to have hardened components directly after the sintering operation.
Instead of an additional heat treatment operation in-house or by subcontractor, the components can move on
directly to secondary operations or in some cases directly for packaging and shipment to end user. As with traditional heat treatment a tempering operation is mandatory for stress relief of the material in order to increase tensile
strength and elongation properties.
To have successful results, it is necessary to do proper set up of the furnace and also perform enough trials to
understand and optimize the end result.
On the market, there are several powder alloys suitable for sinter hardening operations. Many of the alloys could
be sintered in all traditional atmospheres such as endogas, cracked ammonia and nitrogen based atmospheres but
some of the high perfomance materials for sinter hardening require nitrogen based atmospheres.
Key Words: Sinter Hardening, Cost Reduction on Sintering, Astaloy85Mo, Distaloy DH, Astaloy CrA, Astaloy
CrM.
1. INTRODUCTION TO SINTER HARDENING
To continue to expand the PM market into new applications, there is a need for materials with increased performance manufactured in a cost effective way. This can be achieved by different means. Sinter hardening, which
utilizes high performance materials in combination with accelerated post sintering cooling rates, is one example of
such means. As this is a one step process, it combines good manufacturing economy with the ability to achieve a
unique combination of mechanical properties.
Alloying elements such as copper, nickel, molybdenum and chromium all promote hardenability and these are
therefore utilized for sinter hardened PM applications. However, during the last years there have been dramatic
increases and fluctuations in raw material costs of especially nickel and molybdenum. Therefore there is a continuously growing interest to utilize more cost effective and less volatile alloy systems that enable enhanced mechanical
properties after sinter hardening. In this paper cost effective low alloy steel powders and their properties achieved
after sinter hardening will be presented.
The hardenability of a material is characterized as the ability to transform austenite into martensite. In PM, the hardenability of a material is dependent on the content of alloying elements, alloying method and processing. Carbon
content also plays an important role in hardenability.
Alloying increases the hardenability of a material and allows for more martensite transformation at a given cooling
rate, which increases the mechanical properties. Elements such as nickel, copper, and molybdenum were among
the first alloying elements to be used in PM to increase strength and hardenability.
429

Although elements such as chromium and manganese increase hardenability more than nickel and copper, they
were not used in PM alloys due to oxygen sensitivity. Advances in sintering & powder production technology have
made it possible to successfully utilize chromium and manganese and take advantage of their attributes.
Heat treatment of PM components can be performed using a variety of methods. The traditional austenitize, quench
& tempering methods are widely used throughout the PM industry. If a component manufacturer does not want a
secondary heat treatment operation, sinterhardening can be used. Sinter hardening; combines sintering and heat
treatment in one single step in order to produce high strength and wear resistance of the material and minimizing
the number of processing steps. Both conventional quench & tempering and sinter hardening modify the microstructure of a material system through increased cooling rates.
Sinter hardening is a process step that can be fully integrated in the normal sintering operation. The sintering furnace is equipped with a rapid cooling device (gas quenching) between the sintering zone and cooling zone circled
in figure 1.
Figure 1. Belt furnace equipped with rapid cooling device.

The sintering atmosphere is cooled by circulation of gas through heat exchangers as shown in Figure 2.
Figure 2. Rapid cooling device.

Normal cooling rates achieved in production lines are 2 to 5C/s depending upon furnace load, i.e. mass and geometry. After sintering zone (or carbon restoration zone if the furnace is equipped with this section), the rapid cooling
occurs. Figure 3 displays a typical temperature profile where rapid cooling starts directly after the sintering zone.
430

Materials for sinter hardening are tailor made in order harden at slightly higher cooling speeds than for normal sintering operations with cooling speeds between 0.5 to 1.0C/s.
If insufficient hardening was obtained, as in Figure 4a, with too low amount of martensite, the alloying elements
could be modified. In Figure 4b alloying elements have been increased and the pearlite and bainite nose have been
shifted to the right, leading to that hardening occur at lower cooling rates resulting in more martensite. In both cases
the cooling rate was the same. In Figure 4c the original composition of alloying elements was maintained, but the
cooling rate was increased resulting in similar hardening effects as for example in Figure 4b.
Figure 4a. Insufficient hardening.
Figure 4b. Increase of alloying elements.
Figure 4c. Increase of cooling rate.
431

As with traditional heat treatment a tempering operation is necessary in order to reduce internal stresses in the
sinter hardened components, i.e. to temper the brittle martensite obtained during the rapid cooling.
The influence on mechanical properties with/without tempering for Distaloy DH + 0.7%C sintered in 90%N2 /
10%H2 at 1120C for 30 minutes with a cooling rate between 3 to 4C/s is shown in Figure 5. The hardness properties decreases but tensile, yield and elongation properties increase. 200C for 60 minutes proved to be the better
temperature and time for the tempering process for all the materials tested. Tempering at 300C decreases the
elongation due to tempering embrittlement.
Figure 5. Effects of tempering.

The tempering operation could be carried out in a separate line (furnace constructed for lower temperatures without
any additional gas consumption) or be built into the furnace system as shown in Figure 6. With a system like this,
the components can go directly from the furnace to the secondary operations or perhaps even directly to packing
and shipping to the end user after quality control.
Figure 6. Built-in tempering zone, in sintering furnace.

2. COST COMPASRISON BETWEEN SINTER HARDENING AND HEAT TREATMENT
The investment cost for a separate heat treatment furnace is approx. 4 times higher than the costs for the rapid
cooling device that is assembled onto the sintering furnace.
Many of the PM producers use a subcontractor for heat treatment of their components. This means that no investments for a HT furnace are necessary. However, the service has to be bought with additional costs of transportation
+ longer lead times before the components could be sent to the end user. Multiple quality controls will be necessary
in this case; one after sintering and a second one after the components arrive from subcontractor.
According to recent calculations carried out by Hgans AB and a furnace supplier, the cost for external heat treatment + tempering was approx. 70 to 80% of the total cost of a component. These figures were obtained during
calculations of setting up 2000+ ton/year production line in western parts of Europe including a new large capacity
sintering furnace with depreciation costs, operator costs, maintenance costs and energy costs etc. The actual sintering cost was 0.2 /kg and 0.8 /kg for the external heat treatment and tempering.
To perform traditional heat treatment in-house, requires 4 times higher investment costs with higher processing
costs due increased gas consumption and energy costs.
With the sinter hardening process line, a continuous operation results in a through hardened PM component when
leaving the sintering furnace.
432

Figure 7. Comparison of HT and Sinter hardening main highlights.

3. SINTER HARDENING MATERIALS GRADES FROM HGANAS AB
From Hgans AB there are many different grades designed for sinter hardening, three of them are displayed in
Figure 8. Traditional Hgans materials such as Distaloy AE work excellent for sinter hardening but the amount of
alloying elements in the material is high.
*Cr materials are sensitive for oxidization which means that endogas is not suitable as sintering atmosphere. The
recommended atmosphere is nitrogen based with additions of hydrogen. Syntetic DA (75%H2 / 25%N2) atmosphere can be used, but requires carbon control.
The Distaloy DH (Direct Hardening) grade is based on pre-alloyed Astaloy Mo with diffusion bonded Cu. A leaner
version is possible for sinter hardening applications with Astaloy 85Mo + Cu powders. Both grades are used for
sinter hardened synchronizer hubs around the world.
The Distaloy LH grade is based on pre-alloyed Astaloy LH with diffusion bonded Cu.
Distaloy DH, leaner version (Astaloy 85Mo + Cu) and Distaloy LH can be processed in endogas, nitrogen based
atmospheres and DA atmospheres.
Figure 8. Three sinter hardening grades from Hganas AB.

In Figure 9, Astaloy CrM + 0.4%C with two different cooling rates are compared.
Figure 9. Astaloy CrM with two different cooling rates are compared.
433

In Figure 10, Distaloy DH + 0.55%C with two different cooling rates are compared.
Figure 10. Distaloy DH + 0,55%C with two different cooling rates are compared.
4. DISCUSSIONS
With a cost effective lean alloyed material and increasing the cooling rate with 2C/s in a sinter hardening furnace,
results in a fully martensitic structure compared to a bainitic structure with conventional sintering of the materials,
which leads to higher hardness and tensile strength of the components. It is important that a material with high
enough hardenability is used for the process and there are several cost effective lean alloyed materials available
that are suitable for sinter hardening. The structure of these materials after sinter hardening are similar and the
properties are on the same levels as conventional heat treated materials, but produced in one process step without
any subcontractors. Reducing the processing steps results in that the total production costs of a hardened component can be lowered and the properties are on the same level if a material with high hardenability is used.
5. CONCLUSION
In order to cut production costs, it might be possible that sinter hardening could do a successful job. By implementing rapid cooling device to the sintering furnace, it is possible to have through hardened components leaving the
furnace. Time and costs could be reduced due to less logistics and lower production costs.
Thank to Ingo Cremer at Cremer GmbH, Sigurd Berg at Hgans AB
434

SINTERING ACTIVATION AND MASS TRANSFER IN Ni-ALLOYED

PM STEELS WITH ADDITION OF PRE-NITRIDED POWDER
Diyan M. DIMITROV*, Penka ZLATEVA**
**
*Technical University of Varna, Faculty of Shipbuilding,

Department of Mechanical Engineering, 9010, Varna, Bulgaria, dimitrov.diyan@gmail.com
Technical University of Varna, Faculty of Shipbuilding, Department of Heat Engineering, 9010, Varna, Bulgaria,
pzlateva1@abv.bg
ABSTRACT
In the present article sintering activation and mass transfer during microstructure formation, in compacts prepared
from AstaloyCrL and DistaloySA powders with Ni, graphite and pre-nitrided powder addition were discussed. Prenitrided fine grade ASC powder with about 1%N as a sintering activator was used. Rectangular (5x5x15) compacts
were pressed to density of about 6.0-6.2g/cm3. Sintering was done in an industrial mesh belt furnace at 1120oC under flowing 90%N2+10%H2 atmosphere. Dimensional changes after sintering were controlled. In compacts with prenitrided powder the sintering shrinkage is higher, especially in AstaloyCrL compacts. The observed microstructures
of AstaloyCrL compacts were different. The addition of pre-nitrided powder gives higher percent lower bainite and
martensite phases. The microstructures of DistaloySA compacts were similar. It seems that pre-nitrided Fe-powder
is a better sintering activator for Cr prealloyed powders than Cu, Ni, Mo diffusion alloyed ones.
Keywords: Powder Metallurgy, Sintering, Microstructure, Nitriding, Mass Transfer
1. INTRODUCTION
The use of thermal instability of iron nitrides as a possible way of sintering activation in Fe-based systems is topic
of several papers in the last 20 years [1-9]. An iron nitride phase was incorporated by both using pre-nitrided iron
powders in the composition or nitriding of green compacts. Since nitriding potential of the most common N2+H2
sintering atmospheres is very low iron nitrides are instable and disappear during heating, resulting in in situ active
surface. As a consequence such compositions exhibit enhanced sinterability (high sintering shrinkage). Sintering
shrinkage depends on the protective atmosphere and the amount of nitrogen. In hydrogen rich atmospheres iron
nitrides decompose rapidly at lower temperatures, resulting in higher sintering shrinkage [2]. In [3] it was demonstrated that main contribution to sintering shrinkage has the shrinkage in high temperature austenite region. The
denitriding process also favors carbon dissolution into iron matrix and, again, accelerates sintering shrinkage [4].
These theoretical studies dont take into account the isothermal holding for delubrication in industrial sintering process. Investigations at temperature of 650oC (delubrication zone average temperature) show that in nitrogen rich
(<10%H2) atmospheres, there is no sufficient nitrogen loss, but nitrogen diffusion is activated [3, 5]. Taking into account the inhomogeneous N distribution (N is concentrated in nitrided particles) the diffusion process from nitrided
to pure powder particles begins, resulting in nitrogen redistribution into the whole volume i.e. the whole volume of
the compact is activated.
On the other side is the compressibility of such powder mixtures. Nitriding increases hardness of the powder particles, especially Cr prealloyed grades, thus drastically reducing the compressibility of powder mixtures. To solve
this problem in [3,5] short time nitrided fine fraction (<53m) atomized iron ASC100.29 powder with approximately
1wt%N and microhardness 100-120HV0.05, as a sintering activator was proposed. It is shown that mixtures with
25% of such powder have similar green density as the mixture without an addition. It is reasonable to assume that,
since nitride powder in this case is only a nitrogen donor, its quantity can be limited to 10% or even 5% and the
sintering activation to be considered not only as a sintering shrinkage, but the phase composition has also to be
taken into account.
435

The main objective of this paper is to discuss the influence of nitrided powder addition on the alloying behavior of
one of the mostly used alloying elements - Ni. Despite its high price fluctuations and some environmental issues, Ni
is still an attractive alloying element in high performance low alloy PM steels [10-16]. Since Ni increases the ferrite
hardness, thus decreasing the compressibility of powders, usually Ni is added as diffusion bonded or admixed to
keep high compressibility. It is known that due to the slow Fe-Ni interdiffusion and the strong repulsion between Ni
and C Ni-rich C-lean and/or areas form in sintering process [12,15]. These Ni rich areas are soft and prone
to fracture during mechanical loading [15]. The alloying mechanism is reported in [13]. First fast particle and grain
boundary diffusion of Ni was observed, followed by a slow volume Fe-Ni interdiffusion process with preferential
atomic flow from Fe into Ni. As a result, depending on the Fe-Ni concentration profile, the carbon quantity and
the cooling rate, , or (martensitic) phases can form. One possibility to diminish these Ni-rich areas is using a
ultrafine (<0.5m) Ni particles [12,16]. Chromium alloying can diminish the repulsion effect between Ni and C, thus
eliminating Ni-rich soft ferrite and austenite [14].
It is assumed that activated surface due to denitriding process (with a lot of vacancies defects) will increase atomic
diffusion flow from Ni into Fe and will improve Ni alloying.
As a base Fe material the prealloyed AstaloyCrL (Fe-1.5%Cr-0.2%Mo) and the diffusion bonded DistaloySA
(Fe-1.75%Ni-2%Cu-0.5%Mo) powder grades have been used. Fine fraction (<53m) from atomised Fe powder
ASC100.29, short time gas nitrided at 560oC with nitrogen content about 1wt%N (controled by LECO analyzer), as
an activation substance was added to some of the mixtures. Artificial graphite grade (TIMCAL F10), fine (20m)
electrolytic Ni powder, and 0.6%Kenolube as a lubricant was also used. Powder mixtures with composition given
in Table 1 were prepared by tumbling 30min in a turbula mixer. From the powder mixtures, rectangular compacts
(5x5x15 mm3) were formed. Sintering was carried out in an industrial mesh belt furnace under flowing N2+10%H2
atmosphere for 30min at 1120oC. The temperature of the delubrication zone of the furnace is about 650oC, the average cooling rate is about 0.75Ks-1.
Table 1. Composition and green density of compacted samples.
Code
A1_N
A2
D1_N
D2
Powder mixture composition

AstaloyCrL(Fe-1.5%Cr-0.2%Mo)+10%ASC(nitrided)
+0.6%Ni+0.6%C
AstaloyCrL(Fe-1.5%Cr-0.2%Mo)+0.6%Ni+0.6%C
DistaloySA (Fe-1.75%Ni-2%Cu-0.5%Mo)+ +10%ASC(nitrided)+0.45%C
DistaloySA (Fe-1.75%Ni-2%Cu-0.5%Mo)+0.45%C
Green density, g/cm3

6.35
6.26
6.17
6.05

Calculated sintering shrinkage/swelling of samples was shown on Fig.1. On activated samples (A1_N, D1_N) higher
shrinkage was measured. It is clearly seen that activated CrL powder (A1_N) shows higher percent shrinkage compared to non-activated (A2). For Distaloy powder probably Cu inhibits higher shrinkage, dissolving at the activated
grain boundaries. For significant activation of this powder higher percent nitride powder addition is needed.
Figure 1. Shrinkage/swelling of sintered samples. A-astaloyCrL; D-distaloySA ; 1_N-with nitrided powder;

2 without nitrided powder;
436

Data for measured apparent hardness of sintered samples is collected in Table 2. Again the same tendency is
observed. Activated samples have slightly higher hardness and in Cr prealloyed samples hardness improvment is
higher.
Table 2. Apparent hardness of sintered samples.
Code
A1_N
A2
D1_N
D2
Hardness, HV10
130-165
124 -133
101-117
95-101
Observed microstructures of sintered AstaloyCrL based samples are shown on Fig.2. On pictures mainly coarse
(upper) and fine (lower) bainite were registered. The measured mirohardness of coarse bainite is in the range of
167-204HV0.05. Most of the lower values are measured in A2 sample. Fine bainite have microhardness 279427HV0.05. In both samples Ni-rich areas are visible. Their microhardnesses are 205-268HV0.05 for A1_N
activated and 101-120HV0.05 for A2 sample. Traces of Ni grain boundary diffusion (red arrows) can be seen on low
magnification picture (upper row). Additionally little Ni-rich martensite was found. Finally, when nitrided activator
was added the microstructures was improved. More, fine bainite formed at the expense of upper bainite. This result
was due to better Fe-Ni alloying.
On Fig.3 the observed microstructures of sintered DistaloySA based samples are shown. The microstructures of
both samples look similar and consist of pearlite, ferrite, bainite and Ni-rich areas. It seems that the activation of this
sample is not linked with a significant microstructure improvement.
Figure 2. Microstructures of sintered AstaloyCrL based samples; A1_N -left side ; A2 right side.
437

Figure 3. Microstructures of sintered DistaloySA based samples; D1_N -left ;
D2 right.
4. CONCLUSION
For Cr prealloyed PM steels with added Ni, the addition of 10% pre-nitrided powder as a sintering activator, seem
to be a promising way to improve their microstructure. More fine bainite forms, resulting in increased apparent
hardness.
For diffusion bonded samples no significant microstructure improvement was found. Probably Cu diffuses faster into
the activated particles, resulting in its inhomogeneous distribution and altering Ni-diffusion.
5. ACKNOWLEDGEMENTS
Authors wish to thank Gamasinter Ltd Varna, Bulgaria for sintering of investigated samples
REFERENCES
1. T. Pieczonka, S. Harizanova, R. Rusev, E. Ruseva, Dialtometric Analysis of Sintering during Heating Stage of
Nitrided Fe-2 wt.-% Ti Powder Mixtures Proceedings of 2000 Powder Metallurgy World Congress, Kyoto,
2000, p. 785 788
2. Harizanova S., .Russev R, Ruseva E., Petkova R., Pieczonka T., Povedenie na probi ot jelqzo-titanovi prahovi
smesi pri spichane v H2 i bogata na N2 gazova sreda, II International Science- Technical Congress Mechanical Engineering99, Varna, 1999 , p. 61 66 (in bulgarian)
3. Dimitrov, D.M., Structure and Properties of alloyed PM steels on a base of AstaloyCrl powder grade, after sintering and surface heat treatment, PhD Thesis, Technical University of Varna , Varna, 2010.
4. Dimitrov, D.M., T. Pieczonka, S.D. Harizanova. Sintering Behaviour of AstaloyCrL Based Powder Mixtures,
Containing Nitrided AstaloyCrL and Graphite Additions, Proceedings of 5th International Powder Metallutgy
Converence, 08-12.10.2008, Ankara, Turkey, 2008, pp. 1387-1397
5. Dimitrov, D.M., P.N. Zlateva, S.D. Harizanova, S. Gyurov. Structure Forming and Chemical iteractions during
Sintering of Low Alloyed Chromium PMsteels with Addition of Nitrided Powders. Proceedings of Material
Science and New Materials, 04-05.12.2008, Sofia, BAS, 2008,pp.128-132
6. S. Harizanova, T. Pieczonka, E. Ruseva, M. Stoytchev, R. Rusev, Sintering Behaviour of nitrided mixtures
of ASC100.29 Hoganas Grade and Sponge Titanium Powder, Proceedings of Deformation and Fracture in
Structural PM Materials International PM Conference, Piestany .99,IMR SAS Kosice, vol. 2, p. 26 29
7. T. Pieczonka, S. Harizanova, R. Rusev, E. Ruseva, Dialtometric Analysis of Sintering during Heating Stage of
Nitrided Fe-2 wt.-% Ti Powder Mixtures Proceedings of 2000 Powder Metallurgy World Congress, Kyoto,
2000, p. 785 788
8. Harizanova S., Pieczonka T., Ruseva E., Rusev R., Decheva D., Stoytchev M., Thermal Stability of Nitride
Phases in Fe-2Ti sintered Alloys, Proceedings of the PM Congress Valensia, 2003., v.1, . 435 440
9. Pieczonka T., Harizanova S., Decheva D. Sintering of low-temperature gas carbonitrided iron-base materials
containing 2wt.-% Ti Sacaria Powder Metallurgy Conference proceedings, Turkey, 2006
438

10. F. Castro, S. Sainz, Influence of Ni on hardenability of PM steels, Advances in Powder Metallurgy and
Particulate Materials, Lauderdale, Florida, USA, 2010.
11. Hwang et al. Comparison of mechanical properties of Fe175Ni05Mo15Cu04C steels made from PIM
and press and sinter processes, Powder Metallurgy 2002 Vol. 45 No. 2, pp160-166
12. W. Garca, P. Uranga, F. Castro, Influence of Nickel and Cooling Rate on the Microstructural Development of
Mo-Containing PM Steels, Euro PM2008-Sintered Steels, Mannheim, Germany. Vol. 2, pp. 153-158.
13. S. Sainz, W. Garca, A. Karuppannagounder, F. Castro, Microstructural development during sintering of PM
steels with admixed Nickel, Powder Metallurgy Progress, Vol.7 (2007), No 3, pp121-127
14. Wu M.W., K. S. Hwang and K. H. Chuang Improved distribution of Ni and C in sintered steels through addition
of Cr and Mo, Powder Metallurgy 2008 VOL 51 No 2, pp160-165
15. Wu, M.-W. Hwang, K.-S., The Mechanisms of the Formation and Elimination of Weak Ni-Rich Areas in PM
Steels, Advances In Powder Metallurgy And Particulate Materials, 2007, NUMB 2, pages 07-12-07-23
16. T. F. Stephenson, S. T. Campbell, T. Singh, Properties of Prealloyed Mo Steels Admixed with Extra-Fine Ni
Powder, Procs. of EuroPM2003, , Valencia, Spain 2003. Vol.1, pp. 269-275
439

Production Of MWCNT Reinforced Bronze Matrix Composite

By Current Activated Sintering
Ramazan KARSLIOLU, Mehmet UYSAL, mer Faruk YAZICI, Hatem AKBULUT
Sakarya University Engineering Faculty, Department of Metallurgical and Materials Engineering,
rkarslioglu@sakarya.edu.tr
Abstract
In this study, bronze matrix (90 wt. % Cu + 10 wt. % Sn) was reinforced with multi walled carbon nanotubes
(MWCNTs) using mechanical alloying and then produced by subsequent rapid current sintering technique. The
mechanically ball milled bronze matrix powders was reinforced with various amounts of MWCNT (1.0 wt. %, 3.0 wt.
% and 5.0 wt. %). The composites were cold compacted under a constant pressure of 200 MPa. The compacted
structures were sintered at atmospheric conditions almost to the full density within 10 minutes at 1000 A using
current sintering, in which the powders were heated by a low voltage and high amperage current and compressed
simultaneously. Microhardness testing, and scanning electron microscopy (SEM) studies were carried out for the
characterization of the composite. Optimal microstructure was targeted to determine the properties for the resultant
composites.
Key words: Rapid current activated sintering, CNT, Bronze, composite.
1. Introduction
Copper and copper matrix composites have been known as excellent engineering materials for application where
good mechanical and thermal properties are desired [1-2]. Cu-matrix particle MMCs may even be more suitable
for use in brakes and other severe frictional applications because of (1) the higher thermal conductivity of these
MMCs, which makes them better than Al-SiC MMCs at conducting frictional heat away from the sliding interface; (2)
the much higher melting and softening temperatures of copper; and (3) the superior corrosion resistance of copper
and its alloys in chloride environments [3]. Dispersed particles such as oxides, carbides, and borides, which are
insoluble in the copper matrix and thermally stable at the high temperatures, are being increasingly used as the
reinforcement phase. Various methods have been used for making MMCs such as liquid metal infiltration, squeeze
casting, diffusion bonding, electrodeposition, and PM [4]. The relatively high melting point and poor wettability of the
reinforcement phase by the copper make powder metallurgy suitable for production of copper-based composites
[5].
Interest for using multiwall carbon nanotubes (MWCNTs) to reinforce polymers, ceramics and metals has grown
tremendously over the last decade because of their attractive mechanical and thermal properties [6]. Many researchers have reported on mechanical properties of carbon nanotubes that exceed those of any previously existing materials. Although there are varying reports in the literature on the exact properties of carbon nanotubes,
theoretical and experimental results have shown extremely high elastic modulus, greater than 1 TPa (the elastic
modulus of diamond is 1.2 TPa) and reported strengths 10100 times higher than the strongest steel at a fraction
of the weight. Indeed, if the reported mechanical properties are accurate, carbon nanotubes may result in an entire
new class of advanced materials [7]. Also CNTs have very high thermal conductivity (30006000 W (m K)-1) along
the tube direction. Excellent mechanical and thermal properties combined with their low-density make CNTs as
an ideal reinforcement to fabricate high-performance composites for various engineering applications [6]. However, limited research has been done in preparation, structural, physical and mechanical properties of metalCNT
440

nanocomposites. Poor wetting behaviour or weak interfacial bonding to matrix materials, agglomeration among
themselves with Van-der-Waals force, inhomogeneous distribution of CNTs in the matrices and degraded thermal
stability at high processing temperature are the prime drawbacks to use carbon nanotubes as reinforcements of
metal matrix composites. For instance, Kuzumaki et al. [8] reported very little improvement in tensile strength of
CNT reinforced Al nanocomposites prepared by conventional powder mixing, hot-pressing followed by hot extrusion
due to inhomogeneous dispersion of CNTs in the metal matrix.
For any case, the homogeneous dispersion of nanotubes in metal matrices is the prime requirement before fabricating carbon nanotube based metal matrix nanocomposites. Early studies carried out by Uddin et al. [9] showed
that, high energy mechanical alloying involved continuous impact, welding, fracturing and re-welding of powders
to disperse nanotubes in the metal powders. The objective of the present investigation is to prepare bronze-matrix
composite reinforced with five different ratios (1.0, 3.0 and 5 wt. %) MWCNT by using a rapid current activated
sintering technique. Effect of the different ratio MWCNT on the bronze matrix MMCs were investigated. In this contribution, we report on the successful preparation of MWCNT reinforced bronze composites by mechanical mixing
of nanotubes and metal powders followed by current activated sintering. A new approach was taken into account to
obtain rapid and cost effective sintering to improve hardness of MWCNT reinforced bronze matrix.
2. Experimental
Three different ratios MWCNTs reinforced bronze metal matrix composites were produced by rapid current activated sintering technique. The matrix material was a 10 wt. % Sn bronze alloy in the powder state and has an
average particle size of 80 m. The average particle sizes of the MWCNT were 80 nm in diameter and 8 m in
length. The blended and mechanically planetary ball milled bronze matrix powders and MWCNTs were then cold
compacted, which was a disk form in 25 mm diameter, under a pressure of 300 MPa to obtain nanocomposite.
The cold compacted nanocomposite mixture structure was then sintered at atmospheric conditions to nearly a full
density within 10 minutes under an applied pressure of 10 MPa. The compaction processes were accomplished in
a single process. The sintering was carried out at high-current levels as high as 1200-1500 Amperes and constant
voltages (2.5 V).
The current activated sintering system setup is shown in Fig. 1. After sintering treatment the samples were left the
air for cooling, and the samples were cut from the disks and prepared to use standard metallographic techniques.
Polished and lightly etched specimens were examined using for microhadness test. The matrix microhardness
measurements were carried out on polished samples using 50 g load for 10 sec. Also the composites were prepared
to investigate fracture surfaces for scanning electron microscope (SEM) and Energy dispersive X-ray analysis investigation (EDS). A complete fracture surface microstructural characterization was carried out via SEM and EDS
(JEOL 6060LV).
Fig 1. a) Schematic presentation of the current activated sintering system and b) an example of sintering
process application [1].
441

3. Results and Discussion

In an early contribution[21] S.M. Uddin, T. Mahmud, C. Wolf, C. Glanz, I. Kolaric and M. Hulman et al., Thermal
expansion coefficient of nanotube-metal composites, Phys Status Solidi B 246 (1112) (2009), pp. 28362839.
Full Text via CrossRef | View Record in Scopus | Cited By in Scopus (2), it was shown that the planetary ball mill
employed a strong centrifugal force to develop high energy milling action inside the vial, which in fact involved
continuous impact, welding, fracturing and re-welding of MWCNTmetal powders[9]. Milling for time 3 h did not
show good embedment of MWCNTs in the matrix materials and (b)
prolonged milling promoted cold-welding of metal
powders
producing very large metal particles.
(a)
Fig. 2. SEM microphotograph of mechanically alloyed bronze and MWCNT (a)low magnification (b) high magnification
In the current activated sintering process was aimed to produce of the nanocomposite. Fig. 3-4 show the microstructure of the composites that produced by using different voltage applications. In Fig. 3-4 both the fracture
surface microstructures in low magnification and high magnification are presented. In Fig 3 and 4 the MWCNT
distribution is also shown. The fracture microstructure reveals a good bonding is provided and no de-attachment
was observed with low porosity among the grains and MWCNT. All the nanocomposites produced by current sintering show uniform distribution of particles through the matrix. EDS analysis was given in Fig. 5. EDS analysis shows
Cu-Sn elements and also C traces, which belongs to the carbon nanotubes.
Fig.3. Low magnification fracture surface micrographs of the composite produced with different applied voltages;
a) 2 V, b) 2,5V and c) 3 V
442

Fig.4. High magnification fracture surface micrographs of the composite produced with different applied voltages;
a) 2 V, b) 2,5V and c) 3 V
The hardness of the MWCNT/bronze nanocomposites as well as the unreinforced bronze alloy was measured
by Vickers hardness test. Fig. 6 shows the effect of the MVCNTs weight fraction on the hardness of the prepared
MWCNT/Bronze nanocomposites. Micro hardness of unreinforced bronze alloys is 98 Hv. The microhardness of
the nanocomposites dramatically increases with reinforced MWCNTs. Hardness of 1 wt. % MWCNT reinforced
bronze alloys is obtained as 158 Hv. However over the 1 wt. % MWCNTs, The hardness of the composites decreases with increasing MWCNTs. The improvement in the hardness of bronze based nanocomposite matrix is
related to the second phase hardening effect caused by MWCNT in the nanocomposite matrix, which obstructs the
shift of dislocation in nanocomposite. Two reasons are suggested to be responsible for the increase in hardness;
particle-strengthening and grain refining.
Particle-strengthening is related to the incorporation of MWCNT and amount fractions above 1 wt. %. In this case,
the load is carried by both the matrix, and the particles and strengthening is achieved because the particles restrain
the matrix deformation. The second mechanism is related to the nucleation of small grains on the surface of the
incorporated particles, resulting in a general structural refinement. In this case, the presence of smaller grains impedes dislocation motion resulting in an increase in microhardness. Also; MWCNTs resulted to obtain a hardness
value as high as 158 Hv whereas, unreinforced bronze showed only 98 Hv. This corresponds to 61 % hardness
increment.
Fig. 5. EDX analysis of nano composite
443

Fig. 6. Matrix microhardness variation of composite depending volume fraction of MWCNT.

4. Conclusions
Bronze alloys and MWCNTs reinforced bronze metal matrix composites were successfully produced by rapid
current activated sintering technique.
SEM photographs show uniform distribution of MWCNT through the matrix.
EDS analysis shows Cu-Sn elements and also C traces which belongs to the carbon nanotubes.
The microhardness of the nanocomposites dramatically increases with reinforced MWCNT. Introducing MWCNT resulted to obtain a hardness value as high as 158 Hv whereas, unreinforced bronze showed only 98 Hv.
This corresponds to 61 % hardness increment.
The microhardness of the bronze matrix was increased as the increasing applied voltage.
References
1. Karslioglu R., Uysal M., Alp A., Akbulut H., Wear Behavior of Bronze Hybrid MMCs Coatings Produced by Current Sintering on Steel Substrates Tribology Transactions, Vol. 53 pp 779-785, 2010
2. Sornakumar, T., and Senthil Kumar, A. Machinability of BronzeAlumina CompositeWith Tungsten Carbide
Cutting Tool Insert, Journal of Materials Processing Technology, Vol. 202, pp 402-405. 2008,
3. Kennedy, F. E., Balbahadur, A. C., and Lashmore, D. S.), The Friction And Wear of Cu-Based Silicon Carbide
Particulate Metal Matrix Composites for Brake Applications, Wear, Vol. 203/204, pp 715-721. 1997
4.Distribution in Al/Al2O3 Composites Obtained from Composite Powder, Materials Characterization, Vol. 46, pp
189-195.
5. Sapate, S. G., Uttarwar, A., Rathod, R. C., and Paretkar, R. K. (2009), Analyzing Dry Sliding Wear Behaviour
of Copper Matrix Composites Reinforced with Pre-Coated SiCp Particles, Materials and Design, 30, pp 376386.
6. Bhata A., Balla V. K., Bysakh S., Basu D., Bose S., Bandyopadhyay A., Carbon nanotube reinforced Cu10Sn
alloy composites:Mechanical and thermal properties Materials Science and Engineering A Vol. 528 6727
6732. 2011
7. Erik T. Thostenson, Zhifeng Ren, Tsu-Wei Chou, Advances in the science and technology of carbon nanotubes
and their composites: a review Composites Science and Technology Vol. 61 18991912 2001
8. Kuzumaki T, Miyazawa K, Ichinose H, Ito K. Processing of carbon nanotube reinforced aluminium composite.
J Mater Res Vol. 13: 24452454. 1998
9. Uddin SM, Mahmud T, Wolf C, Glanz C, Kolaric I, Hulman M, et al. Thermal expansion coefficient of nanotube-metal composites. Phys Status Solidi B; Vol 246(1112):28362845. 2009
444

Al+%5MgO KOMPOZT MALZEMENN ZELLKLERNE SNTERLEME

SICAKLII VE SNTERLEME SRESNN ETKLER
Yusuf KARAMAN*, Hanifi NC**, Recep ALIN***
*Krkkale niversitesi, Makine Mhendislii Blm, Krkkale
**Gazi niversitesi, Metal Eitimi Blm, Ankara
***Krkkale niversitesi, Malzeme ve Metalurji Mhendislii Blm, Krkkale
ZET
Toz Metalurjisi (T/M) yntemiyle metal matrisli kompozit (MMK) retimi iin, saf alminyum (Al) matris malzemesi
olarak seilmi ve %5 arlk orannda MgO takviye malzemesi olarak belirlenmitir. Hazrlanan toz karmlar 500
MPa basn altnda tek ynl sktrma ilemine tabi tutulmulardr. Arlka %5 takviye oran ieren ham numuneler 570-600-630 C scaklklarda argon (Ar) gaz atmosferinde 1,2 ve 4 saat sreyle sinterleme ilemi uygulanmtr.
Elde edilen numuneler optik mikroskop ve SEM grntleri alnp mikroyaplar incelenerek younluk, sertlik ve
apraz krlma mukavemetleri llmtr. Yaplan alma sonucunda sinterleme scakl ve sinterleme sresinin
artmasna bal olarak younluk, sertlik ve apraz krlma dayanmlarnn artt grlmtr. Deerler incelendiinde en iyi sonularn 630 Cde 4 saat sinterlemede elde edildii tespit edilmitir.
ABSTRACT
In this study, weight percent of 5% MgO reinforcement aluminum (Al) matrix composites were produced by powder
metallurgy (P/M) method. Prepared powder mixes had been mixed for 60 minutes by Turbula. Powders were compacted at 500MPa pressure by single action press. Weight percent of 5% MgO reinforced composite specimens
had been sintered at 570; 600 and 630C for 1-2-4 hours in argon atmosphere. After having the results of density,
hardness and transverse rupture strength (TRS) tests, the best results were obtained on sintering process at 630C
for 4 hours. The increasing sintering temperature and time made the porosity decrease and made the mechanical
properties improve. Specimens surface inspections were applied by optical microscopy (OM) and scanning electron
microscopy (SEM).
Key Words: MgO, TRS, Transverse Rupture Strength, Sintering Temperature, Sintering Time
1.GR
Farkl zellikteki malzemelere olan ihtiya yeni retim tekniklerinin gelitirilmesini salamtr. Tek bir bileenden
oluan malzemeler genellikle ihtiyalar karlayamamaktadr. Bu sebepten dolay kompozit malzemelerin bir grubu olan metal matrisli kompozitler (MMK) gelitirilmektedir [1,2]. MMK malzemeler yksek mekanik zellikleri ve
anma direnleri sayesinde endstride geni kullanm alan bulmaktadrlar. Alminyum matrisli kompozitler dk younluklar, yksek tokluklar ve yksek korozyon direnleri sayesinde endstride geni kullanm alan bulmaktadrlar. Havaclk ve uzay sanayisi, otomotiv, savunma ve elektronik sanayileri bu alanlarn nde gelenleridir.
Alminyum saf halde yksek mekanik zelliklere sahip deildir. Ancak Al2O3, SiC, TiC, B4C ve MgO gibi seramik
malzemelerin takviye eleman olarak kullanlmas sonucunda elde edilen alminyum matrisli kompozitlerin mekanik
zellikleri yksektir [3-7].
Toz metalurjisi (T/M) en yaygn kompozit retim yntemlerinden biridir. Dkm yntemine gre en byk avantaj
homojen takviye eleman dalm sayesinde mikroyapnn kontrol edilebilmesidir [4]. T/Mnin dier bir avantaj da
kat hal sinterlemesi sonucunda matris ve takviye eleman arayzeyinde istenmeyen fazlarn oluumunu en dk
seviyede tutulmas sonucunda arayzeyde kuvvetli bir ba oluumunu salamasdr [3,8]. Bu almada T/M yntemiyle retilen Al-MgO kompozitlerinin mekanik zelliklerine sinterleme scaklnn ve sinterleme sresinin etkileri
aratrlmtr.
445

2.DENEYSEL YNTEM
Bu almada gaz atomizasyonu yntemiyle retilmi %99,7 saflk orannda 76,39 m ortalama toz tane boyutundaki Al tozlar matris malzemesi olarak kullanlmtr. 29,53 m ortalama toz tane boyutuna sahip saf MgO
tozlar takviye eleman olarak kullanlmtr. Arlka %5 MgO oran ieren Al-MgO toz karmlar Turbula cihaznda 60 dakika kartrldktan sonra tek etkili preste 500 MPa basn altnda sktrlarak ASTM standartlarndaki
6,35x12,70x31,75mm boyutlarnda apraz krlma numuneleri elde edilmitir. Elde edilen test numuneleri argon (Ar)
gaz ortamnda yatay tpl frnda 570; 600 ve 630C scaklkta 1; 2 ve 4 saat srelerde sinterlenmilerdir. Arimet
prensibine gre younluklar llen numunelerin gerekli yzey ilemlerinden sonra Vickers yntemi ile sertlikleri
llm ve ASTM standartlarna gre apraz krlma mukavemetleri (KM) llmtr. Numunelerin mikroyap
incelemeleri taramal elektron mikroskobunda (SEM) yaplmtr.
3.DENEYSEL BULGULAR VE TARTIMA
3.1. Younluk sonularnn incelenmesi
Farkl sinterleme scaklk ve srelerinde elde edilen younluk sonular ekil 1de verilmitir. ekil 1 incelendiinde
artan sinterleme scakl ve artan sinterleme sresi sonucunda elde edilen younluk deerlerinin ykseldii grlmektedir. Bu art Eitlik 1de yer alan Arrhenius denklemi [9,10] ile aklanabilir.

(1)
Burada DV hacim difzyonu katsays, D0 malzeme sabiti, Q aktivasyon enerjisi, R gaz sabiti ve T mutlak scaklktr. Denklemin sa tarafndaki T deerinin artmasyla DV deerinin de artaca ak bir ekilde grlmektedir.
ekil 1. %5 MgO takviye

oranl kompozitlerin sinterleme sresi ve sinterleme
scaklna gre
younluk deiimleri.
Ergime scaklna yakn scaklklarda daha fazla atom komular ile balarn kopartp yeni yerlere gitmek iin
daha yksek enerjiye sahiptir [10]. Artan scaklk ile Al paracklar arasnda daha fazla difzyon gerekletii ve
gzeneklerin birleerek daha dk enerji konumuna getii deerlendirilmitir. Sonu olarak scakln artmas
ile sinterlenebilirlik artm [11] ve sinterlenebilirliin artmas younluk deerlerini arttrarak teorik younlua yakn
deerler elde edilmitir.
ekil 2. 630Cde 1 saat (a), 2 saat (b) ve 4 saat (c) sinterlenmi numune yzeylerinin SEM grntleri.
Sinterleme sresinin artmasyla paracklar arasndaki boyunlamann gelitii, gzeneklerin azald [12] artan
sre ile paracklar aras difzyonunda artmas sonucu yksek younluk deerleri elde edilmitir.
446

ekil 3. 4 saat sreyle 570Cde (a) ve 600Cde (b) sinterlenmi numune yzeylerinin SEM grntleri.
ekil 2 ve ekil 3 incelendiinde takviye elemannn kompozit ierisinde homojen dald grlmektedir. Younluk
sonular birbirine yakn olduu iin gzeneklilik oranlar grsel olarak ayrt edilememektedir. Gzeneklerin Al tane
snrlarnda ve Al-MgO arayzeylerinde olduu grlmektedir.
3.2. Sertlik sonularnn incelenmesi
ekil 4de sinterleme scakl ve sinterleme sresinin Al-MgO kompozitlerin sertliklerine olan etkileri verilmitir.
ekil 4 incelendiinde artan sinterleme scakl ile numunelerin sertlik deerlerinin artt grlmektedir.
ekil 4. %5 MgO takviye oranl

kompozitlerin sinterleme sresi
ve sinterleme scaklna gre
sertlik deiimleri.
Buradaki sertlik artnn artan sinterleme scakl ile teorik younlua daha yakn sonular elde edilmesinden veya
dier bir deyile gzenekliliin dmesinden kaynakland [4] deerlendirilmitir. Gzeneklilik oran dk yaplarda sertlik lme cihaznn batc ucunun gzenek zerine gelme olaslnn dk olmas da sebepler arasnda
saylabilir.
3.3. apraz krlma mukavemetlerinin incelenmesi
ekil 5. incelendiinde artan sinterleme scakl ve sinterleme sresi ile KM deerlerinin art grlmektedir.
Yksek scaklklarda alminyumun yzey gerilmesi der, slatma kabiliyeti artar ve daha kuvvetli arayzey balar
oluur [8]. Buradan yola karak KM artnn sebebi; artan sinterleme scakl ve sresiyle paracklar arasnda
oluan boyun apnn (X) toz apna (D) olan oran (X/D) artmasyla [13] olumu olan kuvvetli ba sayesinde paracklar arasndaki yk transferinin daha kolay gereklemesi olarak deerlendirilmitir.
ekil 5. %5 MgO takviye

oranl kompozitlerin
sinterleme sresi ve
sinterleme scaklna gre
KM deiimleri.
447

ekil 6 incelendiinde krlmalarn Al-MgO arayzeyindeki zayf slatma [14] sonucu tane snrlarndan gerekletii
grlmektedir. Tane snrlarnda yer alan gzeneklerin entik etkisi yaparak krlmay kolaylatrd deerlendirilmi
ve KM deerlerini drd sonucuna varlmtr. MgO-Al arayzeyinde slatma kabiliyetinin iyi olmay da [13]
sebepler arasnda yer almaktadr.
ekil 6. 630Cde 1 saat (a), 2 saat (b) ve 4 saat (c) sinterlenmi numunelerin krk yzeylerinin SEM grntleri.
4.SONULAR
Sinterleme sresindeki art ile beraber Al-MgO kompozitlerin younluk, sertlik ve KM deerlerinin artt
tespit edilmitir.
Sinterleme scaklnn artmas ile den gzeneklilik sayesinde younluk ve sertlik deerlerinde ykselme
gzlenmitir. Artan scaklk ile gerekleen kuvvetli arayzey balar sayesinde daha yksek KM deerleri
elde edilmitir.
Artan gzeneklilik ise mikro atlak etkisini artrd iin kompozitlerin KM deerlerini drmtr.
Krk yzeylerin SEM grntleri incelendiinde krlmann arayzeylerde ve matris tane snrlarnda gerekletii grlmtr.
Gzeneklerin takviye eleman etrafnda ve tane snrlarnda yer ald SEM grntleri ile tespit edilmitir.
5.KAYNAKLAR
[1] aln R., tak R., Effect of Mg Content of Matrix on Infiltration Height in Producing MgO Reinforced Al Matrix
Composite By Vacuum Infiltration Method. Material Science Forum Vols.546-549, s.611-614, 2007.
[2] aln R., tak R., Effect of Powder Size on Infiltration Height in Producing MgO Reinforced Al Matrix Composite By Vacuum Infiltration Method. Materials Science Forum Vols., 534-536, s.797-800, 2007.
[3] Rahimian, M., Parvin, N., Ehsani, N., Investigation of particle size and amount of alumina on microstructure and mechanical properties of Al matrix composite made by powder metallurgy. Material Science and
Engineering, Vol 527, s.1031-1038, 2010.
[4] Rahimian, M., Ehsani, N., Parvin, N., Baharvandi, H.Z., The effect of particle size, sintering temperature and
sintering time on the properties of Al-AlO composites, made by powder metallurgy. Journal of
Materials Processing Technology, Vol 209, s.5387-5393, 2009.
[5] Topu, ., Glsoy, H.O., Kadolu, N., Gllolu, A.N., Processing and mechanical properties of BC reinforced
Al matrix composites. Journal of Alloys and Compounds, Vol 482, s.516-521, 2009.
[6] Tatar, C., zdemir, N., Investigation of thermal conductivity and microstructure of the -Al2O3 particulate reinforced Al composites (Al/Al2O3-MMC) by powder metallugy method. Physica B 405, s.896- 899, 2010.
[7] ahin, Y., Kompozit Malzemelere Giri. Gazi Kitabevi, Ankara, 2000.
[8] Wang, H., Zhang, R., Hu, X., Wang, C.A., Huang, Y., Characterization of a powder metallurgy SiC/Cu-Al composite. Journal of Material Processing Technology 197, s.43-48, 2008.
[9] German, R.M., Park, S.J., Mathematical Relations in Particulate Material Processing. John Wiley & Sons Inc.
Publication, USA, 2008.
[10] German, R.M., Toz Metalurjisi ve Parackl Malzeme lemleri. Trk Toz Metalurjisi Dernei Yaynlar, Ankara,
2007.
[11] Min, K.H., Kang, S.P.,Kim, D.G., Kim, Y.D., Sintering Characteristic of AlO-reinforced 2xxx Series Al Composite
Powders. Journal of Alloys and Compounds, Vol 400, s.150-153, 2005.
[12] Kim, T.W., Determination of Densification Behavior of Al-SiC Metal Martix Composite During Consolidation
Processes. Materials Science and Engineering A 483-484, s.648-651, 2008.
[13] Xu, X., Lu, P., German, R.M., Densification and strength evolution in solid-state sintering. Journal of Materials
Science, Vol 37, s.117-126, 72002.
[14] aln R., tak R., Effect of Vacuum on Infiltration Height in Producing MgO Reinforced Al Matrix Composite By
Vacuum Infiltration Method. ICIT-MPT International Conference on Industrial Tools and Materials, Bled, Slovenya,11-14 Eyll 2007.
448

Toz Metal Paralarn ndksiyonla Sinterlenmesinin

NMERK ANALZ
M. Bahattin AKGL*, Gksan AKPINAR*, Can V*, Enver ATK*
*Celal Bayar niversitesi Mhendislik Fakltesi, Makine Mhendislii Blm, 45140, Manisa,mehmet.akgul@
bayar.edu.tr, goksanakpinar105@hotmail.com, can.civi@hotmail.com, enver.atik@bayar.edu.tr
ZET
Toz metal paralarn retiminde sinterleme nemli bir yer tutmaktadr. Bu ilem sinterleme frnlarnda gerekletirilmektedir. Bu sinterleme yntemine alternatif olmak zere toz metal paralarn indksiyonla sinterlenmesi
almalar yaplmaktadr. Bu almada 20 kHz frekansta toz metal paralarn indksiyonla sinterleme ileminin
nmerik analizleri yaplmtr. Bobin tasarmnn s oluumuna etkileri tartlarak optimum bobin tasarm belirlenmeye allmtr. Bu analizlerle toz metal paralarn indksiyonla sinterlenmesinde, sinterleme parametreleri
optimize edilebilmektedir.
Anahtar Kelimeler: Toz Metalurjisi, Sinterleme, ndksiyon, Nmerik Analiz.
NUMERICAL ANALYZING OF INDUCTION SINTERING OF

POWDER METALIC COMPONENT
ABSTRACT
Sintering is taken important part for production of powder metallic component. This operation is practiced in sintering furnace. Alternatively this sintering method it is studied that induction sintering process. In this study, it is done
that numeric analyzing of powder metallic component for 20 kHz induction sintering. It is discussed that coil design
effect to heat production and it is practiced to find optimum coil design. Induction sintering parameters of powder
metal components is optimized with this analyzing.
Key Words: Powder Metallurgy, Sintering, Induction, Numeric analyzing.
1. GR:
Toz metalurjisi ynteminde, uygun bileime sahip toz karmlar ilk aama olarak kalp ierisinde preslenmektedir.
Presleme basncna ve etki ekline bal olarak parann younluu da deimektedir. Bu ilk ilem, elde edilecek
parann mekanik ve fiziksel zelliklerini de etkilemektedir.
Toz metalurjisi ile elde edilecek paralarda ikinci aama sinterlemedir. Sinterleme, ergime scaklnn altnda ve
genellikle koruyucu atmosferde gerekletirilir. Bu aamada para, stlm ve korozyondan korumak amacyla
atmosferle ilgisi kesilmi frn ierisinde nce yalayclardan temizlenmek zere n stmaya tabi tutulur. Oksit indirgenmesinin ardndan frnn scak blgesinde sinterleme ilemi gerekletirilir ve frndan kan para soumaya
braklr [1].
Sinterleme, toz metalurjisinin en karmak konusudur. Sinterleme, ham malzemelerin yksek younluklu paralara
dntrld kilit kademelerin banda gelmektedir [2]. Sinterleme srasnda polimer/yalayc yaklmas, paracklar aras balanma, boyut deiimi ve mikroyapnn irilemesi gibi birok olay gerekleir. Sinterleme uygulamasnda hedeflenen mhendislik amalar iin evrim, ekipman ve gerekli ortamn uygun parametrelerin kullanlmas
gerekir. Sinterlenen parann istenilen zelliklere sahip olmas kadar parann istenilen boyutlarda olmas da bir
zorunluluktur.
449

ndksiyonla stma prosesi; scak ekillendirme, yzey sertletirme, sl ilem, indksiyonla ergitme, indksiyon
kayna, birletirme, lehimleme, yaptrma, sk geme, srtnme kayna vb. uygulamalarda ve otomotiv endstrisi, gda ve kimya endstrisi gibi birok teknolojik uygulamalarda kullanlmaktadr. ndksiyonla stma enerji
younluu, i parasndaki scaklk alannn kontrol ve temassz enerji transferinden dolay son derece etkilidir.
Ancak, indksiyonla stmadaki yksek potansiyel sadece nmerik simlasyon baz alnarak tamamen anlalabilir.
ndksiyonla stma elektromanyetik ve termal fizii kapsamaktadr. Oluacak s i parasnn malzemesine bal
olduu iin bunlar birbiriyle dorudan ilikilidir [3, 4].
ndksiyonla sinterleme, deiken akm tayan iletken bobin ile salanr. Bobinde oluan akm, toz metal malzeme
iinde girdap akma neden olan manyetik alan oluturur. Bobin genellikle bakrdan meydana gelir. erisinden soutma suyu geer. ndksiyonla sinterleme ynteminde kullanlan frekans 50 Hz ile 50 kHz arasnda olabilir.
ndksiyon sisteminin frekansna gre penetrasyon derinlii deiir. Demir gibi ok iletken malzemeler ksa srede
snr. Yksek scaklkta veya yksek frekansta penetrasyon derinlii azalr (ekil 1.). Oda scaklnda 100 mmye
kadar penetrasyon derinlii gerekleebilir ama scaklk artarsa penatrasyon derinliinde azalma meydana gelir.
ekil 1. ndksiyonla sinterlenmi Cu-15Al TM numunenin scaklk ve frekansa gre penetrasyon derinlii [5].
Scaklk avantaj olduu halde indksiyon, sinterlemede ok az kullanlr. Genellikle indksiyon akmn dzelten
grafit ile birlikte yava admlarla stlacak scak presleme ilemlerinde kullanlmaktadr.
ndksiyonla sinterlemede parann tamamnda homojen bir s oluumu hedeflenmelidir. Toz metal paralarn indksiyonla sinterlenmesinde frekans kadar bobin tasarm nemli etkenlerden biridir.
2. MATERYAL VE METOT:
Bu almada, sinterlenecek numuneler ortalama 75 m boyutunda demir tozlarnn 600 MPa basnta tek eksenli
hidrolik presle baslmasyla retilmitir. Numunelerin boyutu 10x10x55 mmdir. Numuneler demir esasl olup arlka %2 Cu, %0,8 grafit ve yalayc olarak %1 inko stearat kullanlarak retilmitir.
Bu toz metal numunelerin indksiyon bobini ierisinde sinterlenmesi, numunelerin bobin ierisinde sabit hzla ilerlemesi srasnda gerekletirilmitir. Ancak deneysel almalarda malzeme zerinden geen manyetik ak tam olarak
llemedii iin nmerik modelleme ile optimum bobin tasarm gelitirilmeye allmtr. Bylece bu boyutlardaki
toz metal numunelerin sinterlenmesinde n stma, sinterleme ve soutma blgesini elde etmek iin en uygun bobin
tasarm elde edilmeye allmtr.
3. NMERK ALIMALAR:
ndksiyonla sinterleme parametrelerinden biri olan optimum bobin tasarmn belirlemek amacyla yaplan nmerik
almalarda Comsol Multiphysics 3.5 program kullanlmtr. Bu modellemede toz metal numuneler, 7 sarml
20 mm apnda bobin kullanlarak 20 kHz frekansta ve 3,5 kA akm iddetinde indksiyonla stma ilemine tabi
tutulmutur. Nmerik almada, sadece bobin sarm ekilleri deitirilerek numuneler arasnda scaklk dalm ve
sreleri bakmndan karlatrlmalar yaplmtr. lgili kurucu denklem aadaki ekildedir;

(1)

450
(2)

Bu formlde younluk, Cp spesifik s kapasitesi, k termal iletkenlik, Q indktif sy temsil etmektedir. Demirin
elektirk iletkenlii, , aadaki eitlikte verilmitir.

Burada
0: referans scaklktaki (T0= 293 Kelvin) dire,
: direncin scaklk katsays ve
T: anlk scakl ifade etmektedir.
ndktif snn bir periyodundaki ortalama zaman aadaki denklemde verilmitir:
(3)
(4)
Modellemede 2 boyutlu eksenel simetri, AC/DC modl, yar statik manyetik, Azimuthal indksiyon akm, vektr
potansiyel, zaman uyumlu analiz olarak seilmitir. Sabitler izelge 1.de verilmitir.
izelge 1. Sabitler izelgesi.
Parametreler
Deer ve Birimi
Akm
3,5 (kA)
Bobin ap
0,02 (m)
Yzey Akm Younluu
15915,494309 (A/m)
Referans Scaklk
293 (K)
T=T0 daki Diren
17,54 e-7 (.m)
Scaklk Katsays
0,0039 (1/K)
Havann Younluu
1,293 (Kg/m)
Havann Is Kapasitesi
1010 [J/(Kg.K)]
Havann Is letkenlii
0,026 [W/(m.K)]
Demirin Younluu
7892 (Kg/ m)
Demirin Is Kapasitesi
452 [J/(Kg.K)]
Demirin Is letkenlii
72 [W/(m.K)]
Para zerinden geen indksiyon akm younluu ve manyetik ak izgilerine bal olarak oluan optimum s
transferini hesaplayabilmek iin 3 adet numune, hava ve 7 sarml bobin meshlenmitir. 3 adet numune soldan saa
doru ilerleyerek bobine girecek, bylece n stma, sinterleme, souma ilemi gerekleecektir (ekil 2).
ekil 2. 3 Adet Temas Halinde Numune, 7 Sarml Bobinin n ve Yan Grn
ekil 3. Meshlenmi 3 adet numune, 7 sarml bobin ve hava ortamnn grn.
451

Bu almada, indksiyonla toz metal paralarn sinterlenmesinde indksiyon bobinlerinin sarm biimleri optimize
edilerek klasik sinterleme frnlarnda elde edilen n stma, sinterleme ve yava souma aamalarndaki gibi (ekil
4) numune scakl erisinin elde edilmesi amalanmtr.
ekil 4. Klasik sinterleme frnndaki ilemler zinciri ve zaman-scaklk profili [6].

3.1. ndksiyonla Sinterlemede Nmerik Bulgular:
Toz metal numunelerin indksiyonla sinterlenmesinde bobin-numune konumlandrmas, bobin ekline gre numunelerde oluan scaklk deiimleri Kelvin olarak model zerinde numerik olarak belirlenmitir. Ayrca numunelerin
yatay eksen zerinde (z-ekseni) oluan scaklk dalm grafik olarak verilmitir. Farkl sarm ekilli numuneler demir esasl malzemeler iin yaklak olarak sinterleme scakl olan 1393 K scakla kncaya kadar sinterlenmi
olup, daha sonra bu scakla kabildikleri sreler esas alnarak karlatrlmtr.
ekil 5. Silindirik sarml ortalanm bobin ekline ve konumuna gre 108,3 saniyede 3 adet numune zerinde
oluan scaklk dalm.
ekil 6. Silindirik sarml ortalanm bobin ekline gre 108,3 saniyede 3 adet numune zerinde oluan scaklkkonum grafii.
452

ekil 7. Silindirik sarml sola dayal bobin ekline gre 87,2 saniyede 3 adet numune zerinde oluan
scaklk dalm.
ekil 8. Silindirik sarml sola dayal bobin ekline gre 87,2 saniyede 3 adet numune zerinde oluan
scaklk-konum grafii.
ekil 9. Konik sarml bobin ekline gre 114,7 saniyede 3 adet numune zerinde oluan scaklk dalm
ekil 10. Konik sarml bobin ekline gre 114,7 saniyede 3 adet numune zerinde oluan scaklk-konum grafii
453

ekil 11. Konkav sarml bobin ekline gre 126,6 saniyede 3 adet numune zerinde oluan scaklk dalm.
ekil 12. Konkav sarml bobin ekline gre 126,6 saniyede 3 adet numune zerinde oluan
ekil 13. Konveks sarml bobin ekline gre 115,4 saniyede 3 adet numune zerinde oluan scaklk dalm.
ekil 14. Konveks sarml bobin ekline gre 115,4 saniyede 3 adet numune zerinde oluan
454

5. SONULAR:
Sinterlemede n stma, sinterleme daha sonrada yava souma koullar istenmektedir. Bu amala 7 sarml bobin
iine sabit bir hzla gnderilen numune olarak modellenen sistemde, soldan saa doru ilerleyen numunenin herhangi bir noktas izlenirse n stma, sinterleme ve yava soumas aamalar gerekleir.
Modellemede sadece bobin sarm ekilleri deitirilerek numuneler zerinde oluturulan scaklk dalmlarnn etkisi aratrlmtr. Modellenen modifiye edilmi bobin tasarmlar incelenecek olursa sinterleme scakl asndan
aadaki sonular elde edilmitir:
Silindirik sarml bobinde 1120C (1413 K) scakla 87,2 saniyede ulalmaktadr (ekil 7.).
Klasik sinterleme frnnda elde edilen n stma, sinterleme ve soutma para scakl erisini salayan indksiyon bobini ekil 13te verilen i bkey (konveks) sarml bobindir.
Numune dorultusunda al ve d bkey (konkav) indksiyon bobinleri, sinterleme srasndaki ilem zinciri
scaklklarna uygun deildir.
Optimum sinterleme parametrelerini belirlemek amacyla yaplan nmerik almalarda numuneler demir esasl
malzeme olarak tanmlanmtr ve demirin termofiziksel zellikleri baz alnarak nmerik model oluturulmutur.
Deneysel almalarda ise toz metal paralar retmek iin yalayc malzemeler ve baka tozlar ilave edilmektedir.
Bunlar demir esasl toz metal paralarn termofiziksel (zellikle elektrik zdiren) zellikleri etkilemektedir.
Daha sonraki almalarmzda, nmerik almalardaki sonularn deneysel almalarla rtp rtmedii belirlenecektir. Sinterleme esnasnda termal kamera, infrared termometreler kullanlarak numunelerin farkl noktalarndan scaklk lmleri yaplarak deneysel sonularla nmerik sonular karlatrlacaktr.
6. KAYNAKLAR :
1. Randall M.G., Editrler; Sarta, S. Trker, M., Durlu, N., Toz Metalurjisi ve Parackl Malzeme lemleri, p.p.
2-9, 143, 233-273, 279-296, TMMD, Ankara/Trkiye, 2007.
2. German, R.M., Powder Metallurgy of iron and steel, Pennsylvania, A willey interscience publication, Jon
Wiley & Sons, INC., USA, pp. 181-209, 232-260, 1998.
3. S. Galunin, M. Zlobina, K. Blinov, A. Nikanorov, T. Zedler, B. Nacke, Numerical analysis of coupled physics
for induction heating of movable workpieces International Scientific Colloquium Modelling for Electromagnetic
Processing Hannover, October 27-29, 2008.
4. enol SERT Yksek Lisans Tezi ndksiyon Isl Ykleme le Bir atlak Etrafnda Olusan Gerilmelerin
ModellenmesiSakarya niversitesi Fen Bilimleri Enstitis, Eyll 2008.
5. German, R.M., Sintering theory and practice The Pennsylvania State Universty Park, Pennsylvania, A willey
interscience publication, Jon Wiley & Sons, INC., USA, pp. 313-362, 373-400, 403-420, 1996.
6. Zinn, S., Semiatin, S.L., Coil design and fabrication, Part 2, specialty coils, 1988.
455

N KARITIRILMI VE SICAK PRESLENM Al-Cu ALAIMI

TOZ METAL PARALARDA KIRKENDALL ETKS VE FZKSEL
ZELLKLERN ARATIRILMASI
Ergn EKC*, Mahmut GLESN ** ve Yusuf ZATALBA***
*
Dzce niversitesi, Cumayeri Meslek Yksekokulu, Makine Blm, 81700, Dzce, ergunekici@duzce.edu.tr
**
Gazi niversitesi Teknik Eitim Fakltesi, Makine Eitimi Blm, Teknikokullar, 06500, Ankara,
gulesin@gazi.edu.tr
***
yusufoz@gazi.edu.tr
zet
Bu almada, arlka % 4,5 Cu ve kalan Al tozlar olmak zere bir saat sreyle turbulada n kartrmaya tabi
tutulmutur. Karm tozlar scak presleme yntemiyle 570 Cde 200 MPa basnta 20 dakika sreyle preslenmitir.
Scak preslenmi blok numuneler 550C scaklkta 2, 4, 6, 8, 10 saat sreyle difzyon tavlamasna tabi tutulmutur.
Toz Metalurjisi (TM) yntemiyle retilen bu numunelerin metalografik incelemeleri ve elektron mikroskop almalar
yaplarak Al-Cu difzyon sreci aratrlmtr. ki saatlik tavlama srecinde nemli miktarda bakr tozunun Al matriste difzyonla znd ancak Kirkendall etkisiyle Cu tozlarnn yerini boluklarn ald belirlenmitir. Bu durum
ise TM paralarn fiziksel zelliklerini olumsuz etkilemitir.
Anahtar Kelimeler: Al-Cu, Toz Metalurjisi, nkartrma, Kirkendall Etkisi.
Investigation of Kirkendall Effect and Physical Properties

in Premixed and Hot Pressed PM Parts with Al-Cu Alloy
ABSTRACT
In this study, the alloy consisting of 4,5% Cu and 95.5% Al powder was exposed to premixing in turbula for an hour.
Then the mixture was pressed for twenty minutes in 570 C under 200 MPa pressure with hot pressing method.
The samples of hot pressed blocks were exposed to diffusion annealing in 550 C for 2, 4, 6, 8, 10 hours. Diffusion
process of the samples produced with powder metallurgy method was investigated by metallographic examination
and electron microscopic study. It was determined that during the two-hour annealing process, great amount of Cu
powder was decomposed with diffusion at Al matrix, but with the effect of Kirkendall, the Cu powder was replaced
with gaps. This affected the physical properties of powder metallurgy pieces negatively.
Keywords: Al-Cu, Powder Metallurgy, Premixing, Kirkendall Effect.
1. GR
Toz metalurjisi teknii n alaml tozlarn ve takviye elemannn vakum kontrol altnda kartrlmas ve kaynaklanmas gibi karmak bir dizi operasyonu gerektirmektedir [1]. Alminyum alamlarna mikro (<0,5) veya makro (%
1-20) arasnda deien miktarlarda Cu, Si, Mg ve Li gibi alam elementlerinin ilavesi ile mekanik zellikleri gelitirilebilir[2,3]. Metal tozlarnn scak preslenmesiyle reaktif sinterleme (HPRS) younlama ve malzemenin kimyasal
reaksiyonun her ikisinin birden tek admda gerekletii bir tekniktir. Nispeten dk sinterleme scakl, tozlarn
dk maliyetinden ve younlama iin herhangi bir takviye elemanna ihtiya duyulmamasndan dolaysyla bu
teknik ekonomik olabilir[4,5]. Toz Metalrjisi (TM) yntemi ile retilen paralarn mekanik zellikleri ile anma ve
456

korozyon direnlerini artrmak amacyla sinterleme sonras farkl mekanik ve sl ilemler uygulanmaktadr [6]. Tane
snrlarnn dalm/bileimi ve gzeneklerin dalm/bykl gibi zellikleri mikro yapnn performans zerinde
etkilidir[7]. Konsantrasyon fark olan ikili bir alamda temas eden yzeylerin difzyon farkndan dolay bir ak
meydana gelir[8]. Kirkendall etkisi, birleme ara yzeyinden metal iftlerine doru atomik aknn farkl olmasndan
kaynaklanmaktadr [9]. Gke ve arkadalar elementel yntemle AlCuMg tozlarnn retilmesinde mikroyap
zelliklerini incelemilerdir[10]. Schaffer ve arkadalar elementel yntemle retilen AlCuMgSi alamlarnda
azot ve kalayn sv faz sinterleme zerindeki etkilerini aratrmlardr[11]. Fogagnolo ve arkadalar mekanik alamlama ile retilen Al-4.5 Cu kat zeltisinin MA sresi ve scakla bal olarak mikroyapsal deiimleri ve yapdaki bakrn durumunu incelemilerdir. Bakr XRD ve SEM incelemelerinde saptayamamalar nedeniyle ok kk
boyutta ikinci bir faz olarak kalan aluminyum ierisinde dalm olabileceini belirtmilerdir. Baka bir olasla gre
ise bakrn yap ierisinde ksm olarak znm olabilecei veya nano boyutta dalm ikinci bir fazn paras
olabileceini belirtmilerdir[12].
Bu almada, scak presleme (SP) yntemiyle Al-Cu alam TM para retilmesi ve retim srecinde Cunun
difzyon mekanizmas ile gzenek oluumu ve fiziksel zelliklere etkisi incelenmitir.
2. MATERYAL VE METOT
almada %99 saflkta 100 m alt Al tozlar ile % 99 saflkta 44 m alt Cu tozlar kullanlmtr. % 4.5 Cu-Al karm 1 saat sreyle turbulada kartrlmtr. Kartrlan tozlar kalp ierisine alnarak n ekillendirilme iin 200
MPa souk olarak preslenmi ve devamnda 570 Cde 200 MPa basn altnda 20 dakika sre ile scak olarak
preslenmitir. Bu sayede 60x60 mm kare kesitli yaklak 10mm kalnlklarnda blok numuneler retilmitir. Scak
preslenmi blok numuneler 550C scaklkta 2, 4, 6, 8, 10 saat sreyle difzyon tavlamas yaplmtr. Tavlama
ncesi ve sonras optik ve taramal elektron mikroskopta (TEM) mikroyap incelemeleri yaplmtr. Karm tozun
gerek para younluk lmleri Sartorius marka 0,1 mg hassasiyetteki terazide younluk kitiyle yaplmtr. Vickers
mikro sertlik lmleri 100 g yk 10 sn sre uygulanarak gerekletirilmitir.
3.1 Difzyon (Yaynm) ve Alamlama
200 MPa basn altnda 20 dakika sre ile scak presleme sonrasnda retilen numunelerin mikroyaplar incelendiinde, bakr tozlarnn Al matris ierisinde homojen olarak dald, gzenek orannn ok dk olduu (ekil 1a)
ve Al matris ile Cu paracklar arasnda dzenli bir arayzey olutuu (ekil 1b) grlmektedir.
ekil 1. Scak presleme sonrasnda retilen numunelerin mikroyaps.

Matris ierisindeki bir Cu parac etrafnda oluan difzyon gradyanlar ve elementsel mikro analizi ekil 2de verilmitir.. Scak presleme ilemi srecinde Al-Cu ikilisinin karlkl ktlesel difzyonu balam fakat tamamlanmamtr. ekil 2ada 1 nolu hat boyunca XRF/EDS analizi yapldnda 2bde verilen grafik elde edilmitir. Herhangi
bir dalayc kullanmakszn dahi Cu parac etrafnda akca grlen ve farkl Al-Cu atomik younluklarna sahip
difzyon gradyanlarnda paracktan uzaklatka Cu oran azalmaktadr. Burada, gradyanlarn merkezine yaklarken Cu miktarnn artt ve merkezde maksimum olduu grlmektedir. Tersine, en dtaki gradyandan balamak
zere merkeze yaklatka ise Al miktar azalmtr. Merkezde bulunan Cu parac ile Al matris arayzeyinde ise
bakrn ktlesel difzyonu sebebiyle oluan halka eklinde boluk grlmektedir (ekil 2ada okla gsterilmitir). Dier bir boluk ise, ekil 2ada gsterilen resmin sol alt kesinde bulunan Cu taneciinin merkezindedir. Muhtemel
bu noktadaki Cu tanecii ok kk hacim ve boyutta idi (yaklak 6 m) ve scak piresleme srecindeki ktlesel
difzyonla Cu tanecii byk oranda Al iine difzyon gereklemitir.
457

ekil 2. Scak preslenmi Al-Cu ikilisinde bileim gradyanlar ve XRF analiz sonular.
Difsyon gradyanlarnn zerindeki farkl noktalardan alnan XRF/EDS sonular ekil 3de verilmitir.
ekil 3. Difzyon gradyanlar zerinde farkl noktalardan alnan mikro analiz sonular.
Bu sonular da akca gstermektedir ki 1 nolu analiz blgesinde Cu iine Al difzyonu yok denecek kadar azdr
(%0.57). Ancak 2nolu blgede maksimum (%66.2) olmak zere 3 ve 4nolu blgelerde Al iine Cu difzyonunun
giderek azald grlmektedir. Difzyon mekanizmasnda atomlar yksek konsantrasyonda bulunduklar bir blgeden konsantrasyonlarnn daha dk olduu bir blgeye g ederler[13]. Atomlar yalnzca yksek scaklkta
ara yzeyin bir kenarndan dier kenarna difze olabilirler bunun iin gerekli olan scaklk genellikle (0.6-0.8Tm)
dir. Tm buradaki ergime scakln gstermektedir[14]. Al-Cu ikili denge diyagramna gre Alminyum blgesinde
bakrn znrl scakla bal deimekle birlikte 548 Cde maksimum arlka %5.65 oranndadr[15]. Bu
orandan sonra Cu orannn artmas ekil 3de 4. blgede gsterildii gibi Al matris iinde AlCu2 intermetalii olan
faznn oluumuna, artan Cu oranyla ile birlikte 2. ve 3. gradyan blgelerinde ise Al faz kaybolarak +2 fazlarnn
olutuu sylenebilir.
Btn bunlarla birlikte Cu taneciinden farkl konstrasyonlarda Al matris iine yaynan Cu atomlarnn, Cu iine
yaynan Al atomlarndan ok daha fazla olduu ve yaynmann Cu dan Al matrise doru olduu aka grlmtr.
Bunun nedeni olarak Cu atomlarnn aplarnn (2.556 ), Al atom aplarndan (2.886 ) daha kk olmas, ve
kk apl atomlarn yaynm hzlarnn byk atomlardan daha hzl olmas sylenebilir[16]. Bu durum sebebiyle Al
iinde Cun yaynm blgesi bymektedir. Bakr tarafnda ise gei blgesinin dar olmasna neden olmaktadr[17].
Bu mekanizmalarn meydana getirdii Al iinde Cun hzl ktlesel yaynm ekil 2de okla gsterilen Cu taneciinin
evresindeki ktle kaybn ve ayn zamanda scak preslenen bu numunelerin 2, 4, 6 ve 10 saatlik difzyon/sinterleme tavlamas srecinde Cun byk oranda Al iine ktlesel yaynm sebebiyle oluan gzenekleri meydana getirmitir. ekil 4de aka grlen ve Cu taneciklerinin neredeyse tamamen yaynmyla meydana gelen gzeneklerin
varl Kirkendall etkisiyle aklanr[18]. Yukarda bahsedilen yaynm etkileriyle oluan Kirkendall etkisiyle ve artan
difzyon/sinter tavlamas ile birlikte Cu paracklarnn boyutlarna yakn (<50m) boluklar belirlenmitir. ekil 4de
2 saat difzyon tavna tabi tutulan numunede bu durum aka grlmektedir. Ayrca, halen tamamen yaynmam,
boluk iinde kalm Cuca zengin kalntlar ve hi yaynmam Cu paracklar grlebilmektedir.
458

ekil 4. 2 saat difzyon/sinter tavlamas sonrasnda oluan boluklar.

3.2 Younluk Deiimleri
retilen numunelerin tavlama ncesi ve sonras llen younluk deerleri ekil 5de verilmitir. Scak presleme ile
retilmi numunelerin younluu %99 civarndadr. Ancak artan difzyon/sinter tav sresiyle birlikte numunelerin
younluk oranlarnda azalma belirlenmitir. zellikle 2 saat tavlama sonundaki younluk d nemli miktardadr. Kirkendall etkisinin zellikle tavlama srecinde belirginletii yukarda aklanmtr. Bu srete, Al matris
iinde yaynan Cu atomlarnn yaklak toplam hacin %95ini oluturan Al matris hacmini arttraca, bununla birlikte
% 4.5 oranndaki Cu partikllerin oluturduu boluklarda ise bzlme olaca literatrde belirtilmektedir[19-20].
Numunelerin ktlelerinin sabit olmasna ramen, tavlanm numunelerde belirgin oranda oluan Kirkendal etkisinin
meydana getirdii bu hacimsel artn younluk azalmasna sebep olduu dnlmektedir.
ekil 5. Difzyon/sinter tav sresine bal younluk deiimi.

3.3 Sertlik Deiimleri
Scak presleme sonrasnda retilen numunelerin tavlama ncesinde elde edilen mikrosertlik deerleri ekil 6da
verilmitir. Bakr paracn merkezinde sertlik maksimum (249 HV) iken difzyon gradyanlar zerinde merkezden
uzaklatka sertlik deeri Al miktarnn artmas ile azalmaktadr.
ekil 6. SP sonras mikrosertlik.
ekil 7. Difzyon/Sinter tavlar sonras sertlik.
459

Farkl srelerde difzyon tav uygulanan numunelerin sertlik deiimleri ekil 7de verilmitir. Genel olarak tavlama
sresinin artmas ile sertlik deerinin artt net olarak grlmektedir. Scak preslenmi numunenin sertlii 38 HV
iken artan tavlama sresi ile 78 HV sertlie kadar art meydana gelmitir. zellikle 4 saate kadar tavlama sresindeki artla artan boluk/gzenek oranna ramen Al matris iinde daha dk konsantrasyon fark oluturarak
znen Cu miktarnn art genel olarak numunenin sertliini de arttrd sylenebilir. Bu sreden sonraki numune
sertliinin 10-15HV aralndaki sapma ile sabit kald, bu sapmaya ise tavlama sresiyle artan boluk oranndaki
artn sebep olduu dnlmektedir.
4. SONULAR
Al+%4,5 Cu n kartrlm tozlarn scak preslenmesi ve devamnda farkl srelerde tavlanmas ile oluturulan
Al-Cu alam tozmetal paralardaki difzyon srecinin ve fiziksel zelliklerin aratrld bu almada aadaki
sonular sylenebilir.
1. n kartrlm Al-Cu tozlarnn 200 MPa basn altnda 570 C scaklkta 20 dakika sre ile preslenmesi sonunda yaklak %99 younlukta TM para retimi gerekletirilmitir. Ancak bu sre iinde Al-Cu difzyonunun
tam olarak gereklemedii ve Cu paracnn evresinde (Al matris iinde) eitli younluklarda Cu ieren
difzyon gradyanlarnn olutuu grlmtr. Bu gradyanlarn Cu younluu bakr tanecikten uzaklatka
azalmaktadr.
2. Scak presleme srecinde Cun alminyum matrise ktlesel difzyonu, Kirkendall etkisiyle Cu taneciin evresinde boluk oluturmutur. Devamnda, Cun Al iinde tamamen yaynmasn salamak iin yaplan tavlama
srecinde Cu taneciklerinin yerini tamamen boluklar almtr.
3. Tavlama ilemiyle artan Kirkendall etkisi, retilen TM numunelerin younluklarnn dmesine sebep olmutur.
4. Genel olarak artan difzyon tav ile birlikte TM numunelerin sertlii de artmtr.
KAYNAKLAR
1. Bedir, F., Characteristic Properties of AlCuSiC and AlCuB4C Composites Produced by Hot Pressing Method Under
Nitrogen Atmosphere, Materials and Design, Vol. 28, pp. 12381244, 2007.
2. Hirosawa, S., Sato, T., Kamio, A., Flower, HM., Classification of the role of microalloying elements in phase decomposition of Al based alloys, Acta Mater, Vol. 48, pp. 1797806, 2000.
3. Bishop, DP., Cahoon, JR., Chaturvedi, MC., Kipouros, GJ., Caley, WF., On enhancing the mechanical properties of
aluminium P/M alloys, Mater Sci Eng, A290, pp. 1624, 2000.
4. Veljovic, D., Jokic, B., Petrovic, R., Palcevskis, E., Dindune, A., Mihailescu, I.N., Janackovic, D., Processing of dense
nanostructured HAP ceramics by sintering and hot pressing, Ceramics International, Vol. 35, pp. 14071413, 2009.
5. Huang, L.J., Geng, L., Li, A.B., Yang, F.Y., Peng, H.X., In situ TiBw/Ti6Al 4V composites with novel reinforcement
architecture fabricated by reaction hot pressing, Scripta Materialia, Vol. 60, pp. 996999, 2009.
6. Boylu, K.S., Varol, R., Pek, M.A., Tam Youn Ve T/M eliklerde Karbon Miktarnn Borr Tabakas Kalnlna Etkisi TMMOB Makina Mhendisleri Odas Konya ubesi H- Makina .Tasarm ve malat Teknolojileri Kongresi 26-27 Eyll 2003
7. Rong, L., Hongqiang, R., Kai, G., Di, T.,Research on Preparation of Zr( OH)JB4 C Composite Powder by Different Processes, Journal of Rare Earths Vo1. 25, p.340, 2007.
8. Shewmon, P.G., Diffusion in Solids, Mc Grow Hill Book Company, 1964.
9. Adda, Y., Philibert, J., La diffusion dans les solides. Bibliothque des Sciences et Techniques Nuclaires, Presses Universitaire de France, Paris, pp. 810853, 1996.
10. Gke, A., Fndk, F., Kurt, A.O., Microstructural examination and properties of premixed AlCuMg powder metallurgy
alloy, Materials Characterization, Vol. 62, pp. 730735, 2011.
11. Schaffer, G.B., Yao, J.Y., Bonner, S.J., Crossin, E., Pas, S.J., Hill, A.J., The effect of tin and nitrogen on liquid phase
sintering of AlCuMgSi alloys, Acta Materialia, Vol. 56, pp. 26152624, 2008.
12. Fogagnolo, J.B., Amador, D., Ruiz-Navas, E.M., Torralba, J.M., Solid solution in Al4.5 wt% Cu produced by mechanical
alloying, Materials Science and Engineering, A 433, pp. 4549, 2006.
13. Ouz, B., Demir D Metaller Kayna, Oerlikon Yayn, stanbul, 468-469 1990.
14. Chen, S., Ke, F., Zhou, M., Bai, Y., Atomistic investigation of the effects of temperature and surface roughness on diffusion bonding between Cu and Al Acta Materialia, Vol. 55, pp. 31693175, 2007.
15. Willamson, J.R., Superplastic Forming Diffusion Bonding of Titanium, Proc. The Ist. Int. Cant. Materials in Areospace. 2.Konf. No. 10817, pp. 373394, 1986.
16. Richmond, O., Morrison, H.L., Devenpeck, M.L.,. Sphere indentation with application to the Brinell hardness test, Int.
J. Mech. Sci, Vol. 16, pp. 7582, 1974.
17. Callistar, W.D., Materials Science and Engineering an ntroduction Diffusion Mechanism, 5th Edition, The Universty
of Utah Johnwilley, 94-111, 2000.
18. Strandlund, H., Larsson, H., Prediction of Kirkendall shift and porosity in binary and ternary diffusion couples, Acta
Materialia, Vol. 52, pp. 46954703, 2004.
19. Srinivasan, D., Subramanian, P.R., Kirkendall porosity during thermal treatment of MoCu nanomultilayers, Materials
Science and Engineering, Vol. 459, pp. 145150, 2007.
20. Hermans, M.J.M., Biglari, M.H., Void formation by Kirkendall effect in solder joints, Netherlands, December
2006.
460

MANYETK NKEL DEMR ALAIMLARININ

MKRODALGA SNTERLEME YNTEMYLE RETLMES
Derya Erdem, Arcan F. Dericiolu
Orta Dou Teknik niversitesi, Metalurji ve Malzeme Mh. Bl
deryae@metu.edu.tr, arcan@metu.edu.tr
ZET
Mikrodalga sinterleme yntemi, ncelikli olarak seramik paralarn retiminde hzl ve niform stma salamas,
malzemelerin teorik younluuna daha yakn deerlerde ve daha iyi mikroyaplarda elde edilebilmesi sebebiyle
kullanlmtr. Ancak, hacimli metalik paralarn mikrodalgalar yanstc zellikleri sebebiyle, uygulama alan seramik
retim sreleriyle snrl kalmtr. Ancak, toz metalurjik paralarn; ounlukla mikroldaga etkileim kalnl ile
orantl byklklerde tozlardan olumasndan tr, mikrodalgalar ile verimli bir ekilde etkileerek mikrodalga
enerjisini sourabildikleri ve mikrodalgalarla hacimsel olarak stlabildikleri grlmtr. Bunun yansra, mikrodalga
enerjisi ile sinterlenerek retilen toz metalurjik paralarn, konvansiyonel yntemle sinterlenen kartlarndan
daha az enerji kullanlarak, daha dk sinterleme scaklk ve srelerinde, iyiletirilmi mekanik zellikler ve
gzenek morfolojileriyle retilmesinin mmkn olduu anlalmtr. Bu almada, manyetik zelliklere sahip toz
metalurjik Ni-Fe (Nikel-Demir) alamlar hem mikrodalga sinterleme yntemiyle hem de konvansiyonel yntemle
retilmi ve retilen alamlar oluan fazlar ile mikroyapsal ve manyetik zellikler bakmndan karakterize edilerek
konvansiyonel ynteme kyasla incelenmitir. Literatrde bulunan pek ok almadan farkl olarak, bu alma
kapsamnda mikrodalga sinterleme ynteminin toz metalurjik numunelerin mikroyapsal ve mekanik zelliklerinin
yansra, yumuak manyetik zelliklerine etkisi de incelenmitir.
Anahtar Kelimeler: Mikrodalga sinterleme, nikel-demir alamlar, mekanik zellikler, manyetik zellikler.
ABSTRACT
In this study, soft magnetic Ni-Fe permalloy compacts were consolidated through microwave and conventional
sintering routes at combinations of various sintering temperatures and compaction pressures. Sintered alloys
were characterized in terms of their densification, microstructural evolution as well as magnetic and machanical
properties. The effect of sintering method in terms of the applied sintering parameters on the final properties of
the compacts were investigated in a comparative manner. It was determined that microwave sintered permalloys
are superior compared to their conventionally sintered counterparts in densification response, microstructural
characteristics such as pore shape and distribution as well as mechanical properties. However, permeabilities
of the microwave sintered permalloys were inferior to their conventionallty sintered counterparts possibly due to
microstructural refinement associated with microwave sintering route.
Keywords: microwave sintering, nickel-iron alloys, mechanical properties, magnetic properties
1.GR
Yumuak manyetik malzemeler, transformatr ekirdekleri, manyetik kayt cihazlar vb gibi elektrik ve
telekominikasyon endstrilerinde geni bir uygulama alanna sahiptir [1]. Yumuak manyetik malzemeler ierisinde,
ktlece %80 Nikel ieren Nikel-Demir (Ni-Fe) alamlar, yksek manyetik geirgenlikleri nedeniyle byk bir nem
arzetmektedir. Hacimli Ni-Fe alamlar, 2kHze kadar olan frekanslara kadar olan uygulamalarda tercih edilirken;
daha yksek frekanslardaki uygulamalarda eddy akmlarndan kaynaklanan AC kayplarn azaltmak iin toz
metalurjik Ni-Fe alamlar kullanlmaktadr [1].
Toz metalurjik yntem, AC kayplarnn azaltlmasnn yansra, kompleks geometrilerde paralarn azalan
gzeneklilik yzdesi, homojen ve kk boyuttaki tanelerden oluan mikroyaplarda elde edilmesi olanaklarn
461

da salamaktadr. Ayrca, sinterleme aamasnn kontrol araclyla, toz metalurjik paralar son ekillerine
yakn halde minimal ekinti ile retilebilirler [2-3]. Toz metalurjik paralarn sinterlenmesi yaygn olarak elektrikli
konvansiyonel frnlarda gerekletirilmektedir. Is enerjisinin frnn stc elemanlarndan numunelerin yzeyine
radyasyon ve konveksiyon meaknizmalar ile iletimi esasna dayanan bu yntemde, sl gerilmeleri ve atlamalar
nlemek araclyla, olduka dk stma hzlar ve ara duraklamalar tercih edilmektedir. Bu nedenle, hem ilem
sreleri ve enerji sayfiyatlar artmakta, hem de numunelerin yksek scaklklara daha uzun sreler maruz kalmas
sebebiyle, mikroyapsal irileme ve tane boyutunda art meydana gelmektedir.
Toz metalurjik alamlarn, hacimli kartlarndan farkl olarak, mikrodalgalar ile verimli bir ekilde etkileebilmeleri ve
hacimsel olarak stlabilmeleri sayesinde, toz metalurjik alamlar mikrodalga sinterleme yntemiyle konvansiyonel
ynteme kyasla azalan ilem sreleri ve enerji sayfiyatlar ile, artan sinterlenmi younluklarda, azalan gzeneklilik
yzdeleri ve tane boyutlar ile iyiletirilmi mekanik zelliklerde, artan korozyon ve anma dayanlar ile
retilebilmektedir [4-12].
Bu almada, yumuak manyetik zellikler gsteren toz meta metalurjik Ni-Fe alamlar hem mikrodalga
sinterleme hem de konvansiyonel yntemle deien sinterleme scaklklarnda retilmi, deien sinterleme sre
parametrelerinin ve sinterleme ynteminin numunelerin younlam, mikroyapsal ve manyetik zelliklerine etkisi
de incelenmitir. Ayrca, bu almada, literatrde bulunan nceki almalara ek olarak, mikrodalga sinterleme
ynteminin toz metalurjik alamlarn yumuak manyetik zelliklerine de etkisi incelenmitir.
2. DENEYSEL YNTEM
2.1. Pelet Hazrlama
Ni ve Fe tozlar (Ni: %99,99 saflk, 7-10 parack boyutu, ekil 1a, Fe: %99,99 saflk, 10 mden kk parack
boyutu, ekil 1b) ktlece 4:1 orannda olacak ekilde tartlm ve istenilen oranda homojen bir karm elde etmek
amacyla izopropilalkol (IPA) ortamnda elde kartrlmtr. Karmn kurumasn takiben, tozlar iki eksenli souk
sktrma yntemiyle 200 MPa sktrma basnc kullanlarak ekillendirilmi ve daha sonra maksimum preslenmi
younlua ulaabilmek amacyla, souk izostatik presleme yntemiyle 1500 bar altnda sktrlmtr. Sktrma
ilemi sonras, disk eklindeki geometriye sahip 15 mm apl ve ortalama 4,5 mm ykseklikli peletler, %71 sinterleme
ncesi younlukla elde edilmitir.
ekil 1a. almada kullanlan Ni tozunun taramal

elektron mikroskobu grnts.
ekil 1b. almada kullanlan Fe tozunun taramal

elektron mikroskobu grnts.
2.2. Sinterleme
retilen peletler, mukavemet art ve pekleme salamak amacyla sinterleme srecine tabi tutulmutur. Sinterleme
ilemi, Ni-Fe alamlar korozyona grece dayankl olduklarndan herhangi bir koruyucu atmosfer kullanmna
gerek duyulmakszn 1200, 1225 ve 12500C scaklklarda 45 dakika sreyle 4,8 kW gcndeki mikrodalga frn
(MKH-4.8???, Linn High Therm GmbH, Eschenfelden, Germany) kullanlarak gerekletirilmitir. Toz metalurjik
numunelerin oda scaklnda mikrodalgalar ile verimli bir ekilde etkileememelerinden dolay, verimli etkileim
scaklklarna n stma salamak amacyla 63mlik -SiC tozu kullanlmtr. SiC yksek kayp tanjant sebebiyle
oda scaklndan itibaren elektromanyetik dalgalar ile etkin olarak etkileerek snmakta ve n stma amacyla
susceptor malzeme olarak sklkla kullanlmaktadr. Mikrodalga sinterleme srasnda, s kayplarn engellemek
amacyla tasarlanan almina fiber-bord yaltm malzemeleri ve almina krozelerden oluan izolasyon kafesi, ekil
2a ve 2bde gsterilmektedir. Mikrodalga sinterleme yntemiyle retilen numunelerin karakterizasyonu esnasnda
kyaslama yapabilmek amacyla, ayn koullarda hazrlanan peletler konvansiyonel sinterleme yntemiyle de ayn
sinterleme parametreleri kullanlarak retilmitir.
462

ekil 2a. Mikrodalga sinterleme izolasyon

kafesi.izolasyon kafesi.
ekil 2b. Mikrodalga sinterleme

dzeneginin x-x kesiti
2.3. Malzeme Karakterizasyonu

Younluk lm: Sinterleme sreci sonrasnda elde edilen numuneler, yzeylerinde bulunan oksit tabakasnn
giderilmesi amacyla kaba zmparalandktan sonra, 24 saat sreyle ksilende bekletilmi ve daha sonra Arimet
Yntemi kullanlarak deneysel younluklar llmtr. Elde edilen sonularn allmakta olan Ni-Fe alamnn
teorik younluuna (hacimli nikel ve demir metallerinin younluklarnn ktlece yzdelerine gre oranlanmasyla
elde edilen younluk deeri) oranlanmasyla ulalan %younlam deerleri belirlenmitir.
Faz Analizi: Sinterlenen alamlar X nlar krnm (XRD) yntemiyle10-90 aralnda 2/dak. tarama hzyla
oluan fazlar bakmndan incelenmitir.
Mikroyap Analizi: Mikrodalga ve konvansiyonel sinterleme sreleriyle retilen alamlarn metalografik olarak
parlatlm ancak dalanmam yzeyleri gzeneklilik yzdeleri ve gzenek morfolojilerinin incelenebilmesi
amacyla, Taramal Elektron Mikroskobu kullanlarak incelenmitir. Elde edilen mikroyaplar yardmyla mikrodalga ve
konvansiyonel sinterleme yntemlerinin %gzeneklilik ve gzenek morfolojileri zerindeki etkileri karlatrlmtr.
Manyetik Karakterizasyon: Titreimli rnek Manyetometresi (VSM) (EasyVSM EV10, ADE Electronics, Wisconsin,
USA) kullanlarak, alamlarn manyetik zellikleri llm ve mikrodalga sinterleme ynteminin manyetik zelliklere
etkisi konvansiyonel ynteme kyasla incelenmitir.
3. Bulgular ve Tartma
Mikrodalga enerjisi ve SiC tozlarnn salad stma sayesinde, mikrodalga sinterleme sreci esnasnda 300C/dky
geen stma hzlar ile numuneler sinterleme scaklklarna stlabilirken, konvansiyonel yntemde stma hz 100C/
dky geememitir. Bu balamda, mikrodalga sinterleme yntemiyle, konvansiyonel ynteme kyasla toz metalurjik
numuneler azalan ilem sreleri ve maliyetleri ile retilebilmitir.
ekil 2de mikrodalga (MW) ve konvansiyonel (C) sinterleme yntemi ile retilen numunelerin sinterleme sonras
younluk sinterleme scakl erileri incelendiinde; ayn koullarda mikrodalga sinterleme yntemiyle retilen
numunelerin konvansiyonel kartlarndan daha yksek younluklara eritii grlmektedir. Bunun yansra,
konvansiyonel sinterleme yntemiyle retilen numunelerin sinterlenmi younluklarnn, 12500Cde optimize
olduu, ve artan sinterleme scaklklar ile d gsterdii saptanmtr. Bu durumun, tane bymesi, gzeneklerin
birlemesi ve tane snrlarnn oksitlenmesinden ileri geldii dnlmektedir. Mikrodalga sinterleme yntemiyle
retilen numunelerde ise, sinterlenmi younluklarn sinterleme scaklklar ile artt grlmtr. ki yntem
arasnda gzlemlenen bu farklln, mikrodalga sinterleme yntemiyle salanan hzl ve hacimsel stmadan
kaynakland dnlmektedir. Mikrodalga sinterleme yntemiyle olduka hzl olarak sinterleme scaklna
stlan numuneler, konvansiyonel ynteme kyasla azalan tane boyutuna sahip olduklarndan, sinterleme esnasnda
atomlarn kolaylkla difzyon yapabilecei daha fazla yzey alan bulunmakta ve mikrodalga sinterleme yntemi ile
ayn koullarda konvansiyonel ynteme kyasla daha yksek younluklara eriilebilmektedir. Ayrca, sinterleme
sreci mikrodalga sinterleme yntemi ile daha ksa olduundan, tane snrlarnn oksitlenmesinin konvansiyonel
ynteme kyasla daha az miktarda gerekletii dnlmektedir.
463

ekil 2. Mikrodalga (MW) ve konvansiyonel (C) sinterleme yntemiyle 1200, 1250 ve 1300C scaklklarda retilen
numunelerin sinterlenmi younluk sinterleme scakl grafii
Numunelerin taramal elektron mikroskobu ve optik mikroskop aracl ile mikroyapsal zellikleri incelendiinde
ise, mikrodalga sinterleme yntemi ile retilen numunelerin, konvansiyonel kartlarna kyasla azalan gzeneklilik
yzdesi ve tane boyutu ile yuvarlaklam gzenek morfolojileri ile elde edilebildikleri grlmtr (ekil 3, Tablo
1). Ayrca, her iki yntemle retilen numunelerde; sinterlenmenin iyi bir derecede gerekletiini gsteren tavlama
iftleri bulunmaktadr.
Tablo 1. Mikrodalga (M) ve konvansiyonel (K) sinterleme yntemleriyle 1200, 1250, 1300C scaklklarda retilen
numunelerin ortalama tane boyutu deerleri.
Sinterleme Scakl (C)
Ortalama Tane Boyutu (m)

M
K
1200
96
109
1250
106
135
1300
110
150
ekil 3. Mikrodalga sinterleme yntemiyle 1200 (a), 1250 (c) and 1300 C (e) ve konvansiyonel
sinterleme yntemiyle1200 (b) and 1250 (d) and 1300 C (f) scaklkarda retilen numunelerin taramal
electron mikroskobu grntleri
464

Numunelerin mekanik zelliklerinin mikrosertlik deerleri zerinden karakterizasyonu gerekletirildiinde ise (ekil
4), her iki yntemle retilen numunelerin optimum sertlik deerlerine maximum younlama denk gelen sinterleme
scaklklarnda ulatklar grlmektedir. Bu durum, sinterleme sonras younluklarn toz metalurjik numunelerin
fiziksel zelliklerini belirleyen nemli parametrelerden biri olmas sebebiyle, beklenen bir durumdur.
ekil 4. Mikrodalga (M) ve konvansiyonel (K) sinterleme yntemleri ile 1200, 1250 ve 1300C scaklklarda
retilen numunelerin ortalama mikrosertlik deerleri
Diferansiyel manyetik geirgenlik erileri zerinden numunelerin manyetik zellikleri incelendiinde ise (ekil 5 a-b),
her iki metodlar retilen numunelerin, daha dk scaklklarda retildiklerinde daha yksek manyetik geirgenlik
deerlerine ulatklar grlmektedir. Dk scaklklarda toz metalurjik alamlarn ulatklar sinterlenmi
younluk deerleri dk olmasna ramen, bu scaklklarda bile 100mye yaklaan ortalama tane boyu deerleri
sayesinde, yksek scaklklarda etkin olan tane snr oksitlenmesi nedeniyle, dk scaklklarda daha yksek
manyetik geirgenlik deerlerine ulalabilmitir. Ayrca, mikrodalga sinterleme yntemiyle retilen numunelerin,
konvansiyonel sinterleme yntemiyle retilen kartlarna kyasla daha dk manyetik geirgenlik deerlerine
sahip olduklar tespit edilmitir. Bu durumun, konvansiyonel sinterleme yntemi srasnda mikroyapsal irileme ve
ortalama tane boyutundaki artdan kaynakland dnlmektedir.
ekil 5. Mikrodalga (a) ve konvansiyonel (b) yntemle 1200, 1250, 1300C scaklklarda retilen numunelerin
diferansiyel geirgenlik deerlerinin uygulanan manyetik alanla (H) deiimi
4.Sonu
Bu alma kapsamnda elde edilen bulgular, mikrodalga sinterleme yntemiyle toz metalurjik yumuak manyetik
Ni-Fe alamlarnn konvansiyonel yntemel kyasla azalan ilem sreleri ve enerji safiyatlar ile, daha yksek
465

sinterlenmi younluklarda, azalan gzeneklilik yzdesi ve tane boyutu, iyiletirilmi mekanik zellikler ile
retilebildiklerini gstermitir. Diferansiyel geirgenlik erileri zerinden numunelerin manyetik karakterizasyonu
yapldnda ise, sinterleme sonras ok daha byk ortalama tane boyutu deerlerine sahip olan konvansiyonel
yntemle retilmi numunelerin, mikrodalga sinterleme yntemiyle retilmi numunelerden daha iyi yumuak
manyetik zellikler gsterdii tespit edilmitir. Ancak, sinterleme sonras manyetik numunelere tatbik edilecek olan
tane iriletirme tavlamas ilemi nedeniyle, mikrodalga sinterleme yntemi ile retilen numunelerin de tane boyutu
artrlacandan, yumuak manyetik toz metalurjik Ni-Fe numunelerin, azalan ilem sreleri ve artan sinterlenmi
younluk deerleri ile mikrodalga sinterleme yntemiyle avantajl bir ekilde retilebilecei dnlmektedir.
KAYNAKA
[1] W.F.T. Gale, Terry C, in: Smithells Metals Reference Book, pp. 9-12.
[2] F. Fausto, in: Measurement and characterization of magnetic materials, Elsevier Academic Press, 2004, pp.
62-65.
[3] R.M. German, Powder Metallurgy Science, Metal Powder Industries Federation, 1989.
[4] R.M. Anklekar, K. Bauer, D. Agrawal, R. Roy, Powder Metallurgy, 48 (2005) 39-46.
[5] V.D. Buchelnikov, D.V. Louzguine-Luzgin, A.P. Anzulevich, I.V. Bychkov, N. Yoshikawa, M. Sato, A. Inoue,
Physica B: Condensed Matter, 403 (2008) 4053-4058.
[6] M. Celuch, W. Gwarek, M. Soltysiak, in: 2008 International Conference of Recent Advances in Microwave
Theory and Applications, MICROWAVE 2008, 2008, pp. 404-405.
[7] P. Chhillar, D. Agrawal, J.H. Adair, Powder Metallurgy, 51 (2008) 182-187.
[8] S. Das, A.K. Mukhopadhyay, S. Datta, D. Basu, Bulletin of Materials Science, 31 (2008) 943-956.
[9] H. Katsuki, S. Komarneni, Funtai Oyobi Fummatsu Yakin/Journal of the Japan Society of Powder and Powder
Metallurgy, 50 (2003) 745-750.
[10] C. Leonelli, P. Veronesi, L. Denti, A. Gatto, L. Iuliano, Journal of Materials Processing Technology, 205 (2008)
489-496.
[11] K. Saitou, Scripta Materialia, 54 (2006) 875-879.
[12] S. Takayama, G. Link, M. Sato, M. Thumm, in: Conference Digest of the 2004 Joint 29th International
Conference on Infrared and Millimeter Waves and 12th International Conference on Terahertz Electronics,
2004, pp. 729-730.
466

Akm Destekli Sinterleme Yntemi le retilen Al2O3

Takviyeli Bronz Matriksli MMKin Karakterizasyonu
Mehmet UYSAL Ramazan KARSLIOLU, Ahmet ALP
Hatem AKBULUT,
Sakarya niversitesi, Mhendislik Fakltesi, Metalurji ve Malzeme Mhendislii Blm
54187 Adapazar/SAKARYA mehmetu@sakarya.edu.tr
zet
Bu almada bronz (% 90 Cu - %10 Sn) matriks ierisine 80 m boyutlarnda hacimce %10, 20 ve 30
takviyeli almina (Al2O3) ilave edilerek metal matrisli kompozit malzeme (MMK) retimi amalanmtr.
stenen bileimdeki tozlar bilyal deirmende homojen bir ekilde kartrlp basn altnda souk olarak
ekillendirilmitir. Oluturulan mukavemetsiz malzeme yaps, yksek akm ve dk voltaj kullanlarak
hzl bir ekilde sinterlenmitir. retilen numunelerin mikro yap, mikro setlik zellikleri ile oluan
fazlar ve matriks yap iersindeki partikl dalmlar Taramal Elektron Mikroskobu (SEM) kullanlarak
incelenmitir.
Anahtar Kelimeler: Akm destekli sinterleme, Bronz, SiC, MMK
Abstract
In this study, a bronze matrix (90 wt. % Cu + 10 wt. % Sn) was reinforced with Al2O3 particles
using mechanical alloying and then produced by subsequent rapid current sintering technique. The
mechanically ball milled bronze powders were reinforced with electroless Ni coated 80 m Al2O3 particles
with different volume fractions of 10 vol. % 20 vol. % 30 vol. % Microstructure of the bronze / Al2O3
composite produced by these techniques have been investigated by means of SEM.
Keywords: current sintering, bronze, Al2O3, MMC
1.Giri
MMKlerin retim ve kullanmlar son 20 ylda teknolojik gelimelerle birlikte, havaclk, uzay, savunma,
otomotiv, spor ve denizcilik gibi uygulamalarda art gstermitir Gnmzde zellikle otomotiv, uzay,
denizcilik, demiryolu tamacl ve spor malzemeleri gibi endstriyel sanayi alanlarnn birounda,
kompozit malzemelerin geleneksel malzemelerin yerine kullanmlar gn getike artarak devam
etmektedir [1, 2]. Bunun nedeni olarak, kompozit malzemelerin zellikle yksek spesifik mukavemet
(/E), spesifik modl (/E) ve dk younluk zellikleri gsterilebilir. Kompozit malzemeler ayrca
metaller gibi geleneksel malzemelere gre daha dk younluklar, artan korozyon ve scaklk gibi
zellikleriyle birtakm avantajlar sunmaktadr [3].
Partikl takviyeli kompozitler, matriks malzemesinin ierisine takviye malzemesi olarak partikllerin ilave
edilmesi ile oluur. Partikller farkl boyutlarda olabilen, tahmin edilebilir izotropik zellikler salayan
malzemelerdir. Ayrca birok partikl takviyeli kompozit malzeme iyi mekanik, termal ve tribolojik
zellikleri sebebiyle ilgi ekmekte, ok eitli endstriyel uygulamada kullanlmaktadr. Yaygn olarak
kullanlan partikller SiC ve Al2O3 olmakla birlikte, TiB2, B4C, SiO2, TiC, WC, BN, ZrO2 gibi partikl
takviyeler zerine birok alma yaplmaktadr [4].
Metal matriksli kompozit malzemelerin retiminde karlalan en temel problem, seramik fazn
slatlamamas ve buna bal olarak iyi bir ba oluturulamamasdr. Bu problem kompozit malzemelerin
ara yzey zelliklerini nemli lde etkiler. Ara yzeyin yaps kompozit malzemenin zellikleri zerinde
nemli bir etkiye sahiptir. Takviye faz ile malzemenin zelliklerinin glendirilmesi, matriks ve takviye
467

faz arasndaki ara yzey bann gcne baldr. Gl bir ara yzey ba, ykn matriksden takviye
fazna doru transferine izin verir. Bununla beraber malzemenin sertlik, krlma tokluu, sl genleme, s
iletkenlii srtnme katsays da ara yzeyin yapsyla etkilenir. Ara yzey ba dayanmn artrabilmek
iin kompozit retim ileminden nce genel olarak farkl n ilem;
-Seramik partikllere metalik kaplamalarn uygulanmas,
-Reaktif metallerle metal matrisin alamlandrlmas,
-Seramik partikllere sl ilem uygulanmas, suretiyle salanr [5, 6].
Dk termal genleme katsays, yksek sertlik, yksek elastik modl, iyi elektriksel iletkenlik, yksek
termal iletkenlik, iyi anma dayanm gibi zelliklerinden dolay bakr esasl kompozitler, yksek hibrid
modll malzemelerin, elektronik rlelerin, elektrikli yaylarn, birok elektrik/elektronik paralarn,
frenlerin, srtnmeye direnli malzemelerin retimi gibi amalar iin kullanlmaktadr [7, 8].
Bu almada bronz matriks iersine farkl hacim oranlarnda Al2O3 tozlar ilave edilerek, akm destekli
sinterleme yntemiyle kompozit malzeme retilmitir. Akm sinterleme ynteminin seilme nedeni,
ksa srelerde youn ve dk maliyetli kompozitlerin elde edilmesidir. retim prosesi uygulanmadan
nce Al2O3 seramik partikllerinin matriks yapya daha kolay girmesini kolaylatracak slatma artlarn
salamak amacyla yzeyleri akmsz yntemle nikel ile kaplanmtr. retilen kompozit malzemelerin
mikroyap ve sertlik zellikleri incelenmitir.
2. Deneysel almalar
2.1. Malzemeler
MMK malzeme retiminde matriks malzemesi olarak bronz (%90bakr-%10 kalay), takviye malzemesi
olarak hacimce % 10, 20 ve 30 oranlarnda, ortalama 80 m boyutunda Al2O3 seramik partiklleri
kullanlmtr.
2.2. Seramik Tozlarn Akmsz Yntemle Nikel Kaplanmas
Kompozit malzeme retiminde, metal/seramik partikl ara yzeyi byk sorun oluturmaktadr. Bu
ara yzey sorununu ortadan kaldrabilmek ve metal ile seramik arasndaki slatabilirlii artrmak iin,
seramik partikllerin yzeyi metal ile kaplanmaktadr. Bu amala yaplan almalarda alkali zeltiler
kullanlm olup, Al2O3 seramik partikllerinin yzeyleri Ni ile akmsz artlarda kaplanmtr. ekil 1 de
kullanlan akm destekli sinterleme ynteminin grnts verilmitir.
ekil 1. Akm sinterleme deney dzeneinin grnts [9]

2.2.1. Kaplama ncesi Uygulanan n Yzey lemleri
Seramik Tozlarnn Temizlenmesi: Kaplama yaplacak Al2O3 seramik tozlarnn yzey zellikleri
kaplamann verimlilii asndan ok nemlidir. Bu yzden seramik tozlarn kaplama ncesi yzeyleri
ultrasonik temizleme cihaznda aseton zeltisi iinde yaplarak, kaplamaya engel olabilecek eitli
kirlilikler giderilmeye allmtr.
Hassaslatrlma lemi: Bu ilemden ama toz yzeylerinde kalay iyonlarnn adsorbsiyonudur.
Seramik tozlar aseton ile temizlendikten sonra SnCl2 zeltisinde belirli srelerde tutulmak suretiyle
468

hassaslatrma denilen bu ilemin uygulanmas suretiyle yzeyde adsorbe olmu +2 deerlikli kalay
iyon tabakasnn oluturulmasdr.
Aktivasyon lemi: Bu ilem genellikle hassaslatrma ilemi akabinde uygulanmaktadr. Bu ilem
srasnda tozlar aktivasyon amacyla PdCl2 zeltisinde belirli bir sre bekletilmektedir. Bu esnada toz
yzeylerindeki kalayn ykseltgenmesi srasnda aa kan elektronlar alarak indirgenen Pd, ok
ince bir tabaka oluturmaktadr. Tozlar daha sonra 90 oCde etvde kurutularak kaplamaya hazr hale
getirilmitir.
2.2.2.Seramik Tozlarnn Nikel le Kaplanmas lemleri
Al2O3 seramik tozlarnn kaplanmasnda kullanlan akmsz nikel kaplama banyosu bileimi ve
parametreleri Tablo 1de verilmitir. Kaplamalar, pH 8 olan alkali zeltide ve 70 0C scaklkta
gerekletirilmitir.
Tablo 1. Akmsz nikel kaplama banyosu ierii ve parametreleri
Banyo bileenleri ve parametreleri
Datalar
NiCl2
(45.0 g/l)
Na-citrate (C6H5Na3O7. 2H2O)
(100.0 g/l)
NH4Cl
(50.0 g/l)
sodium hypophosphite
8.0 g/l)
pH
8
Scaklk
70oC
Sre
10 dak
Partikl miktar
10 g/l
2.3. Kompozit Malzeme retimi

Bronz matrisli kompozit malzeme retimi iin ncelikle akmsz nikel ile kaplanm Al2O3 seramik
ve bronz tozlar kartrma ilemine tabi tutulmutur. Al2O3 tozlar hacimce % 10, 20 ve 30 olacak
ekilde bronz matriks iersine ilave edildikten sonra gezegensel bilyal deirmende kartrma ilemi
2 saat sreyle gerekletirilmitir. Kartrma ileminde numune/bilya arlka oran 1/15 orannda
olacak ekilde WC bilyeler kullanlmtr. Bu ilemden sonra tozlar 300 kg/cm2lik basn altnda 10
dakika sreyle souk izostatik preslenerek ham numuneler elde edilmitir. Akabinde akm destekli
sinterleme yntemi ile bronz matrisli, hacimce % 10, 20 ve 30 Al2O3 takviyeli kompozit malzemeler elde
edilmitir. ekil 1 deki dzenee yerletirilen numune 10 dk sreyle 2,0 V altnda ortalama 1200 A akm
etkisinde braklm, malzemenin akma kar gsterdii diren sonucu aa kan syla hzla ykselen
scaklklarda sinterleme ilemi gerekletirilmitir.
2.4. Kompozit Malzemelerin Karakterizasyonu
retilen bronz matrisli kompozit malzemeler metalografik numune hazrlama teknikleri ile srasyla 600,
800, 1200 lk elmas zmpara kullanlarak kaba ve ince olarak zmparalanmtr. Daha sonra elmas
pastalar yardmyla kaba ve ince parlatma ilemlerine tabi tutulmutur. Metalografik olarak hazrlanan
yzeyler daha sonra etanol ile temizlenmi ve yzeydeki kirlilikler giderildikten sonra tozlarn dalm
ve morfolojisinin belirlenmesi iin JEOL JSM 6060LV marka taramal elektron mikroskobu (SEM) ile geri
salml elektron dedektr kullanlarak incelenmitir.
Matristeki zellik deiimlerinin tespiti amacyla retilen kompozit numunelerin mikrosertlikleri
incelenmitir. Leica VMHT MOT Mikro sertlik cihaznda her bir numune iin en az 5 alandan vickers
setlik lmleri yaplm ve 5 lmn ortalamas alnmtr. lmler 15 saniye sre ile 50 gr yk
altnda gerekletirilmitir.
3. Deneysel Sonular
3.1. Mikroyap almalar
3.1.1. Akmsz Nikel Kaplanm Numuneler
Kompozit malzeme retiminden nce Al2O3 seramik toz yzeyleri akmsz yntem ile nikel ile kaplanmtr.
ekil 2 de Al2O3 seramik tozlarnn nikel kaplanm ve kaplanmam fotoraflar grlmektedir. ekil
469

2a da kaplanmam Al2O3 tozlarnn temiz yzeyleri, homojen nikel kapl Al2O3 seramik tozlarnn SEM
resimleri ise ekil 2b de grlmektedir. SEM resimlerinden grld gibi Al2O3 seramik tozlarnn zeri
nikel ile baarl bir ekilde kaplanmtr. Nikel partiklleri seramik tozlarnn yzeyini homojen ekilde
kaplam ve tozlarn keskin kelerinde youn olarak birikmitir. ekil 2c deki EDS analizinde ise Al2O3
seramik tozlarnn zerinin Ni-P ile kapland ak bir ekilde grlmektedir.
ekil 2. a)Kaplanmam Al2O3 seramik tozlar, b)Ni kaplanm Al2O3 seramik tozlar, c) Ni kaplanm
Al2O3 seramik tozlarn EDS analizi.
3.1.2. Kompozit Malzemeler
Bronz matrisli kompozit malzemeler, bronz iersine hacimce %10 % 20 ve %30 oranlarnda Al2O3
takviyesi yaplmak suretiyle ve akm destekli sinterleme yntemi kullanlarak retilmitir. Sinterleme
ilemi btn malzemeler iin 1200 A akm altnda ve 10 dak. sre ile gerekletirilmitir. Farkl hacim
oranlarnda Al2O3 ile takviye edilmi kompozit malzemelerin SEM grntleri ekil 3de verilmitir. Bronz
matrisli kompozit malzemelerin mikroyap almalarnda Al2O3 seramik partikllerinin bronz matris
ierisine homojen olarak daldklar grlmektedir. Al2O3 seramik partikllerin matris iersine homojen
dalmn, Al2O3 partiklleri ile matris malzemesi arasnda arayzey bann iyi olmas ve alam
tarafndan Al2O3 partikllerinin iyi slatabilirlilii salamtr. Seramik partiklleri ile matris arasndaki
arayzeyin grnmnn de ok iyi olduu sylenebilir. Ayrca artan partikl hacim oranyla yapya
daha byk partikl girmesine ramen matris partikl faz uyumunun bozulmad, partikl dalm ve
homojenliinin saland da grlmektedir.
ekil 3. Bronz matrisli kompozit malzemelerin SEM grnts:a) %10 Al2O3, b) %20 Al2O3,
c) %30 Al2O3
470

3.2. Sertlik lmleri

Numunelerin sertlik lmleri mikro-sertlik cihaznda Vickers sertlik yntemi kullanlarak yaplmtr.
Sertlik deerleri, metalografik olarak hazrlanm numunelerden 50 gr yk altnda 15 sn sreyle ve 5
farkl lmn aritmetik ortalamas alnarak yaplmtr.
ncelenen kompozitlerin sertlik deerleri ekil 4 de verilmitir. Takviye edilen Al2O3 seramik tozlarn
hacm oranlar sonucu yapya giren partikl miktar arttka kompozit malzemenin sertliinde art
grlmektedir. Kompozit malzemelerde en yksek sertlik, % 30 hacimce Al2O3 ilave edilen malzemede
elde edilmitir. Bunun sebebi bronz matrisin iindeki sert Al2O3 seramik partikllerinin bulunmasndan
dolay matris takviye faz arayzeyinde dislokasyon younluunun artmas ve partiklerin dispersiyon
sertlemesi etkisi yapmasdr. Bylece partikller ana metal fazna gre daha sert malzemeler olarak
kompozit yapnn sertliine direkt olarak takviye yapmaktadr.
ekil 4. Bronza Al2O3 ilavesiyle sertlikte meydana gelen deiim

4.Sonular
Akm destekli sinterleme yntemi kullanlarak Al2O3 takviyeli kompozitler ksa srede baarl bir ekilde
retilmitir. Takviye faz ile matris arasndaki ara yzeyi iyiletirmek iin Al2O3 seramik tozlarn yzeyleri
akmsz nikel ile homojen bir ekilde kaplanmtr. Bronz matris iersine 80 m boyutunda hacimce
%10, %20 ve %30 oranlarnda Al2O3 takviye faz ilave edilerek akmla sinterleme yntemiyle kompozit
malzemeler retilmitir. Al2O3 partiklleri matris iersine homojen olarak dalarak baarl bir kompozit
retilmitir. Matris iersine ilave edilen Al2O3 partikllerinin miktar arttka kompozit malzemenin
sertliinde art meydana gelmitir.
Kaynaklar
1. Altnsoy Almina Takviyeli Bakr Kompozitlerin retimi Ve Karakterizasyonu Yksek Lisans Tezi, ,
Sakarya niversitesi, Fen Bilimleri Enstits, 2009
2.Kl F. Elektrolitik Nano Sic Partikl Takviyeli Nikel Kompozitlerinin zellikleri Yksek Lisans Tezi, ,
Sakarya niversitesi, Fen Bilimleri Enstits, 2008
3.Sur, G., Sahin, Y., Gkkaya, H., Ergimis Metal Karstrma ve Basnl Dkm Yntemi ile Alminyum
Esasl Tanecik Takviyeli Kompozitlerin retimi, J. Fac. Eng. Arch. Gazi Univ.,Vol.20, 2, 233-238,
2005
4.Gltekin, D., Metal matrisli kompozit fren diski balatas retimi ve karakterizasyonu, Yksek Lisans
Tezi, , Sakarya niversitesi, Fen Bilimleri Enstits, 2007
5. Yng, D. Y., Zhang, D.L., Processing of Cu-Al2O3 metal matrix nanocomposite materials by using
high energy ball milling, Materials Science & Engineering A, Vol. 286, pp. 152-156, 2000
6.Aslan, S., SiC ve Grafit takviyeli inko alminyum hibrit kompozit malzemelerin asnma
davranslarnn incelenmesi, Doktora Tezi, Sakarya niversitesi, Fen Bilimleri Enstits, 2005
7.Tjong S.C. Lau K.C. Tribological behaviour of SiC particle-reinforced copper matrix composites
Materials Letters Vol. 43 pp 274280 2000
8.Ramesh C.S. , Noor Ahmed R. , Mujeebu M.A. , Abdullah M.Z. Development and performance analysis
of novel cast copperSiCGr hybrid composites Materials and Design Vol.30 pp 19571965(2009)
9. Karsliolu R., Uysal M., Alp A., Akbulut H., Current Actvated Snterng Of Bronze Hybrd Mmcs
Coatngs On Steel Substrates 5th International Powder Metallurgy Conference October 8-12, 2008
Ankara TURKEY
471

Cu + % 5 Al/ Cr3C2 TOZU LE KAPLANAN TABAKALARIN YAPIMA

MUKAVEMET VE YZEY PRZLLNN NCELENMES
Serkan ZEL* ve Hseyin TURHAN**
*Bitlis Eren niversitesi, Mhendislik ve Mimarlk Fakltesi, Makina Mhendislii Blm, 13000,
Bitlis, sozel@beu.edu.tr
**
Frat niversitesi, Teknik Eitim Fakltesi, Metal Eitimi Blm, 23119, Elaz, hturhan@firat.edu.tr
ZET
Bu almada, Cu + 5 % Al toz karm ierisine farkl yzdelerde ilave edilen Cr3C2 tozlar, atmosferik
plazma pskrtme teknii kullanlarak Cu alam yzeyine kaplanmtr. Cu + 5 % Al ierisine % 5, % 10
ve % 20 Cr3C2 oranlar kullanlarak yaplan kaplamalarda Cr3C2n yzeye yapma mukavemeti ve yzey przllne olan etkisi incelenmitir. Bu amala, kaplanan tabakalara ekme deneyi uygulanm
ve yzey przllk deerleri llmtr. Deney sonular incelendiinde, Cu + 5 % Al/ Cr3C2 tozlar
ile kaplanan tabakalarn yapma mukavemetleri arayzey balanmasnn az olmasndan dolay dk
seviyelerde kmtr. Cr3C2 ilavesine bal olarak yzey przll deerinin artt tespit edilmitir.
Anahtar Szckler: Plazma Pskrtme, Cr3C2 tozu, Yapma mukavemeti, Przllk.
THE INVESTIGATION OF BONDING STRENGHT AND SURFACE

ROUGHNESS OF COATNG LAYERS WITH Cu + 5 % Al/ Cr3C2
POWDERS
ABSTRACT
In this study, the Cr3C2 added at different concentrations (5, 10 and 20 wt.%) to the Cu + 5 % Al content powders were coated on the surface of Cu alloy by using the atmospheric plasma spraying (APS)
method. The effect of Cr3C2 on bonding strenght and surface roughness was examined in four different
coatings. For this aim, bonding strenght and surface roughness values were measured. The results
showed that the bonding strenght of coating layer with Cu + 5% Al / Cr3C2 powders are low because of
the low interfacial adhesion. The surface roughness values were increased depending on the addition
of Cr3C2.
Keywords: Plasma Spraying, Cr3C2 powder, Bonding strenght, Roughness.
1. GR
Gelien teknoloji ile metal ve alamlarnn yzeyleri, yksek scaklk, anma ve korozyon dayanmn
arttrmak amac ile eitli kaplama ilemlerine tabi tutulmaktadr. Isl pskrtme kaplama teknikleri, tel
veya toz halindeki kaplama malzemelerinin bir pskrtme tabancasnda tayc, yanc ve yakc gazlarn eliinde pskrtlerek altlk zerinde biriktirilmesi ve koruyucu tabakann elde edilmesi esasna
dayanan ilemlerdir [1]. Toz pskrtmede, ince toz paracklar yksek s kaynann iinden geerek
ergimi ya da yar ergimi duruma gelirler. Ergiyen kaplama malzemesi kaplanacak olan parann souk
olan yzeyine pskrtlr. Yzeye darbe etkisiyle arpan tanecikler, dzlemekte ve esas metale olan
s transferi ile souyarak katlamaktadr. Birbirleri ile temas haline gelen bu tanecikler malzeme yzeyinde kaplama tabakasn meydana getirmektedirler [2]. Metallerden ve oksitlerden, oksit seramik ve
472

cams metallere kadar geni bir dalm aralndaki malzemeleri ieren sl pskrtme kaplamalar, ana
malzemenin beklenilmeyen ve gereksiz olan hasarndan dolay bata reticiler olmak zere herkesin
dikkatini ekmektedir. Paray tamamen yenilemek iin gerekli olan masrafn az bir ksm ile ve eitli sl
pskrtme yntemleri ile uygulanan yeni yzey malzemesi, bu tr paralara ilave mr kazandrmaktadr [3]. Plazma pskrtme yntemi, sl pskrtme tekniklerinin ierisindeki kaplama yntemlerinden
bir tanesidir. Plazma pskrtme yntemi ile sl bariyer, anma direnci, korozyon direnci gelitirilmi ve
biomedikal amal zel kaplamalar yaplabilmektedir [4, 5, 6].
Sert krom kaplamalar, mhendislik uygulamalarnda (havaclk, otomotiv, denizcilik vb.) kullanlan valf,
piston, ubuklar ve birok dier paralar gibi kritik mekanik bileenlerin yzey zelliklerini gelitirmede
yaygn olarak kullanlmaktadr [2]. Krom karbr, son derece sert olan refrakter bir seramik malzemedir.
Krom karbr, metal malzemelerin yzeylerinin sert olmasnn, korozyona ve anmaya kar dayankl
olmasnn istenedii yerlerde sl pskrtme malzemesi olarak kullanlmaktadr [7,8, 9].
Bu almada, Cu alam yzeyine Cu + 5 % Al/ Cr3C2 tozlar plazma pskrtme yntemi ile kaplanmtr. Kaplama deneyleri sonunda numunelerde, kaplama tabakasnn yzeye yapma mukavemeti
ve kaplama sonras yzey przllk deerlerine farkl oranlarda ilave edilen Cr3C2n etkisi aratrlmtr.
Alt malzeme olarak kullanlan Cu alam, % 5 Al, % 2 Fe ve % 2 Ni katk oranlarnn bakr ierisine
katlmasyla meydana gelmitir. 100 x 20 x 5 mm llerinde hazrlanan bakr alam numuneler, yzey
przllnn salanmas amac ile 60 PSIlik basn altnda Al2O3 kullanlarak yzey przlendirme
ilemine tabi tutulmutur. Yzey przlendirme ilemine tabi tutulan numunelerin yzeylerine, Cu + %5
Al ierisine farkl yzdelerde ilave edilen Cr3C2 tozlar ile elde edilen toz karmlar kaplanmtr. Bu toz
karmlarna ait karm yzdeleri Tablo 2de verilmitir. Kaplama tabakasna ilave edilen Cr3C2 + 7 %
(Ni20Cr) tozun SEM fotoraf ekil 1de grlmektedir.
Tablo 1. Cu + % 5 Al tozu ve Cr3C2 tozunun (%) karm oranlar.
Numuneler
Kaplama Tozlar (%) Karm Oranlar

Cu + % 5 Al
*Cr3C2
A1
100
A2
95
A3
90
10
A4
80
20
* Cr3C2 tozu METCO 430NS kodu ve Cr3C2 + 7 % (Ni20Cr) bileimi ile standart bir tozdur.
ekil 1. Cr3C2 + % 7 (NiCr) tozunun SEM fotoraf.

Plazma pskrtme kaplama ilemleri atmosferik plazma pskrtme kaplama nitesindeki 3 MB tabancasnn elle kullanlarak uygulanmas ile gerekletirilmitir. Plazma pskrtme ynteminin ematik grn ekil 2de verilmitir. Kaplamada kullanlan plazma pskrtme parametreleri Tablo 2de verilmitir.
473

ekil 2. Plazma pskrtme kaplama sisteminin ematik grn.

Tablo 2. Cu + Al + % Cr3C2 karbr karm tozlarna ait kaplama parametreleri.
Parametreler
Cu + Al + Cr3C2 Tozu
Akm
400 A
Gerilim
70 V
Sprey Mesafesi
100 mm
Plazma Gaz
145 l/dk Ar
10 l/dk H2
Tayc Gaz
37 l/dk Ar
Nozul ap
7,6 mm
Toz Besleme Oran
53 g/dk.
Kaplama sonras, kaplama tabakalarnn st yzeylerinden yzey przllk lmleri Mitutoyo Surftest-211 marka cihazda ayn yzeyin farkl blgelerinden lmler tekrarlanp aritmetik ortalamas hesaplanarak tespit edilmitir. Kaplama tabakalarnn ba mukavemet deerleri, ASTM C-633 standartna
uygun olarak hazrlanan numuneler ile ekme deneyine tabi tutularak tespit edilmitir. ekme deneyi
iin 25,4 mm apnda dairesel test kuponlar kullanlmtr (ekil 3-a). Ayn parametrelerle kaplama ilemine tabi tutulan ekme deney test kuponlar, zel epoksi yaptrclar ile ekme deney balklarna yaptrlm ve 2 saat sre ile 200 C scaklkta bekletilerek kurutma ilemine tabi tutulmutur (ekil 3-b).
Kurutma ilemi sonrasnda ekme deney balklar, ekil 4te verilen ekme deney cihaz ile yapma
mukavemeti testine tabi tutularak kaplama tabakas ile altlk malzeme arasndaki yapma mukavemet
deerleri tespit edilmitir.
474

ekil 3. a) Kaplanacak numuneler ve ekme deneyinde kullanlacak test kuponlar, b) ekme testi
deney balklar ve test numunesi.
ekil 4. Dillon marka ekme deney cihaz.

3. DENEYSEL SONULARIN NCELENMES
3.1. Kaplamalarn Yapma Mukavemet Deerleri
Kaplanm numunelere ekme deneyi sonras tespit edilen yapma mukavemetlerine ait grafik ekil
5te verilmitir. Numunelerin yapma mukavemet deerleri incelendiinde, plazma pskrtme kaplamalar iin n grlen mukavemet deerlerinin (34-69 MPa aras) [10] altndaki seviyelerde olduu grlmtr. Yapma mukavemeti deerlerindeki bu dklk, arayzeyle ilgili olarak Yeildal ve Gney [11]
tarafndan belirtilen, kaplama tabakas ile bakr alamndan oluan alt malzeme arasnda oksit tabakas
oluumlarnn varlndan ileri gelmektedir (ekil 6). Plazma pskrtme yntemi ile gerekletirilen kaplamalarda, kaplama esnasnda alt malzemenin snmas sz konusudur. Cu alam alt malzememizin
yzeyinin genelinde bu snmadan dolay bir oksit film tabakas olumaktadr. Cu + % 5 Al + Cr3C2
ile kaplanan numunelerde kaplama tabakas alt malzemeye, yzeydeki oksit tabakasna bal olarak
oluan gzenekten dolay tam olarak balanamamtr. Ara yzeyde gzenekli bir yap elde edilmitir.
Arayzeyde oluan bu gzenekler, kaplama tabakas ile alt malzemenin yapma mukavemetini drmtr. Yapma mukavemeti en dk seviyede 7,96 MPa deeri ile Cu + % 5 Al tozu ile kaplanan A1
numunesinde tespit edilmitir. Cu + % 5 Al toz ierisine ilave edilen Cr3C2 tozu ile yapma mukavemet
deeri artmtr. Ara yzeydeki tutunmaya bal olarak en yksek yapma mukavemeti 19,16 MPa deeri ile % 10 Cr3C2 ilaveli A3 numunesinde tespit edilmitir.
475

ekil 5. A grubu numunelere ait yapma mukavemeti deerleri.
ekil 6. A grubu numunelerde ara yzeydeki oksite bal olarak oluan gzenekler.
3.2. Kaplamalarn Yzey Przll Deerleri
Kaplama ileminde numunelerin, kaplama ncesi, yzey przlendirme ilemi sonras ve kaplama sonras yzey przllk deerleri llmtr (ekil 7). lmlerde; hehangi bir ilem uygulanmam
numunede 3,824 m ve yzeyi sadece przlendirilmi numunede de 5,125 m yzey przllk deerleri tespit edilmitir. Numune yzeyine yaplan kaplamalar ile A1, A2, A3 ve A4 numunelerinde farkl
yzey przllk deerleri tespit edilmitir. Yzeye Cu + % 5 Al tozu kaplanan A1 numunesinde 5,28
m przllk deeri elde edilmitir. % 5 Cr3C2 tozu ilaveli A2 numunesinde yzey przll 8,75 m
llrken; % 10 Cr3C2 tozu ilaveli A3 numunesinde 8,43 m ve % 20 Cr3C2 tozu ilaveli A4 numunesinde de 8,13 m yzey przllk deerleri tespit edilmitir. ekil 6da grld gibi Cu + % 5 Al tozu
ile kaplanan A1 numunesinde; A2, A3 ve A4 numunelerine gre daha iyi bir yzey kalitesi olumutur.
lave edilen Cr3C2 ile kaplama tabakasnn ergime scakl olaanst ykselmekte, taneciklerin birbiriyle olan sinterlemesi ktlemekte ve bu da yzey przllnn bir miktar ykselmesine neden
olmaktadr. A1 numunesinde yzey przllnn en dk olmas bu numunenin tamamyla istenen
kalitede olduunu gstermez. Cu + % 5 Al tozu ierisine ilave edilen Cr3C2 ile yzey przllk deeri
artmtr, fakat ilave edilen Cr3C2 miktarnn artmas ile yzey przllk deeri derek yzey kalitesi
ksmen iyilemitir.
ekil 7. A grubu numunelere ait alt malzeme ve kaplanan numunelerin yzey przllk deerleri.
476

4. Sonular
Plazma pskrtme yntemi ile Cu alam yzeyine Cr3C2 tozlarnn kaplanmas gerekletirilmitir. Kaplama ilemi sonrasnda numunelere uygulanan yapma mukavemeti testi sonucunda, alt malzemenin
kaplama esnasnda oksitlenmesi ve buna bal olarak ara yzeyde gzenek oluumunun meydana
geldii tespit edilmitir. Bu nedenle kaplama tabakalarnn tmnde standart deerlerin altnda bir yapma mukavemeti deeri llmtr. En yksek yapma mukavemeti A3 nolu numunede 19,16 MPa
deeri ile tespit edilmitir. Numunelere uygulanan yzey przllk testinde, ilave edilen Cr3C2 ile yzey
przllk deerinin artt ve en dk yzey przllnn A1 nolu numunede 5,28 m deeri ile
olutuu grlmtr.
Teekkr
Bu alma, FBAP-1471 nolu proje ile maddi olarak desteklenen bir doktora tez almasdr. Bu
proje ile maddi destek salayan Frat niversitesi Bilimsel Aratrma Projeler (FBAP) Birimine, kaplamalarn yaplmasnda ve ekme deneyinde yardmc olan THY Teknik A.. ve alanlarna sonsuz
kranlarmz sunarz.
KAYNAKLAR
1. . Ylmaz, E. Ercenk, C. Bindal, AISI 316L elii zerine Plazma Sprey Yntemi le Kaplanm
Al2O3 ve Al2O3 - % 13 TiO2 Kaplamalarn zelliklerine Ba Tabakann ve Al Katksnn Etkisi, 13.
Uluslararas Metalurji Ve Malzeme Kongresi, s. 690-696, stanbul, 2006.
2. S. zel, Alminyum alam ve bronzu yzeyine oksit ve karbr bileiklerinin plazma sprey yntemiyle kaplanmasnn aratrlmas, Doktora Tezi, Frat niversitesi Fen Bil. Ens., 2009.
3. N. Y. Sar, E. Kalu, K. Tlbenti, Alevle Isl Pskrtme Uygulanarak 1050 (C45 E) eliinin
Abrazif + Erozif Anma Davrannn yiletirilmesi, Kaynak Teknolojisi II. Ulusal Kongresi, s.
177-185, Ankara, 1999.
4. S.B. Mishra, K. Chandra, S. Prakash, B. Venkataraman, Characterisation and erosion behaviour of
a plasma sprayed Ni3Al coating on a Fe-based superalloy, Materials Letters, Vol. 59, pp. 3694
3698, 2005.
5. G. Bolelli, V. Cannillo, L. Lusvarghi, T. Manfredini, Glass-alumina composite coatings by plasma
spraying. Part I: Microstructural and mechanical characterization, Surface & Coatings Technology, Vol. 201, pp. 458473, 2006.
6. S. zel, H. Turhan, F. Sarslmaz, AA2024 Alminyum Alam Yzeyine Al2O3/Al2O3+TiO2 Tozunun
Plazma Sprey Yntemiyle Kaplanmas, Frat niversitesi Fen ve Mhendislik Bilimleri Dergisi,
20 (3), s. 503-508, 2008.
7. J.M. Guilemany, N. Espallargas, P.H. Suegama and A.V. Benedetti, Comparative study of Cr3C2
NiCr coatings obtained by HVOF and hard chromium coatings, Corrosion Science, Vol. 48, 10,
pp. 2998-3013, 2006.
8. G. C. Ji, C. J. Li, Y. Y. Wang and W.Y. Li, Microstructural characterization and abrasive wear performance of HVOF sprayed Cr3C2NiCr coating, Surface and Coatings Technology, Vol. 200, 24,
pp. 6749-6757, 2006.
9. N. Espallargas, J. Berget, J.M. Guilemany, A.V. Benedetti and P.H. Suegama, Cr3C2NiCr and
WCNi thermal spray coatings as alternatives to hard chromium for erosioncorrosion resistance,
Surface and Coatings Technology, Vol. 202, 8, pp. 1405-1417, 2008.
10. R. C. Tucker, Thermal Spray Coatings, Vol. 5: Surface Engineering, ASM Handbook, ISBN:
0-87170-384-2, Ohio, pp. 499-509, 1994.
11. R. Yeildal, Y.Z. Gnay, Plazma sprey yntemi ile kaplama ve sprey karakteristiklerinin incelenmesi, DE Mhendislik Fakltesi Fen ve Mhendislik Dergisi, 9, 1, s. 59-76, 2007.
477

MAGNEZYUM BOLUK YAPICI KULLANILARAK RETLEN TiNi

KPKLERNDE BASMA VE SPERELASTSTE DAVRANII
aydogmus@yyu.edu.tr
**
*
ZET
Bu almada boluk yapc olarak magnezyum kullanlarak retilen, % 38-59 gzenee sahip Ti-50.6 at %Ni kpklerinin basma ve sperelastisite davranlar incelenmitir. Kresel gzeneklere sahip stenitik TiNi kpkleri
farkl scaklklarda dngsel olarak basma yklemesine ve boaltmaya tabi tutulmutur. Mukavemet, Young modl
ve martensit oluturmak iin gereken kritik gerilmenin artan gzenek miktar ile ters orantl olduu bulunmutur.
Kpklerin ksmi sperelastisite gsterdikleri gzlemlenmi, geri kazanlamayan gerinme miktarlarnn artan test
scakl ile azald grlmtr. Dngsel ykleme-boaltma sonras % 5e kadar gerinimin tamamyla geri kazanld tespit edilmitir. % 38-51 gzeneklilikteki TiNi alamlarnn kemik implantasyonu gibi biyomedikal uygulamalarn gerektirdii mekanik zellikleri karlad sonucuna varlmtr.
Anahtar kelimeler: TiNi Kpkler, Martensitik Dnmler, Sperelastisite, Biyomedikal Uygulamalar, Dngsel
Basma.
COMPRESSION AND SUPERELASTICITY BEHAVIOR IN TiNi FOAMS

PRODUCED USING MAGNESIUM SPACERS
ABSTRACT
In the present study, compression and superelasticity behavior of Ti-50.6 at %Ni foams with porosities in the range
38-59% and produced by use of magnesium powders as space holders were investigated. Austenitic TiNi foams
with spherical pores were subjected to loading-unloading cycles under compression at different temperatures. It
has been found that strength, elastic moduli and critical stress for inducing martensite were inversely correlated
with increasing porosity. Partial superelasticity was observed for all the foams and unrecovered strain was found
to decrease with increasing test temperature. Strains up to 5% were recovered fully after cyclic loading-unloading.
TiNi foams produced with porosities in the range of 38-51% meet the main requirements of biomaterials in terms of
mechanical properties for use as bone implant.
Keywords: TiNi Foams, Martensitic Transformations, Superelasticity, Biomedical Applications, Cyclic Compression.
1. GR
Metalik kpkler, polimer ya da seramik gibi dier malzemelerden retilmi kpklere benzer ekilde srad fiziksel
ve mekanik zellikler gsterirler. Dk younluklarna ramen yksek rijitlik, yksek gaz geirgenlii ile yksek
478

termal iletkenlik gsterirler. Bu birbirine zt zellikleri birarada iermeleri nedeniyle otomotiv, havaclk, demiryolu, ve
inaat endstrilerinde yapsal amal kullanmlarnn yansra, susturucu, pil elektrodlar, sv depolama ve transferi
aygtlar gibi fonksiyonel uygulamalarda da ska kullanlmaktadrlar [1].
Metalik kpkler iin dier nemli bir uygulama alann biyomalzeme sektr oluturmaktadr. Bu uygulamalarn
byk bir blmnde kpn hem yapsal hem de fonksiyonel zelliklerinden yararlanlmaktadr. ekil bellek etkisi
ve sperelastisite gibi iki srad fonksiyonel zellik gsteren TiNi kpkler biyomedikal uygulamalarda ne kan
alamlar olmutur.
Bu zellikler sayesinde TiNi kpkler implant yaplacak blgeye kolaylkla yerletirilebilmekte ve vcut dokularyla
ok iyi bir temas salanabilmektedir [2]. Vcut iinde yer alan canl dokular ve kemiklerin % 2 civarndaki gerinimleri
tamamyla geri kazanabildikleri tespit edilmitir [3]. Bu davrana benzer bir mekanik davran gsteren sperelastik
TiNi alamlar bu adan da dier kpklere gre nemli bir avantaja sahiptir.
Biyouyumluluu kantlanm olan [4,5] TiNi kpklerin implant malzemesi olarak kullanlabilmeleri iin yeterli gzenek miktar, uygun gzenek boyutu ve gerekli mekanik zellikleri salamas zorunludur. Bu almada magnezyum
(Mg) boluk yapc tozlar kullanlarak retilen tek fazl, kresel gzenekli TiNi kpklerin yapsal ve fonksiyonel
zellikleri tespit edilerek implant malzemesi olarak kullanlmalarnn uygun olup olmad belirlenmeye allmtr.
zellikle mekanik basma ve sperelastisite davranlar sistematik deneylerle aratrlm, bu zelliklerin gzeneklilik, scaklk ve dngsel ykleme-boaltmayla olan deiimleri ortaya konulmutur.
2. DENEYSEL YNTEM
TiNi kpkleri retmek iin balang tozlar olarak nikelce zengin (Ti-50.6 at. %Ni, % 99.9 saflkta, Nanoval GmbH
& Co. KGdan temin edilmi), ortalama ap 21 m olan, inrt gaz atmosferi altnda atomizasyon yntemiyle retilmi, kresel TiNi alam tozlar kullanlmtr. Boluk yapc olarak ise 100-600 m aralnda elenen ve eleme
sonras ortalama 450 m apnda olan, yine inrt gaz altnda atomize etmek suretiyle retilmi, kresel Mg tozlar
(% 99.82 saflkta, Tangshan Weihao Magnesium Powder Co. LTDden satn alnm) kullanlmtr.
TiNi tozlarnn i yaps sadece B2 stenit fazndan olumaktadr [6-7]. retim yntemi daha nceki almalarmzda optimum hale getirdiimiz ve uyguladmz [7-9] yntemin aynsdr. Mg boluk yapc miktar uygun mekanik
zellikleri elde edebilmek iin bu almada hacimce % 20-50 aralnda ayarlanmtr. Balayc yardmyla kartrlan tozlar, 400 MPa basn altnda ift ynl presleme sonras 1100 C scaklkta, koruyucu argon atmosferi
altnda 1 saat sreyle sinterlenmilerdir. % 50 Mgden daha az Mg ieren kompaktlar sinterleme esnasnda toplam
Mg miktar % 50 olacak ekilde ekstra Mg, koruyucu olarak, ilave edildikten sonra sinterlenmitir. Frn stma hz
10 C/dak olarak sabit tutulurken, sinterleme sonrasnda pota frnn souk blgesine ekilerek yaklak 60-75 C/
dak bir hzda numunelerin oda scaklna soutulmalar salanmtr.
Sinterlenen numunelerin younluk ve gzenek miktar Arimet yntemi kullanlarak llmtr. Gzenek boyutlar
ve dalm, Noran System 6 enerji dispersiv spektrometresine sahip Jeol JSM 6400 taramal elektron mikroskobunda (SEM) kk bytmelerde (10X, 20X) alnan grntlerin Clemex Vision, professional edition, version 3.5.020
grnt analiz programnda deerlendirilmesiyle tespit edilmitir, (ekil 1). TiNi kpklerin dnm scaklklar
Perkin Elmer Diamond diferansiyel taramal kalorimetresi (DSC) ile 10 C /dak stma ve soutma hzlar kullanlarak belirlenmitir.
Basma ve sperelastisite testleri 10X10 mmlik silindirik numuneler kullanlarak 30 kN kapasiteli, stma haznesi olan Instron 3367 mekanik test cihaz yardmyla 0.1 mm/dak basma hzyla gerekletirilmitir. Elastik modl
deerleri gerilim-gerinim diyagramnn dorusal ksmndan hesaplanrken, stenit-martensit dnm gerilimi %
0.2-offset metodu ile hesaplanmtr. Sperelastisite testleri 0-250 MPa aralnda dngsel ykleme ve boaltmalarla farkl scaklkta yaplmtr: oda scakl (25 C), vcut scakl (37 C) ve stenit biti (Af) scaklnn
10-20 C zerindeki bir scaklk. Uygulanan maksimum gerilim deeri yksek gzenekli numuneler iin dk tutulurken azalan gzenek miktar ile birlikte artrlmtr.
479

ekil 1. Clemex Vision grnt analiz programnda % 59 gzenekli TiNi kpn gzenek boyutlarnn ve dalmnn belirlenmesi.
3.1. Gzeneklilik, Gzenek Boyutu ve Dalm
ekil 2den grld gibi artan Mg miktaryla younluun dorusal olarak derken gzenek miktarnn dorusal
olarak ykseldii gzlenmitir. retilen tm numunelerde toplam gzenekliliin eklenen Mg miktarndan fazla olduu grlmektedir. Bunun nedeni TiNi tozlarn iinde atomizasyon srasnda oluan boluklar ve TiNi tozlar arasnda
yer alan ksmi sinterlemeden kaynaklanan mikro-boluklardr. % 20 Mg eklenmi kpkteki gzenek miktar % 38
iken, % 50 Mg eklenmi kpkteki gzenek miktar % 59 olmutur. Karmdaki Mg miktar artarken TiNi tozu miktar azalmaktadr bu yzden de TiNi tozlar arasnda oluan mikro-boluklarn says da azalmaktadr. Dolaysyla
eklenen Mg miktar arttka toplam gzeneklilikteki art daha az olmaktadr.
Eklenen Mg miktarndan bamsz olarak makro-gzenek boyutu 380 130 m olarak belirlenmitir. ekil 3 % 20
ve % 50 Mg boluk yapc ilave edilerek sinterlenen dolaysyla farkl miktarda gzenek ieren iki farkl numunedeki
makro-gzeneklerin boyut dalm erisini vermektedir. Her iki kmlatif eri incelendiinde gzeneklerin % 90dan
fazla bir ksmnn 130-650 m aralnda olduu grlmektedir. Gzenekler Mgun buharlamasyla olutuu iin
gzenek boyutu dalm da kullanlan Mg tozun dalm ile bir paralellik gstermektedir. Mevcut almada retilen
tm kpklerde ak gzeneklilik oran % 95 ve zeri olarak belirlenmitir. Dk gzenek miktarlarnda dahi bu
orann yakalanmas mikro-gzeneklerin varl ile aklanabilir.
ekil 2. Younluk ve gzenekliliin eklenen Mg miktar ile deiimi.
480

Biyomedikal uygulamalarda kemik dokunun implant malzemesi iinde geliimi iin 100-600 m arasnda deien
gzenek boyutlar istenilmektedir [10]. Bunun yannda yapay kemik deiimi uygulamalar iin gzenek miktar %
30-90 aralnda olmaldr [2]. Ayrca kemik bymesi ve vcut svlarnn tanm iin gzenekler ak tipte ve birbirleriyle balantl olmaldr. Bu bilgilerin nda, retilen TiNi kpklerin btn gzenek miktarlarnda yapay kemik
implant olarak istenilen tm yapsal artlar salad grlmektedir.
3.2. Mikroyap ve Dnm Scaklklar
retilen btn kpklerin mikroyaps balangta kullanlan TiNi tozlarnn mikroyaps ile ayndr. Tm kpkler
yalnzca B2 stenit fazn iermektedirler. Mikroyap ile ilgili detayl bilgiler daha nceki almalarmzda [7-9] verilmitir. DSC erilerinden elde edilen ve izelge 1de verilen dnm scaklklarndan grld zere Af scaklklar
vcut scakl civarndayken martensit balama (Ms) scaklklar oda scaklnn altndadr. Bu sonular da XRD
verilerini (burada verilmemitir) desteklemektedir, yani tm kpkler oda scaklnda sadece stenitten olumaktadrlar.
ekil 3. (a) % 20 (b) % 50 Mg ilave edilerek retilen numunelerde sinterleme sonras gzenek dalm.
izelge 1. TiNi kpklerin dnm scaklklar.
Gzeneklilik (%)
Dnm scaklklar (C)

Ms
Mf
As
Af
38
17
-28
12
42
43
-34
21
36
51
15
-37
15
40
59
-40
33
3.3. Mekanik Basma ve Sperelastisite

ekil 4 farkl gzenek oranlarna sahip TiNi alamlarnn oda scaklndaki gerilim-gerinim diyagramlarn vermektedir. Gzenekli TiNi kpkler retim sonras herhangi bir termomekanik ileme tabi tutulmamlardr. ekilden
de grld zere mukavemet, elastik modl ve martensit oluturmak iin gereken kritik gerilim artan gzenek
miktaryla azalmaktadr. Sperelastisite mekanizmasyla geri kazanlabilen gerinim miktar da gzenek miktarnn
azalmasyla art gstermektedir. rnek olarak % 38 gzenekli TiNi alamnda % 7.7 lik bir gerinim uygulandktan
sonra sadece % 2.7lik bir kalnt gerinim kalmaktadr. te yandan daha yksek gzenee sahip (% 51) numune ise
benzer bir gerinime kadar deforme edildiinde (% 7.2) geri dnemeyen kalc gerinim miktar % 3.75 dzeyindedir.
481

ekil 4. Farkl gzeneklilikteki TiNi kpklerin oda scaklndaki gerilim-gerinim erileri.

Sperelastik gerinim kazanmnn tam olmamas da ekil 4ten aka gzlenmektedir. Bunun nedeni test scaklnn Af scaklndan daha dk olmas veya geri dnm mmkn olmayan plastik deformasyonun martensitik
dnme elik etmesi olabilir. Her iki etki ayn anda da grlebilir. Tam bir sperelastik dngnn gerekleebilmesi iin iki temel unsurun karlanmas gerekmektedir. lk olarak deformasyon yalnzca martensitik dnmle gereklemeli dislokasyon hareketi ile meydana gelen kayma mekanizmas aktif olmamaldr. Bunun salanabilmesi
iin kayma iin gereken kritik gerilimin martensitik dnmn mmkn hale gelmesini salayan kritik gerilimden
daha yksek olmas gerekmektedir. kinci olarak test scakl malzemenin Af scakl deerinden daha yksek olmaldr. Bu art salanmazsa oluan martensit faz test scaklnda stabil olacandan ykn kaldrlmasyla birlikte
stenit fazna dnmeyecektir. Deformasyon srasnda dnm scaklklarnn artmas da bilinen bir gerektir. Bu
scaklk artn telafi etmek iin genellikle sperelastisite testleri Af scaklnn 10-20 C zerindeki bir scaklkta
yaplrlar [11] ve en iyi ekil geri kazanm (tam bir sperelastik dng) bu scaklklarda salanr. Md diye tanmlanan
ve hemen altnda gerilim ile martensit oluturulabilen maksimum bir scaklk vardr. Her ne kadar bu scakla kadar
sperelastisite mmkn olsa da tam bir sperelastik dng dar bir scaklk aralnda elde edilebilir. nk artan
scaklkla birlikte martensitik dnm iin gereken gerilim artmakta iken kayma iin gereken gerilim azalmaktadr.
ekil 5. % 51 gzenekli TiNi kpn gerilim-gerinim erilerinin ve sperelastisite davrannn scaklkla

deiimi.
ekil 5 farkl scaklklarda % 51 gzenee sahip TiNi alamlarnn gerilim-gerinim erilerini gstermektedir. Dayan, Young moduli ve martensit oluturacak kritik gerilme artan scaklkla birlikte art gstermektedir. izelge 2
ayn numunelerde ve % 59 gzenekli TiNi kpklerde geri kazanlamayan gerinim miktarlarn zetlemektedir. Artan
scaklkla birlikte kalnt gerinimlerin miktarndaki dme aka grlmektedir. ekil 5 ve izelge 2 ayn anda analiz
edilirse geri kazanlamayan gerinimlerin nedeninin deformasyonun sadece martensitik dnmle deil ayn zamanda kayma mekanizmasyla gereklemesi olduu grlecektir. Af scaklnn zerindeki scaklklarda yaplan
testlerde bile kalnt gerinimlerin olmas bu sonucu desteklemektedir. Oda scakl ya da vcut scaklnda test
482

edilen numuneler daha sonra Af scaklklarnn zerine stldklarnda bir miktar gerinimi daha kazandklar tespit
edilmitir. Yine de mutlak bir miktar gerinim her zaman kalmtr. rnein % 51 gzenekli numunede oda scaklndaki ykleme-boaltma admlarndan sonra kalan % 3.75lik gerinim Af scaklnn zerine stldnda % 1.8e
dmtr. Buradan martensitik dnmle birlikte kayma mekanizmasnn da altn syleyebiliriz.
izelge 2. ki farkl gzenee sahip gzenkli TiNi alamlarnn farkl scaklklarda testi sonucu kazanlmayan
gerinim miktarlar.
Geri kazanlmayan gerinim (%)
Gzeneklilik (%)
Oda scakl
Vcut scakl
T>Af (60 C)
51
42
32
22
59
51
31
26
ekil 6 oda scaklnda sabit gerilim altnda yaplan dngsel ykleme ve boaltma testlerinin sperelastisite zerindeki etkilerini gstermektedir. Kalnt gerinim miktarnda artan dng saysyla birlikte bir d gzlenmitir ve 5.
dng sonunda ekil 6 (b) den de grlecei zere kalnt gerinim miktar sfra inmitir. Bu tespit farkl gzeneklere
sahip TiNi alamlarnn hepsi iin geerlidir. 4 ya da 5. dngnn sonunda geri kazanlamayan gerinim hemen
hemen olmamtr.
ekil 6. Sabit gerilimde yaplan dngsel ykleme ve boaltmalarn TiNi kpklerin sperelastisite zellikleri
zerindeki etkisini gsteren gerilim-gerinim erileri (a) ve (b) % 51 gzenekli, 10 dng 125 MPada, (c) % 43
gzenekli, artan gerilimlerde dngler.
483

ekil 6 (c) % 43 gzenee sahip TiNi kpn tipik gerilimgerinim erisini gstermektedir. Testler 6 farkl gerilim
deerinde ilkinde 10 dng sonrakilerde 5 dng olmak zere yaplmtr. lk dngden sonra yaplan ikinci ykleme esnasnda dorusal bir deformasyon davran gzlenmektedir. Gerilim miktar artrldnda da deformasyonun
bir nce uygulanan gerilim miktarna kadar dorusal ilerledii daha sonra dorusallktan saparak klasik bir ekilde
devam ettii grlmektedir.
TiNi kpklerin basma ve sperelastisite davran hacimli (gzenek iermeyen) TiNi alamlarnnkinden bariz bir
ekilde farkllk gstermektedir. Hacimli TiNi alamlar optimum artlarda retilip gerekli termomekanik ilemler
uygulandnda belirli gerilim deerlerinde tam bir sperelastik dng davran sergilerler. Fakat ekme esnasnda
hem ileri (stenitten martensite) hem de geri (martensitten stenite) ynde olan dnmler neredeyse sabit ya da
ok az eimli gerilimlerde vuku bulurken basma durumunda bu eim artmaktadr. Gzenekli malzemelerde uygulanan yk hcre duvarlar tamaktadr. Bu almadaki gibi ksmi sinterleme ile retilen ve makro-gzeneklerin yannda mikro-gzenekler de ieren alamlarda uygulanan yk byk bir ounlukla sinterleme boyunlar tarafndan
tanmaktadr. Yap ierisinde rastgele olumu farkl boyut, ekil ve farkl ynlenmelerde bir ok sinterleme boynu
mevcuttur. Uygulanan yk her ne kadar ayn olsa da sinterleme boyunlar kanlmaz olarak farkl gerilimlere maruz
kalacaktr. Sonu olarak da her bir boyun farkl zamanlarda martensitik ya da stenitik dnme urayacaklardr.
Ayn ekilde farkl zamanlarda plastik deformasyona da urayabilirler. Bu yzden deformasyon sabit bir gerilim
seviyesinde ilerlemek yerine gittike artan gerilimlerde gereklemektedir. Bu da sabit ya da az eimli gerilimlerin
TiNi kpklerin basma testi srasnda neden gzlemlenemediini aklamaktadr.
Ykleme esnasnda martensitik dnmlerin balamas iin gereken kritik gerilim de ayn ekilde sabit olamaz.
Aslnda sabittir ama herbir boyun bu gerilime fakl zamanlarda ya da dier bir deyile farkl uygulanan gerilim deerlerinde ular. Bu yzden elastik deformasyon blgesinde dahi martensitik dnmler ya da plastik deformasyon
meydana gelebilir. Sperelastik TiNi kpklerin elastik modllerinin dk olmasnn nedeni byle aklanabilir.
Gzlenebilen ya da % 0.2 off-set metoduyla bulunabilecek kritik gerilime ulaldnda ilk yklemede dorusallktan
sapma grlmektedir. Bu gerilimden itibaren plastik deformasyonun ciddi bir biimde arttn sylemek mmkn
grnmektedir.
Ayn gerilim deerine yeniden ykleme yapldnda yeni dislokasyon hareketleri olmayacaktr ve deformasyon
sadece elastik deformasyon ve martensitik dnmler yolu ile gerekleecektir. Bu ykleme esnasnda neredeyse
tamam ile dorusal bir gerilim-gerinim davrannn grnmesi plastik deformasyonun ilk yklemedeki dorusallktan sapmann balad gerilimden itibaren gerekletii tezini dorulamaktadr. Bylelikle ikinci ykleme sonrasnda gerinimin tamam geri kazanlacaktr. Elbette test scaklnn Af scaklndan uygun miktarda yksek olmas ve
martensit stabilizasyonunun (ar deformasyon nedeniyle) olumamas artyla.
Biyoimplantasyon amacyla kullanlabilecek TiNi kpklerinin mekanik zellikler asndan yksek dayan (en az
100 MPa % 2 gerinimde) ve % 8lik gerinime yklendikten sonra % 2den daha fazla gerinimi geri kazanmas gibi temel nartlar yerine getirmeleri zorunluluu vardr [2]. Gerinim kazanm miktar koulunu retilen btn numuneler
hibir ilem yapmadan yerine getirebilmektedirler. Fakat yksek dayan koulunu oda scakl testlerinde en youn
numunenin (% 38 gzenekli) dahi salayamad grlmektedir. Vcut scaklnda ve daha yksek scaklklarda
ise bu kpn ve % 43 gzenee sahip TiNi alamnn bu dayanc salad gzlenmitir. Dngsel yklemeboaltma yapldnda ise % 38 ve % 43 gzenee sahip alamlar btn scaklklarda gerekli koulu salarken %
51 gzenekli kpk ise ancak Af scaklnn zerindeki scaklklarda bu zorunluluu yerine getirebilmektedir. % 59
gzenekli numunenin ise zaten maksimum dayanc 90 MPa civarndadr.
TiNi kpklerin dngsel ykleme-boaltma ilemine tabi tutulmas sperelastisite zelliklerinin iyiletirilmesi asndan yalandrmaya alternatif ucuz ve basit bir yntem olarak kullanlabilir. Bu ilem sonucu iyi bir dorusal
sperelastisite elde edilebilmektedir. % 43 gzenee sahip numune 150 MPada 5 dng ile yklenip boaltldnda son dngde % 3.8 olan gerinimin tamamn kazanabilmitir. Dngsel ykleme-boaltma sonras dorusal
sperelastisitenin elde edilmesi istenilen geri kazanm miktarnn hangi gerilimde elde edilebileceinin de kolaylkla hesaplanabilmesini salamaktadr. Elastik moduli deerlerinde dngsel ykleme-boaltma sonras belirgin
bir farkn olmad ilk bakta anlalmaktadr. nk hemen hemen btn ykleme ve boaltma erileri birbirine
paraleldirler.
ekil 7 dngsel ykleme-boaltmann mukavemet ve sneklie olan etkisini sunmaktadr. Maksimum basma dayanc az bir miktar derken krlma gerinimindeki dme yar yaryadr. Bu ileme maruz braklmayan numunede
% 15 gerinimde ilk atlak oluurken, 150 MPada 20 dng sonras 21. dngde krlan numunede ilk atlak % 7 ye
yakn bir gerinimde ortaya kmtr. Test edilen numunenin gzeneklilik oran % 51 dir.
484

ekil 7. Dngsel ykleme-boaltmann basma mukavemeti ve krlma gerinimi zerindeki etkisi.

ekil 8 farkl gzenekteki numunelerin farkl scaklktaki elastik moduli deerlerini vermektedir. Artan gzenek
miktaryla elastik modln dorusal olarak azald gzlemlenmitir ve beklenildii gibi artan scaklklarla elastik
modlde de bir art kaydedilmitir. Daha nce de belirtildii zere martensit dnmn mmkn hale getiren
kritik gerilme scaklkla dorusal olarak artmaktadr ve bu gerilme martensit Ms scaklnn hemen zerinde minimumdur. Yani Ms scaklndan uzaklatka gereken gerilme miktar da artacaktr. Bu da martensitik dnm
zorlatracandan elastik modlde artmaya neden olacaktr. Youn kemiin elastik modl 10-20 GPa arasnda
deiirken gzenekli kemiinki 3 GPadan kktr [12-13]. % 38 ve % 43 gzenee sahip TiNi alamlarnn elastik
modl deerleri vcut scaklnda youn kemiinki ile ayn aralkta yer almaktadr. % 51 gzenekli TiNi alam da
60 Cde bu arala girmekte daha dk scaklklarda da fazla dk olmamaktadr. Btn bu mekanik zellikler
birlikte deerlendirildiinde % 38-51 arasnda gzenek ieren TiNi kpklerin yapay kemik olarak kullanlmalarnda
mekanik adan da bir sorun tekil etmedikleri grlmtr. Daha yksek sinterleme scaklklar ve nikelce zengin
alam tozlar kullanlarak mekanik zellikler daha da gelitirilebilir ve bylelikle % 51den daha fazla gzenek ieren
TiNi kpklerin de mekanik zellikleri yapay kemiinkiyle ayn seviyelere getirilebilir.
ekil 8. Elastik modl deerlerinin gzenek miktar ve scaklkla deiimi.

4. SONULAR
1. Mg boluk yapc kullanlarak retilen TiNi kpklerin gzenek yaps, miktar ve boyutlar kemik implantasyonu
uygulamalar iin uygundur.
2. TiNi kpklerin basma ve sperelastisite davran hacimli TiNi alamlarnnkinden farkldr. Dorusal spere-
lastisite gsteren kpklerde elastik modl, dayan ve martensit oluturmak iin gereken gerilim deeri artan
gzeneklilikle azalmaktadr.
485

3. Btn kpklerde ksmi sperelastisite gzlenmi olup, geri kazanlamayan gerinme miktarlarnn artan test
scakl ile azald grlmtr. Dngsel ykleme-boaltma sonras % 5e varan gerinimler tamamen geri
kazanlabilmitir. Kalnt gerilmelerin nedeni test scakl ya da farkl geometrik yapda olan hcre duvarlar ve
sinter boyunlarnn farkl gerilmelere maruz kalmas sonucu meydana gelen martensit stabilizasyonuna balanmtr.
4. % 38-51 gzeneklilikteki TiNi alamlarnn kemik implantasyonu gibi biyomedikal uygulamalarn gerektirdii
mekanik zellikleri karlad tespit edilmitir.
TEEKKR
KAYNAKLAR
1. Banhart, J., Manufacture, Characterisation and Application of Cellular Metals and Metal Foams, Progress in
Materials Science, Vol. 46, pp. 559-632, 2001.
2. Bansiddhi, A., Sargeant, T.D., Stupp, S.I., Dunand, D.C., Porous NiTi for Bone Implants: A Review, Acta Biomaterialia, Vol. 4, pp. 773-782, 2008.
3. Gjunter, V.E., Sysoliatin, P., Temerkhamor, T., Superelastic Shape Memory Implants in Maxillofacial Sur-
gery, Traumatology, Orthopaedics, and Neurosurgery, Tomsk University Publishing House, Tomsk, Russia,
1995.
5. Pelton, A.R., Stoeckel, D., Duerig, T.W., Medical Uses of Nitinol, Materials Science Forum, Vol. 327-328,
pp. 63-70, 2000.
6. Aydomu, T., Bor, A.., Production and Characterization of Porous TiNi Shape Memory Alloys, Turkish
Journal of Engineering and Environmental Sciences, Vol. 35, pp. 69-82, 2011.
7. Aydomu, T., Bor, ., Gzenekli TiNi ekil Bellekli Alamlarnn retilmesi ve Karakterizasyonu, 15. Uluslararas Metalurji ve Malzeme Kongresi, Dzenleyen: TMMOB Metalurji Mhendisleri Odas, s. 665-675,
stanbul, 2010.
8. Aydomu, T., Bor, ., Processing of Porous TiNi Alloys Using Magnesium as Space Holder, Journal of Alloys and Compounds, Vol. 478, pp. 705-710, 2009.
Powder Metallurgy Using Magnesium as a Space Holder, Metallurgical and Materials Transactions A, in
press, DOI: 10.1007/s11661-011-0714-z.
10. Itin, V., Gyunter, V., Shabalovskaya, S., Sachdeva, R., Mechanical Properties and Shape Memory of
Porous Nitinol, Materials Characterization, Vol. 32, pp. 179-187, 1994.
11.
Liu, D.Y., Galvin, S.P., Criteria for Pseudoelasticity in Near-equiatomic NiTi Shape Memory Alloys, Acta
12. Rho, J.Y., Ashman, R.B., Turner, C.H., Youngs Modulus of Trabecular and Cortical Bone Material:
Ultrasonic and Microtensile Measurements, Journal of Biomechanics, Vol. 26, pp. 111-119, 1993.
13. Suchanek, W., Yoshimura, M., Processing and Properties of Hydroxyapatite-based Biomaterials for Use
as Hard Tissue Replacement Implants, Journal of Materials Research, Vol. 13, pp. 94-117, 1998.
486

TiNi KPKLERDE EKL BELLEK DAVRANII VE FAZ DNM

SICAKLIKLARININ NCELENMES
aydogmus@yyu.edu.tr
**
*
ZET
Mevcut almada Ti-50.4 at. %Ni alam tozu kullanlarak boluk yapc toz metalurjisi yntemiyle retilen % 5373 gzeneklilie sahip TiNi kpklerinde gzenek miktarnn serbest ekil kazanm ve faz dnm scaklklar
zerindeki etkisi incelenmitir. Boluk yapc olarak kresel magnezyum tozlar kullanlmtr. ekil bellek etkisiyle
kazanlan gerinim miktarnn artan gzeneklilik ile % 95lerden % 78e kadar azald gzlenmitir. Uygulanan gerinim miktarnn artmasyla grece dk gzenekli kpklerde (% 53-59) ekil kazanm fazla etkilenmezken yksek
gzenekli kpklerde % 20ye varan azalmalar meydana gelmitir. Faz dnm scaklklarnn gzeneklilikten
nemli lde etkilenmedii artan gzenek miktar ile yavaa ykseldii tespit edilmitir. te yandan kullanlan
alam tozu ile kpklerin dnm scaklklar karlatrldnda 25 C ye varan artlar belirlenmitir. Bu artn
nedeni boluk yapc olarak kullanlan magnezyumun proses esnasnda oksitlenmeyi nlemesiyle aklanmtr.
Anahtar kelimeler: ekil Bellek Etkisi, Gzeneklilik, Faz Dnm Scaklklar, Martensitik Dnmler, TiNi Alamlar.
INVESTIGATION OF SHAPE MEMORY BEHAVIOR AND PHASE

TRANSFORMATION TEMPERATURES IN TiNi FOAMS
ABSTRACT
In the present study, effect of porosity on free shape recovery and phase transformation temperatures of porous TiNi
alloys with porosities in the range of 53-73% which were produced using Ti-50.4 at. %Ni alloy powders and space
holder technique has been investigated. Spherical magnesium powders were used as space holder material. It has
been observed that strain recoveries by shape memory mechanism decreased from 95% to 78% with increasing
porosity. While shape recovery in 53% and 59% porosity samples, relatively low porosity, was not dependent on
the amount of applied strain considerably, in higher porosity samples shape recovery exhibited up to 20% decrease
with increasing strain. It has also been found that phase transformation temperatures has not affected much from
porosity content; just a slight increase was observed with increasing porosity. On the contrary, increase in the transformation temperatures of the foams produced compared to that of the starting prealloyed powders reached up to
25 C. This has been explained by the deoxidation of TiNi alloy by the magnesium used as space holder during
processing.
Keywords: Shape Memory Effect, Porosity, Phase Transformation Temperatures, Martensitic Transformations, TiNi
Alloys.
487

1. GR
ekil bellekli alamlar (hafzal ya da akll alamlar olarak da bilinirler), termomekanik yklerin uygulanmasyla termoelastik martensitik dnm gsteren ve belirli bir scakln zerine stldklarnda kalc ekil deiimlerini geri
kazanabilme yeteneine sahip metalik alamlar olarak tanmlanrlar. Fakat ekil bellek etkisi ayn zamanda baz
seramik ve polimerik malzemelerde de grlmektedir. [1]. Atomik olarak % 50 titanyum ve % 50 nikelden oluan TiNi
alamnda benzersiz ekil bellek etkisi ilk olarak 1963 ylnda Buehler ve arkadalar tarafndan tesadfen farkedildi [2]. Her ne kadar ayn etki baka alamlarda daha nceden bulunmu olsa da aratrmaclarn fazla dikkatini
ekmemitir. Buna karlk TiNi alam bulunuundan hemen sonra olduka popler hale geldi. Bunda alamn
bulunduu Naval Ordinance Laboratory tarafndan dnya apnda yaplan yaynlar ve birok uygulama iin gerekli
olan stn mekanik zellikleri salamas ile ekil bellek etkisi gsteren dier alamlar iinde en iyi performans
gstermesi etken olan faktrler olarak sralanabilir [3]. ekil bellek etkisi gsteren eitli alamlardan sadece TiNi
ve bakr bazl olanlar ticari uygulama alan bulmutur.
Yapay sert doku nakillerinde metaller ve alamlar en ok kullanlan malzemelerdir. Biyomalzeme endstrisinin
dnya apnda pazar paynn 2013de 140 milyar dolara ulamas beklenmektedir [4] ve bunun nemli bir ksmn
sert doku onarm ve nakilleri oluturmaktadr. Bu malzemelere olan ihtiya gn getike artmaktadr ve bu artn
nmzdeki yllarda ok daha hzl olaca ngrlmektedir. u anda kullanlan geleneksel biyomalzemeler, nakil
malzemesinin ve kemiin uyum sorunlar nedeniyle deiik problemler yaratmaktadr. Fizikokimyasal ve mekanik
zellikleri ne olursa olsun herhangi bir implant, vcut dokularyla iyi ve kalc bir temas salayamad mddete,
vcut tarafndan kabul grmez. Olduka basit grnen ancak vida, yaptrc, dolgu malzemesi, plastik ya da
karmak mekanik sistemlerin kullanlmasyla tatmin edici bir ekilde zlemeyen bu sorunun TiNi ekil bellekli
alamdan yaplm, snger kemiinkine benzeyen bir yap ieren gzenekli implant paralar kullanlarak baaryla
zlebilme olasl ok yksektir.
TiNi alamnn biyouyumluluu 316L paslanmaz eliininkiyle ayn seviyededir [5]. Malzemenin yzeyinde oluan
ve biyouyumluluu salyan TiO2 tabakas ayn zamanda alam iindeki nikel ve dier elementlerin znmesini
ve vcuda yaylmasn engellemektedir. Bunun yannda TiNi alamlar mkemmel mekanik zellikler, iyi korozyon
dayanc ve stn ekil bellek etkisi gibi ekici zellikleri bir arada iermektedir. mplant uygulamalarnda, gzenekler
iine kemik bymesine, vcut svlarnn serbeste dolamna izin verir, nakil parann vcutla btnlemesini
salayarak implant ve dokular arasnda muntazam uyumlu bir ban olumasn mmkn klar. Vcut iinde yer alan
canl dokular ve kemikler ekme ykleri altnda yksek geri kazanlabilir gerinimlere sahiptir ( > % 2) [6]. Olduka
iyi bir elastikiyet gerektiren bu davrana benzer bir davran ancak ekil bellekli alamlar gsterebilmektedir.
Gzenekli TiNi alamlarnn elastik modlleri kemiin elastik modl seviyelerine gzenek miktar ve boyutunun
ayarlanmasyla kolaylkla indirilebilmektedir. Bu yzden gzenekli TiNi alamlar kala ve eklem bozukluklarnn
tedavisinde, travmatolojide, kemik ve sert doku nakillerinde ve diilikte implant malzemesi olarak kullanlma potansiyeli yksek malzemelerdir [7-9].
Yakn zamanda yaplan almalarda gzenekli TiNi alamlarnda da bir dereceye kadar ekil bellek etkisi gzlenmitir [10,11]. Pratik uygulamalar iin ok nemli olan bu zelliin ve dnm scaklklarnn belirlenmesi son
derece gerekli bir almadr. Literatrde gzenekli TiNi alam retme yntemleri ile ilgili ok sayda yayn [12-27]
varken bu malzemelerin ekil bellek etkisi [10,11] ve dnm scaklklarn gzenek miktar ile ilikilendirerek
inceleyen makale [28-30] says olduka azdr. Bu almada magnezyum boluk yapc kullanlarak retilen TiNi
alamlarnda gzenek miktarnn ekil bellek etkisi ve martensitik dnm scaklklar zerindeki etkileri sistematik
bir ekilde ortaya konulmutur.
2. DENEYSEL YNTEM
Metalik kpk retiminde balang tozlar olarak hafif nikelce zengin (Ti-50.4 at. %Ni, % 99.9 saflkta, Special
Metals Corp.dan temin edilmi) TiNi tozlar kullanlmtr. Gaussian (log-normal) dalm gsteren TiNi alam tozunun ortalama ap 40 m (ekil 1(a)) iken boluk yapc kresel Mg tozunun (%99.82 saflkta, Tangshan Weihao
Magnesium Powder Co. LTDden satn alnm) ap ortalama 450 m (ekil 1(b)) olarak belirlenmitir. Her iki tozda
inrt argon gaz altnda atomize edilmek suretiyle retilmitir. TiNi alam tozlarnn ekli, sinterleme esnasnda
kirlenmeye ve istenmeyen Ti-Ni bileiklerinin oluumuna yol aabilecek oksitlenme vb. reaksiyonlar minimuma
488

indirmek iin yzey alan en dk olan kre (ekil 2(a)) olarak seilmitir. ekil 2(b)den grlecei zere oda
scaklnda (25 C) elde edilen X n difraksiyon (XRD) sonularna gre TiNi tozun iyapsnda B2 stenit ve
B19 martensit fazlar bulunmaktadr. Diferansiyel taramal kalorimetre (DSC) ile llen dnm scaklklar da
bu sonu ile uyum iindedir. Martensit balama (Ms) ve martensit biti (Mf) scaklklar srasyla 28 ve 10 C olarak
belirlenmitir. stenit balama (As) ve stenit biti (Af) scaklklar ise 36 ve 58 C olarak bulunmutur.
ekil 1. (a) TiNi, (b) Mg tozuna ait parack boyut dalmn gsteren histogramlar.
Gzenekli TiNi alam retiminde kullanlan boluk yapc yntem daha nceki almalarmzda [7,8,23] ayrntl
olarak aklanmtr. zetle hacimce % 40-70 aralnda Mg ieren TiNi ve Mg karmlar % 5 polivinil alkol (PVA)
zeltisi (% 2.5 PVA + su) ilavesiyle hazrlanmtr. Elde edilen karmlar souk olarak basma kalplar iinde
400 MPa basn altnda ift ynl olarak baslmlardr. Presleme sonras kalplardan karlan yaklak 10 mm
apnda ve 12 mm yksekliindeki numuneler 1100 C scaklkta, koruyucu argon atmosferi altnda 2 saat sreyle
sinterlenmilerdir. % 40 Mg ieren kompakt sinterleme esnasnda toplam Mg miktar % 50 olacak ekilde ekstra Mg
koruyucu olarak ilave edildikten sonra sinterlenmitir. Oda scaklndan 1100 Cye stma hz 10 C/dak olarak
sabit tutulmutur. Sinterleme sonrasnda pota frnn souk blgesine ekilerek yaklak 60-75 C/dak bir hzda
numunelerin oda scaklna soutulmalar salanmtr.
ekil 2. TiNi tozuna ait (a) SEM grnts ve (b) XRD paterni.
Tozlarn parack boyut dalmlar Malvern Mastersizer 2000 cihaz ile belirlenmitir. TiNi tozda ve sinterlenmi
gzenekli TiNi alamlarnn i yapsnda oluan fazlar belirlemek iin Rigaku D/Max 2200/PC model XRD cihaz
kullanlmtr. Toz morfolojileri ve mikroyap incelemeleri Noran System 6 enerji dispersiv spektrometresine sahip
Jeol JSM 6400 taramal elektron mikroskobu (SEM) kullanlarak gerekletirilmitir. TiNi kpklerin gzeneklilikleri
Arimet yntemiyle belirlenmitir.
489

ekil bellek davran 10X10 mmlik silindirik numuneler kullanlarak 30 kN kapasiteli Instron 3367 mekanik test
cihaz ve bu cihaza ait ekstensometre yardmyla belirlenmitir. Sv azotta 5 dak bekletilen farkl gzenek miktarna
sahip numuneler (% 100 martensit elde etmek iin) daha sonra oda scaklnda % 2 gerinime kadar basma yklemesine maruz braklmtr. Yk boaltldktan sonra numuneler yaklak 100 Cde kaynamakta olan saf su ierisinde martensit-stenit dnmn salamak iin 5 dak sreyle tutulmutur. Serbest ekil kazanm numunelerin
yksekliinin soutma ve stma sonras llmesiyle hesaplanmtr. Bu lmler 1m hassasiyetli bir mikrometre ile yaplmtr. Ayn prosedr ayn numuneler kullanlarak % 4, 6 ve 8lik gerinimler iin de tekrarlanmtr.
retilen TiNi kpklerin ve balang TiNi alam tozunun dnm scaklklar Perkin Elmer Diamond model DSC
kullanlarak +150 C ile -60 C scaklk aralnda yaplan 10 C/daklk stma ve soutma dnglerinden tesbit edilmitir. Referans malzeme olarak indiyum kullanlmtr. Numuneler sl dengenin salanmas iin stma ve soutma
esnasnda, limit scaklklar olan 150 ve -60 Cde srasyla 2 ve 5 dak bekletilmitir. Faz dnm scaklklar, ikinci
stma ve soutma erilerine ASTM F2004-05 standardnda [31] verilen prosedr uygulanarak tespit edilmitir.
3.1. Mikroyap
ekil 3de sinterlenmi % 53 gzenekli TiNi kpn XRD diyagram ve SEM grnts verilmitir. retilen numunelerin oda scaklnda martensit ve stenit fazlarndan olutuklar bulunmutur. Sinterleme sonras kullanlan tozlarla kyaslama yapldnda i yaplarn deimedii ve ayn kald gzlenmitir. Ayrca istenmeyen ikincil fazlarn,
oksit ya da karbon bileiklerinin olumad da gze arpmaktadr.
ekil 3. Sinterlenmi % 53 gzenekli TiNi kpe ait (a) XRD paterni, (b) SEM grnts.
3.2. Serbest ekil Geri Kazanm
% 53 gzenekli TiNi kpn oda scaklnda elde edilen gerilim-gerinim erileri ekil 4te verilmektedir. Uygulanan btn gerinim miktarlarnda farkl gzenek oranlarna sahip dier kpklerin davran da benzer olmutur.
lk etapta elastik deformasyon gsteren kpkler gerinimin artmasyla birlikte ikizlenmeye maruz kalarak dorusala yakn bir dnm gstermilerdir. Ykn boaltlmasyla birlikte uygulanan gerinimin ok az bir ksmnn geri
kazanld ekil 4ten net bir ekilde grlmektedir. Maksimum basma dayanlar % 53 gzenekli kpk iin 55
MPa iken % 59 gzenekli kpk iin 30 MPa civarndadr. Daha yksek gzenekli kpklerin dayancysa olduka
dk olmutur. Elastik modl deerleri de ok dk olan kpklerde en dk gzenekli kpk iin bu deer 1
GPa olarak hesaplanmtr. Mekanik zelliklerin olduka dk olmasnn nedeni ksmi sinterleme sonras yapda
kalan mikro-gzeneklerin varl, balang tozlarnn byk boyutlu olmas ve kompaktlarn sinterleme scaklna
stlrken ekil geri kazanm gstermeleri ile aklanabilir.
TiNi kpkler dk mekanik zellikler gsterse de olduka iyi ekil bellek etkisi sergilemilerdir. Martensit faznda
iken uygulanan gerinim sonras stenit biti scaklnn zerine stlarak salanan gerinim kazanm miktarlar %
olarak ekil 5de gsterilmitir. % 53 ve % 59 gzenekli kpklerde uygulanan gerinimin yaklak % 90 ve fazlas
geri kazanlrken daha yksek gzenekli numunelerde bu deer % 78e kadar azalmtr. Dk gzenekli nu-
490

munelerdeki gerinim kazanm miktar uygulanan gerinime daha az bal iken gzenekliliin artmasyla birlikte bu
bamllk daha duyarl bir hale gelmi ve % 73 gzenekli numunelerde uygulanan gerinimin artmasyla birlikte ekil
geri kazanmnda ciddi bir azalma gzlenmitir.
ekil 4. % 53 gzenekli TiNi kpn oda scaklndaki gerilim-gerinim erileri.
ekil 5. Geri kazanlan gerinimin uygulanan maksimum gerinim ve gzeneklilikle deiimi.
3.3. Martensitik Dnm Scaklklar

ekil 6da TiNi tozun ve gzenek miktar % 53-73 arasnda deien TiNi kpklerin DSC erileri sunulmaktadr.
Dnm scaklklarnn en yksek gzenekli numune dnda artan gzenek miktaryla daha yksek scaklklara
doru kayma eilimi gsterdikleri btn numunelerin stma-soutma erilerinden aka grlmektedir. Balang
tozlaryla kyaslandnda, gzenekli malzemelerde sz edilen bu kayma miktarlarnn Ms scakl iin 12-19 C ve
Af scakl iin 15-25 C olduu belirlenmitir. Pik dnm scaklklarnn da benzer bir kayma eilimi gsterdii
yine ayn ekilden ve izelge 1den izlenebilmektedir.
Dnm slar TiNi kpklerde hacimli TiNi alamlaryla benzerlik gstermektedir. retilen TiNi kpks malzemeler kimyasal homojenlie sahip olduundan, yani Ti-Ni ikili sistemindeki ikincil intermetalik fazlar bulunmadndan, dnm scaklklarndaki artn kkeni gzenek miktarna, Ti3Ni4 faznn kelmesine ya da proses esnasndaki olas oksitlenmeye atfedilebilinir. Fakat bu bileimdeki TiNi alamlarnda Ti3Ni4 faz oluumu grlmemektedir
[1,3], kald ki bu faz XRD sonularnda da grlmemitir. Bu almada retilen TiNi alam ierisindeki gzenekler
kresel ekilde olduklarndan lokal gerilmeler yaratmayaca iin gzenekliliin de dnm scaklklar zerinde
etkisi olmamas gerekir. Geriye sinterleme esnasnda numunelerin oksitlenme derecelerinin farkl olmas nedeniyle
dnm scaklklarnn deimesi seenei kalmaktadr. Bilindii gibi TiNi alamlarnda oksijen miktarnda % 1
oranndaki bir art dnm scaklklarnda 100 C de yol amaktadr [1].
ekil 6. Farkl gzeneklere

sahip TiNi alamlarnn DSC
erileri.
491

Bu almada, gzenekli malzemelerin retiminde boluk yapc olarak kullanlan magnezyum, sinterleme srasnda
indirgeyici bir atmosfer yarattndan, balang tozlarnn kompozisyonuna bal olarak sinterleme sonras mikro
yap yine stenit ve martensit fazlar karmndan olumaktadr. TiNi alamlarnda oksijenin znrl dk
scaklklarda 0.045 at.% [1] olduundan yksek oksijen konsantrasyonlar Ti4Ni2O faz oluumuyla sonlanr. Bu oluum srasnda ana fazdaki titanyum atomlar nikel atomlarna kyasla iki kat daha fazla kullanldklarndan oksijenin
varlnda nikelce zenginlemi ana fazda TiNi3 faz belirir. zetle, ok az oksijenli ortamlarda bile TiNi alamlarnn tek faz olarak retilmeleri mmkn olamamaktadr. Termodinamik hesaplamalar gstermitir ki oksijen ksmi
basncnn 1100 Cde 5 10-25 atmden az olmas durumunda TiO2 oluumu engellenebilmektedir. Dier taraftan
ayn scaklkta MgO oluumu iin gerekli oksijen ksmi basnc 10-34 atmdir. Oksijen ekicilii bakmndan yaklaldnda, magnezyum Elingam erisinde kalsiyumun ardndan gelen ikinci elementtir ve titanyumun oksitlerini etkin
bir ekilde indirgeyebilir. TiNi sinterleme atmosferi olarak yksek saflkta argon gaz kullanmak veya vakum artlar
oluturmak oksijen ksmi basncn ancak 10-8 atmosfere kadar drebilir ki hala ok yksek bir deerdir. Titanyum
alamlarnn sinterlenmesinde olas oksijen kaynaklar, koruyucu atmosfer olarak kullanlan gazlar ve balang
tozlarndan gelen yzey oksit katmanlardr. Bu almada sinterleme atmosferindeki oksijenin ortamdan uzaklatrlmas oksijen giderici olarak kullanlan kk boyutlu snger titanyumla yaplmaktadr. Snger boyutlarnn kk
tutulmas olayn kinetiini hzlandrmaktadr, argon gaz ak ise minimumda tutulmaktadr. Balang tozlarnn
yzeyindeki oksijeni indirgemede ise magnezyumun ok etkili olduu gzlenmitir. Alnan bu nlemler sonucunda
alamlarda ikincil faz olumad belirlenmitir. Titanyum alamlar karbrleme ve nitrrlemeye de eilimlidirler
ancak titanyum ve magnezyumun karbon ya da azota olan yksek afiniteleri argon gaznn bu safszlklardan da
arndrlmasn salamaktadr. Ayrca magnezyumun hidrojene kar yksek ekicilii sebebiyle TiNi alamlarnn
olas hidrojenlenmesi engellenmektedir. Dier retim yntemlerinde titanyum ya da magnezyum gibi ortamn ksmi
oksijen basncn dren malzemeler kullanmadklarndan alam tozu dahi kullanldnda oksitlenme ve/veya
ikincil intermetalik fazlarn oluumu kanlmazdr. Ek olarak, elemental tozlar kullanldnda homojen olmayan
kartrmalar difzyon mesafelerinin artmasna ve sonu olarak titanyum ya da nikelce zengin blgeler olumasna
yol aar. zetle, TiNi alamlarnn koruyucu magnezyum atmosferi altinda sinterlenmesi kirlenmelerden arndrlm olmalarn garanti eder.
izelge 1. Sinterlenmi numunelere ait dnm scaklklar ve entalpileri.
Gzeneklilik (%)
Dnm entalpileri
(H, J/g)
Dnm scaklklar (C)

Ms
Mp
Mf
As
Ap
Af
-Hforw
Hrev
TiNi toz
28
20
10
36
50
58
18.3
18.3
53
40
31
20
49
62
73
23.6
23.1
59
43
31
21
50
62
75
22.5
22.7
66
47
34
21
48
68
80
24.2
24.8
73
46
27
13
42
66
83
27.5
24.7
Bunun yannda magnezyumun dnm scaklklarna etkisi, zerinde durulmas gereken nemli bir konudur. Gzenekler eklenen magnezyumlar ile oluturulduundan magnezyum miktarnn ve gzeneklerin dnm scaklklarna etkisi ayndr. Bunun dorulanmas % 40 ve % 50 magnezyum eklenerek retilen % 53 ve 59 gzenekli alamlarn dnm scaklarnn karlatrlmasyla yaplabilir. Bunlarn dnm scaklklar nerdeyse ayndr nk
sinterleme srasnda ayn miktarda magnezyum kullanlmtr. % 40 Mg eklenerek retilen numunelerin kenarna
ekstra Mg ilave edilerek pota ierisinde toplamda % 50 Mg olmas salanmtr. Daha nce de belirtildii zere TiNi
alamlarnda oksijen miktarnda % 1 oranndaki bir art dnm scaklklarnda 100 C de yol amaktadr.
Magnezyumun balang TiNi tozlarndaki oksijeni indirgemesi nedeniyle dnm scaklklarnda bir artma grlmtr. Ayn ekilde eklenen magnezyum miktarnn artmasyla dnm scaklklar grece ykselmitir ta ki %
73 gibi ok yksek bir gzenek oranna ulalncaya kadar. Gzenekliliin ak fazla artmasyla magnezyum buhar
potay daha abuk terketmekte ve bunun sonucunda da dnm scaklklarnda az da olsa bir azalma meydana
gelmektedir.
4. SONULAR
ekil bellek etkisiyle TiNi kpklerde kazanlan gerinim miktarnn artan gzeneklilik ve gerinim ile % 100lerden %
78e kadar azald gzlenmitir. Gzenek miktarnn ayn zamanda geri kazanlan gerinimin uygulanan gerinime
492

duyarll da artrd gzlenmitir. Mg boluk oluturucu yntemiyle retilen gzenekli TiNi ekil bellek alamlarnn gzenek miktarlarnn, dnm scaklklar zerinde dorudan bir etkiye sahip olmad grlmtr. Artan
gzeneklilikle birlikte dnm scaklklarnda grlen artn, eklenen Mg orannn artmasyla birlikte sinterleme
srasnda oluan sv veya gaz magnezyumun gzenekli TiNi alamndan oksijen giderme etkisinin artmasna bal
olduu tespit edilmitir. Gzenekli TiNi alamlarnn neredeyse tam dnm gsterdii grlmtr.
TEEKKR
KAYNAKLAR
1.
2.
Otsuka, K., Wayman, C.M., Shape Memory Materials, Cambridge University Press, Cambridge, UK, 1998.
Buehler, W.J., Gilfrich, J.W., Wiley, R.C., Effect of Low-Temperature Phase Changes on the Mechanical Properties of Alloys near Composition TiNi Journal of Applied Physics, Vol. 34, pp. 1475-1477, 1963.
3. Otsuka, K., Ren, X., Physical Metallurgy of Ti-Ni-based Shape Memory Alloys, Progress in Material Science, Vol. 50, pp. 511-678, 2005.
4. http://www.biyomalzeme.org.tr/haberler.html, Eriim Tarihi: 25.06.2011.
6. Gjunter, V.E., Sysoliatin, P., Temerkhamor, T., Superelastic Shape Memory Implants in Maxillofacial Surgery, Traumatology, Orthopaedics, and Neurosurgery, Tomsk University Publishing House, Tomsk, Russia,
1995.
stanbul, 2010.
press, DOI: 10.1007/s11661-011-0714-z.
9. Bansiddhi, A., Sargeant, T.D., Stupp, S.I., Dunand, D.C., Porous NiTi for Bone Implants: A Review, Acta
Biomaterialia, Vol. 4, pp. 773-782, 2008.
10. Bansiddhi, A., Dunand, D.C., Shape-Memory NiTi Foams Produced by Solid-State Replication with NaF,
Intermetallics, Vol. 15, pp. 1612-1622, 2007.
12. Itin, V., Gyunter, V., Shabalovskaya, S., Sachdeva, R., Mechanical Properties and Shape Memory of Porous
Nitinol, Materials Characterization, Vol. 32, pp. 179-187, 1994.
13. Li, B.Y., Rong, L.J., Li, Y.Y., Gjunter, V.E., Synthesis of Porous Ni-Ti Shape-Memory Alloys by Self-Propagating High-Temperature Synthesis: Reaction Mechanism and Anisotropy in Pore Structure, Acta Materialia,
Vol. 48, pp. 3895-3904, 2000.
14. Yuan, B., Zhang, X.P., Chung, C.Y., Zeng, M.Q., Zhu, M., A Comparative Study of the Porous TiNi ShapeMemory Alloys Fabricated by Three Different Processes, Metallurgical and Materials Transactions, Vol.
37A, pp. 755-761, 2006.
15. Kaya, M., Orhan, N., Kurt, B., Khan, T.I., The Effect of Solution Treatment under Loading on the Microstructure and Phase Transformation Behavior of Porous NiTi Shape Memory Alloy Fabricated by SHS, Journal of
Alloys and Compounds, Vol. 475, pp. 378-382, 2009.
16. Tosun, G., Ozler, L., Kaya, M., Orhan, N., A Study on Microstructure and Porosity of NiTi Alloy Implants Produced by SHS, Journal of Alloys and Compounds, Vol. 487, pp. 605-611, 2009.
Research, Vol. 13, pp. 2847-2851, 1998.
493

22. Zhao, Y., Taya, M., Kang, Y.S., Kawasaki, A., Compression Behavior of Porous NiTi Shape Memory Alloy,
Acta Materialia, Vol. 53, pp. 337-343, 2005.
23. Aydomu, T., Bor, ., Processing of Porous TiNi Alloys Using Magnesium as Space Holder, Journal of
25. Grummon, D.S., Shaw, J.A., Gremillet, A., Low-Density Open-Cell Foams in the NiTi System, Applied Physics Letters, Vol. 82, pp. 2727-2729, 2003.
29. Yuan, B., Zhang, X.P., Chung, C.Y., Zhu, M., The Effect of Porosity on Phase Transformation Behavior of
Porous Ti-50.8 at.% Ni Shape Memory Alloys Prepared by Capsule-free Hot Isostatic Pressing, Material
Science and Engineering A, Vol. 438-440, pp. 585-588, 2006.
30. Li, H., Yuan, B., Gao, Y., Chung, C.Y., Zhu, M., High-porosity NiTi Superelastic Alloys Fabricated by Lowpressure Sintering Using Titanium Hydride as Pore-forming Agent, Journal of Materials Science, Vol. 44,
pp. 875-881, 2009.
31. ASTM F 2004-05, Standard Test Method for Transformation Temperature of Nickel-Titanium Alloys by Thermal
Analysis, ASTM, Philadelphia, PA, 2010.
494

Akm Destekli Sinterleme Yntemi le retilen SiCp Takviyeli

Bronz Matriksli MMKin Karakterizasyonu
Mehmet UYSAL Ramazan KARSLIOLU, Ahmet ALP Hatem AKBULUT,
Sakarya niversitesi, Mhendislik Fakltesi, Metalurji ve Malzeme Mhendislii Blm
54187 Adapazar/SAKARYA mehmetu@sakarya.edu.tr
zet
Bu almada bronz (% 90 Cu - %10 Sn) matriks ierisine farkl boyutlarda(65-52-45 ve 37 m) hacimce %20
takviyeli silisyum karbr (SiC) ilave edilerek metal matrisli kompozit malzeme (MMK) retilmesi amalanmtr.
stenilen bileimdeki tozlar, bilyal deirmen kullanlarak homojen ekilde kartrlp souk olarak basn altnda
ekillendirilmitir. ekillendirilen bu yap yksek akm ve dk voltaj kullanlarak hzl bir ekilde sinterlenmitir.
retilen numunelerin mikro yap, mikro setlik zellikleri ile oluan fazlar ve matriks faz iersindeki partikl dalm
Taramal Elektron Mikroskobu (SEM) kullanlarak incelenmitir.
Anahtar Kelimeler: Akm destekli sinterleme, Bronz, SiC, MMK
Abstract
In this study, a bronze matrix (90 wt. % Cu + 10 wt. % Sn) was reinforced with SiC particles using mechanical alloying and then produced by subsequent rapid current sintering technique. The mechanically ball milled bronze
powders were reinforced with electroless Ni coated 20 vol. % SiC particles with four different particle sizes of 65, 52,
45 and 37m. Microstructure of the bronze /SiC composite produced by these techniques have been investigated
by means of SEM.
Keywords current sintering, bronze, SiC, MMC
1.Giri
Kompozit malzemeler; sergiledikleri mkemmel dayanm zellikleri, farkl birlesim ve geometrilerde retilebilmeleri, yorulma, tokluk, yksek scaklk, oksitlenme ve asnma dayanmlarnn yksek olmas nedeniyle, endstriyel
alanlarda gn getike daha fazla kullanlmaktadr Yksek elastik modl, yksek mukavemet ve yksek anma
direnci gibi zellikleri salamak zere metal alamlarna yaplan ilaveler, partikl eklinde SiC, TiC, B4C ve Al2O3
gibi seramik takviyeler olabilmektedir [1-3].
Gnmzde metal matris kompozit malzeme retiminde sv yntemler, partikl takviyeli metal matris kompozit
sistemlerinde olduka tercih edilen retim prosesleridir. Genel olarak stn dkm kalitesi ve yksek retim kapasitesine sahip olmas ve son ekle yakn retim imkan salamas gibi avantajlar nedeniyle sktrma dkm prosesi
nemli retim tekniklerinden birisidir.[4]
Dk termal genleme katsays, yksek sertlik, yksek elastik modl, iyi elektriksel iletkenlik, yksek termal iletkenlik, iyi anma dayanm gibi zelliklerinden dolay bakr esasl kompozitler, yksek hibrid modll malzemelerin,
elektronik rlelerin, elektrikli yaylarn, birok elektrik/elektronik paralarn, frenlerin, srtnmeye direnli malzemelerin retimi gibi amalar iin kullanlmaktadr [5,6].
Bu almada kompozit malzemeler, bronz matriks iersine farkl boyutlarda hacimce %20 SiC tozlar ilave edilerek,
akm destekli sinterleme yntemi kullanlarak retilmitir. Akm sinterleme ynteminin seilme nedeni, ksa sre-
495

lerde youn ve ekonomik kompozitlerin elde edilmesidir. Yntem ayn zamanda sinterlenen kompozitlerin istenildiinde bir altlk zerine kaplanmasna imkan verebilecek esneklikte olmasndan dolay da tercih edilmitir. retim
prosesi uygulanmadan nce SiC seramik partikllerinin matriks yapya daha kolay girmesini salayacak slatma
artlarn salamak amacyla da akmsz yntemle nikel kaplanmtr. retilen kompozit malzemelerin fiziksel ve
yapsal zelliklerinin tespiti amacyla mikroyap, sertlik ve anma zellikleri incelenmitir.
2.DENEYSEL ALIMALAR
2.1. Malzemeler
MMK malzeme retiminde matriks malzemesi olarak bronz (%90bakr-%10 kalay), takviye malzemesi olarak % 20
hacimce orannda 65, 52, 45 ve 37 m boyutlarnda SiC seramik partiklleri kullanlmtr.
2.2. Seramik Tozlarn Akmsz Yntemle Nikel Kaplanmas
Kompozit malzeme retiminde, metal ile seramik partikller arasndaki arayzey byk sorun oluturmaktadr. Bu
ara yzey sorununu ortadan kaldrabilmek iin metal ile seramik arasndaki slatabilirlii arttrmak gerekmektedir.
Metal ile seramik partiklleri arasndaki slatabilirlii gelitirmek iin birka yol vardr. Seramik partikllerin zerini
metal ile kaplamak bunlardan biridir. Yaplan bu almada bazik zeltide ve akmsz kaplama artlarnda SiC
seramik partikllerinin yzeyleri Ni kaplanmtr.
ekil 1. Akm sinterleme deney dzeneinin grnts [4]

2.2.1. Kaplama ncesi Uygulanan n Yzey lemleri
Seramik Tozlarnn Temizlenmesi: Kaplama yaplacak SiC seramik tozlarnn yzey zellikleri kaplamann verimlilii
asndan ok nemlidir. Bu yzden seramik tozlarn kaplama ncesi yzeyleri ultrasonik temizleme cihaznda
aseton zeltisi iinde yaplmtr.
Hassaslatrlma lemi: Bu ilemden ama toz yzeylerinde kalay iyonlarnn adsorbsiyonudur. Seramik tozlar
aseton ile temizlendikten sonra SnCl2 zeltisinde belirli srelerde tutulmak suretiyle hassaslatrma ilemi uygulanmtr.
Aktivasyon lemi: Bu ilem genellikle hassaslatrma ilemi akabinde uygulanmaktadr. Bu ilem srasnda tozlar
aktivasyon amacyla PdCl2 zeltisinde belirli bir sre bekletilmektedir. Bu esnada toz yzeylerinde kalayn ykseltgenmesi srasnda indirgenen Pd, ok ince bir tabaka oluturmaktadr. Tozlar daha sonra 90 oCde etvde kurutula-
496

rak kaplamaya hazr hale getirilmitir.

2.2.2.Seramik Tozlarnn Kaplanmas lemleri
SiC seramik tozlarnn kaplanmasnda kullanlan akmsz nikel kaplama banyosu bileimi ve parametreleri Tablo
1de verilmitir. Kaplamalar, pH 8 olan alkali zeltide ve 70 0C scaklkta gerekletirilmitir.
Tablo 1 Aksz kaplama parametreleri
Banyo bileenleri ve parametreleri
Datalar
NiCl2
(45.0 g/l)
Na-citrate (C6H5Na3O7. 2H2O)
(100.0 g/l)
NH4Cl
(50.0 g/l)
sodium hypophosphite
8.0 g/l)
pH
Scaklk
70oC
Sre
10 dak
Partikl miktar
10 g/l
2.3. Kompozit Malzeme retimi

Bronz matrisli kompozit malzeme retimi iin ilk nce, akmsz nikel ile kaplanm SiC seramik tozlar ile bronz tozlar, kartrma ilemine tabi tutulmutur. Farkl boyutlardaki SiC tozlar hacimce % 20 olacak ekilde bronz matriks
iersine ilave edildikten sonra gezegensel deirmende kartrma ilemi gerekletirilmitir. Kartrma ilemi numune/bilya arlka oran 1/15 orannda olacak ekilde WC bilyeler kullanlarak 1 saat sreyle gerekletirilmitir.
Bu ilemden sonra tozlar 300 kg/cm2lik basn altnda 10 dakika sreyle souk izostatik preslenerek ham numuneler elde edilmitir. Akabinde akm destekli sinterleme yntemi ile bronz matrisli, hacimce %20 SiC takviyeli kompozit malzemeler elde edilmitir. ekil 1 de akm destekli sinterleme ynteminin grnts verilmitir. Dzenee
yerletirilen numune 10 dk sreyle 2,0 V altnda ortalama 1000 A akm etkisinde braklarak hzla yksek scakla
karlm ve sinterleme ilemi gerekletirilmitir.
2.4. Kompozit Malzemelerin Karakterizasyonu
retilen bronz alam ve kompozit malzemeler metalografik numune hazrlama teknikleri ile srasyla 600, 800,
1200 lk elmas zmpara kullanlarak kaba ve ince olarak zmparalanmtr. Daha sonra elmas pastalar yardmyla
kaba ve ince parlatma ilemlerine tabi tutulmutur. Metalografik olarak hazrlanan yzeyler daha sonra etanol ile
temizlenmi ve yzeydeki kirlilikler giderildikten sonra tozlarn dalm ve morfolojisinin belirlenmesi iin JEOL JSM
6060LV marka taramal elektron mikroskobu (SEM) ile geri salml elektron dedektr kullanlarak incelenmitir.
Matriksteki zellik deiimlerinin tespiti amacyla retilen kompozitlerin mikrosertlikleri incelenmitir. Leica VMHT
MOT Mikro sertlik cihaznda her bir numune iin en az 5 alandan vickers setlik lmleri yaplm ve 5 lmn
ortalamas alnmtr. lmler 15 saniye sre ile 50 gr yk altnda gerekletirilmitir.
3. Deneysel Sonular
3.1. Mikroyap almalar
3.1.1. Akmsz Nikel Kaplama Numuneleri
Kompozit malzeme retiminden nce SiC seramik tozlarna akmsz yntem ile nikel kaplama yaplmtr. ekil 2de
nikel kaplama yaplmam ve nikel kaplama uygulanm SiC seramik tozlarnn SEM yaplar grlmektedir. SEM
resimlerinden grld gibi SiC seramik tozlarnn zeri nikel ile baarl bir ekilde kaplanmtr. Nikel partiklleri
497

a)
b)
c
seramik tozlarnn yzeyini homojen ekilde kaplam ve tozlarn keskin kelerinde youn olarak birikmitir.
498

ekil 2 a) a) Kaplanmam SiC seramik tozlar b)Ni kaplanm SiC seramik tozlar c) Ni kaplanm SiC seramik
tozlarn EDS analizi
3.1.2. Kompozit Malzemeler
Bronz matrisli kompozit malzemeler, bronz iersine farkl boyutlarda ve %20 orannda SiC takviyesi yaplmak suretiyle ve akm destekli sinterleme yntemi kullanlarak retilmitir. Sinterleme ilemi btn malzemeler iin 1000 A
akm altnda ve 10 dak. sre ile gerekletirilmitir. Farkl boyutlarda SiC ile takviye edilmi kompozit malzemelerin
SEM grntleri ekil 3de verilmitir. Bronz matrisli kompozit malzemelerin mikroyapsal almalarnda SiC seramik partikllerinin bronz matris ierisine homojen olarak daldklar grlmektedir. SiC seramik partikllerin matris
iersine homojen dalmn, SiC partiklleri ile matris malzemesi arasnda arayzey bann iyi olmas ve alam
tarafndan SiC partikllerinin iyi slatabilirlilii salamtr. Ayrca n ilem safhasnda uygulanan, gezegensel deirmen ortamnda yaplan kartrma ileminin etkin ve ideal artlarda yaplm olmas da bu sonu zerinde ciddi etki
dourmutur. Seramik partiklleri ile matris arasndaki arayzeyin grnmnn de ok iyi olduu sylenebilir.
ekil 3 Bronz SiC kompozit malzemelerim SEM grnts a) 65m b) 52 m c) 45 m d) 37 m
3.2. Sertlik lmleri
Numunelerin sertlik lmleri mikro-sertlik cihaznda Vickers sertlik yntemi kullanlarak yaplmtr. Sertlik deerleri, metalografik olarak hazrlanm numunelerden 50 gr yk altnda 15 sn sreyle ve 5 farkl lmn aritmetik
ortalamas alnarak yaplmtr.
ncelenen kompozitlerin sertlik deerleri ekil 4 de verilmitir. Takviye edilen SiC seramik tozlarn boyutlar dtke kompozit malzemenin sertliinde art grlmektedir. Kompozit malzemelerde en yksek sertlik, 37 m partikl
boyutuna sahip SiC seramik tozlarn ilavesiyle elde edilmitir.
Bunun sebebi bronz matrisin iindeki sert SiC seramik partikllerinin bulunmasndan dolay matris takviye faz
arayzeyinde dislokasyon younluunun artmas ve partiklerin dispersiyon sertlemesi etkisi yapmasdr. Ayrca
SiC seramik partikllerinin boyutlarnn dk olmas, daha fazla yzey alannn olumasna ve sertliin daha da
ykselmesine neden olmutur.
499

ekil 4. Bronza SiC ilavesiyle sertlikte meydana gelen deiim

4.Sonular
Akm destekli sinterleme yntemi kullanlarak SiC takviyeli kompozitler ksa srede baarl bir ekilde retilmitir.
Takviye faz ile matris arasndaki ara yzeyi iyiletirmek iin SiC seramik tozlar akmsz yntem ile nikel kaplanmtr. SiC seramik tozlarnn yzeyi homojen bir ekilde kaplanmtr. Bronz matris iersine 65-52-45-37 m boyutlarnda hacimce %20 orann SiC takviye faz ilave edilerek akmla sinterleme yntemiyle kompozit malzemeler
retilmitir. SiC partiklleri matris iersine homojen olarak dalarak baarl bir kompozit retilmitir. Matris iersine
ilave edilen SiC partikllerinin boyutlar dtke kompozit malzemenin sertliinde art meydana gelmitir.
Kaynaklar
1.Ramesh, C.S. , Noor Ahmed R. , Mujeebu M.A., Abdullah M.Z. Development and performance analysis of novel
cast copperSiCGr hybrid composites Materials and Design Vol. 30, pp 19571965 2009
2. Pul M, aln R., Seker U. nfiltrasyon Yntem ile retilmi Al Matrisli MgO Takviyeli Yel_ Kompozitlerin lenebilirliin Asl Kesme Kuvvetleri Asndan Degerlendirilmesi 2. Ulusal Tasarm _malat ve Analiz Kongresi 1112 Kasm
2010 - Balkesir
3. Mindivan H., Kayali E.S SiC takviyeli 2618 Al matrisli kompozitlerin anma davran itdergisi mhendislik
Cilt:6, Say:2, 63-70 Nisan 2007
4. Karsliolu R., Uysal M., Alp A., Akbulut H., Current Actvated Snterng Of Bronze Hybrd Mmcs Coatngs On
Steel Substrates 5th International Powder Metallurgy Conference October 8-12, 2008 Ankara TURKEY
5. Sapate S.G., Uttarwar A., Rathod R.C., Paretkar R.K. Analyzing dry sliding wear behaviour of copper matrix
composites reinforced with pre-coated SiCp particlesMaterials and Design Vol.30 pp 376386 2009
6. Tjong S.C., Lau K.C. Tribological behaviour of SiC particle-reinforced copper matrix Composites Materials Letters
Vol. pp 43. 274280 2000
7. Jianhua Z., Lei L., Bin S., Wenbin Hu Mechanical properties of Cu/SiCp composites fabricated by composite
electroformingMaterials Letters Vol. pp 61 28042809 2007
500

Demir esasl toz alamnda SNTERLEME iLE SERTLETRMe

ileminin mekanik zelliklere ETKS
Hakan HAFIZOLU*, Nuri DURLU*, Ayta ATA**, Hsn ZDURAL**
*TOBB Ekonomi ve Teknoloji niversitesi, Makine Mhendislii Blm, Stz Caddesi No:43, Ankara,
**Toz Metal Ticaret ve Sanayi A.. stanbul Caddesi No:75 Grpnar, Bykekmece, stanbul
ZET
Sinterleme ile sertletirme ilemi ikincil bir sl ileme gerek kalmakszn yksek mekanik zellikler veren dk
maliyetli ve tek aamal bir imalat ilemidir. Bu almada Fe-1,5Cu-0.62C toz alamnda sinterleme ile sertletirme
ileminin mekanik zelliklere etkisi incelenmitir. Numuneler 600 MPa basn altnda preslendikten sonra 1120
Cde sanayi lekli frnda metan gaz ortamnda 20 dakika sre ile sinterlenmitir. Sinterleme ileminden sonra
numuneler iki farkl soutma hznda soutularak, sertletirilmitir. Sinterlenmi numunelerin bir blmne ikincil
bir sl ilem uygulanmtr. Sinterlenmi, sinterleme ile sertletirilmi, sinterlenmi ve ikincil sl ilem uygulanm
numunelerde yaplan mekanik testler ile makro sertlik deerleri, apraz krlma dayanm deerleri belirlenmi ve
numunelerin mikroyaplar incelenmitir. alma, Fe-1,5Cu-0,62C alam iin sinterleme ile sertletirme ileminde
kullanlan soutma hzlarnn yeterli olmadn ve sinterleme ile sertletirme ileminin ikincil sl ileme kyasla daha
dk sertlik deerlerine yol atn gstermitir.
Anahtar Kelimeler: Toz metalrjisi, sinterleme ile sertletirme, sl ilem, demir esasl tozlar
EFFECT OF SINTER HARDENING ON MECHANICAL PROPERTIES OF AN

IRON BASED POWDER ALLOY
ABSTRACT
Sinter hardening is a low cost one step manufacturing process which gives high enough mechanical properties
without the need of a secondary heat treatment. In this study, the effect of sinter hardening on the mechanical
properties of Fe-1,5Cu-0,62C powder alloy was investigated. Samples were pressed under 600 MPa and sintered at
1120C under methane for 20 minutes. After sintering, sinter hardening was done under two different cooling rates.
Some of the sintered samples were heat treated as a secondary operation. The macrohardness and transverse
rupture strength values of the sintered, sinter hardened, sintered and heat treated samples were determined.
Microstructural analysis of the samples were done with optical and scanning electron microscopy. The study show
that for the alloy with the composition Fe-1,5Cu-0,62C with the cooling rates utilized one step sinter hardening
process did not improve the hardness of the samples in comparison to the sintered and heat treated samples.
Key Words : Powder metallurgy, sinter hardening, heat treatment, iron based powders
1. GR
Sinterleme ile sertletirme ilemi son zamanlarda nemi artan, dk maliyetli ve yksek performansl para
imalatnda kullanlan bir imalat tekniidir [1]. Sinterleme ile sertletirme ileminin geleneksel sinterleme ve sonrasnda
yaplan ikincil sl ileme kyasla eitli avantajlar bulunmaktadr. Bunlardan ilki, sinterleme ile sertletirme ilemi
uygulanan paralarda ikincil bir sl ileme gerek kalmamas nedeni ile retim maliyetlerinin dmesidir. lemin
501

dier bir avantaj, sinterleme ile sertletirilen paralarda su verme ilemi ile sertletirilen paralara kyasla daha az
boyutsal deiimin gzlenmesi ve imalat ileminin kolaylamasdr [2]. Geleneksel sinterleme ve ikincil sl ilemde
paralar ya banyosunda soutulmaktadr. Sinterlenmi paralarn gzenekli olmas, soutma ilemi srasnda
yan gzeneklere szmasna neden olmaktadr. Yan gzeneklerde birikmesi ve sonrasnda belirli bir scaklkta
uzaklatrlmamas mekanik zellikleri olumsuz etkilemektedir. Sinterleme ile sertletirme ileminde soutma
ileminin sinterleme frn iinde yaplmas bu tr sorunlarn oluumunu engellemekte ve dk maliyetli yksek
performansl para retimine yol amaktadr.
Sinterleme ileminden sonra yaplan zellik artrc sl ilemlerde para yzeyinde veya tm para kesiti boyunca
menevilenmi martensitli mikroyaplarn elde edilmesi esas amatr [2]. Sinterleme ile sertletirme ileminde
martensitli mikroyaplar oluturmak iin sinterleme ilemi sonrasnda srasnda soutma hznn ayarlanmas
gerekmektedir. Soutma hznn martensit oluumu iin gerekli dzeyde olmas, i parasnn kimyasal bileimi
ve ktlesi ile ilgili olup, bu hz 900-425 C aralnda genellikle 1-10C/sn olarak belirtilmitir [1]. Sinterleme ile
sertletirme ileminde soutma hzn etkileyen eitli unsurlar bulunmaktadr. Para geometrisi, frn tasarm,
soutucu akkann s kapasitesi, paradaki gzeneklilik miktar gibi unsurlar soutma hzn etkilemektedir.
Sinterleme ile sertletirme ileminde, soutma hz dnda alamlama elementlerinin paralarn sertleebilirliini
artrmas asndan nemi byktr. Alam elementleri, srekli souma dnm diyagramlarnda (CCT) martensitli
dnm iin gerekli soutma sresini artrarak, daha uzun bir srede martensit oluumu salamaktadr [3].
Sertleebilirlii artrmak iin kullanlan alam elementleri Mn, Cr, Si, Mo, Ni, C, Cu olarak gsterilebilir. Ni, Mo, Cu
elementlerinin oksijen ile tepkimeye girme eilimleri az olduu iin sertleebilirlii arttrmas asndan en yaygn
kullanlan alamlama elementleridir. Karbon, sertleebilirlii dier alam elementlerine kyasla daha dk oranda
artrmaktadr. Alam elementi olarak karbon kullanld taktirde bu element sadece oluan martensitin sertliini
artrmaktadr. Alam elementlerinin yksek miktarda kullanlmas tozun sktrlabilirliini azaltrken ilemdeki
maliyetlerin artmasna neden olur [4]. Bu nedenle, son zamanlarda soutma yaplacak paralar ile soutucu akkan
arasndaki s iletiminin artrlmas amalanmtr. Daha hzl soutma, parada istenilen zelliklerin olumas iin
gerekli koullardan biridir. Yksek hzda soutma ilemi, endstriyel frnlarda bandn daha hzl almasn ve
retimin artmasn salar. Sertleebilirlii etkileyen bir dier unsur da stenit tane boyutudur. stenit tane boyutu
arttka tane snr azalacandan, tane snrlarnda oluan prlit oluumu zorlaacaktr. Sertlii dk olan prlitin
olumamas parann sertleebilirliini olumlu bir ekilde etkilemektedir.
Toz metalurjisiyle retilmi paralarda, gzeneklilik mekanik zellikleri etkilemektedir [5]. En nemli deiken toplam
gzeneklilik miktardr ve parann nihai younluu gzeneklilik hakknda fikir vermektedir. Bir dier deiken ise
gzeneklerin geometrisidir. Geni ve dzensiz gzenekler mekanik zellikleri olumsuz etkilemektedir.
Bu almann amac, Fe-1,5Cu-0,62C toz alamnda sinterleme ile sertletirme ileminin ve sinterleme ileminden
sonra yaplan ikincil sl ilemin mekanik zelliklere etkisinin incelenmesidir.
2. DENEYSEL YNTEM
Bu almada, Hganas firmasnn su atomizasyon yntemiyle rettii saf demir tozu (ASC100.29) kullanlmtr.
Tozun tane boyutu 50-150 mikron arasnda deimektedir. Saf demir tozuna arlka %1,5 orannda bakr (toz
boyutu 149 mikron) ve %0,62 orannda grafit tozu ilave edilmitir. almada kullanlan toz bileimi ve zellikleri
izelge 1 de verilmitir. Demir esasl tozlarda bakr sinterlenmi paradaki boyutsal deiimi en aza indirmek iin
kullanlr [6] . Grafit ise hem sertlii arttrmak hem de yalayc etkisi yaratmak iin kullanlan bir alam elementidir.
Toz karmna yalayc olarak %0,5 MnS ve balayc olarak %0,9 amide mumu eklenmitir.
izelge 1. Fe-1,5Cu-0,62C tozunun bileimi ve zellikleri.
Miktar
Grafit
Cu
Fe
Grnr younluk
Akkanlk
% arlk
0,62
1,5
kalan
3,00 g/cm
35 s/50 g
Numuneler 600 MPa basn altnda 60 tonluk Instron marka ekme-basma cihaznda tek ynl preslenmitir.
Presleme ileminden sonra numunelerin ham younluklar 7,07 g/cm3 olarak llmtr. Deneysel almalarda
iki farkl geometride numune preslenmitir. Bu numuneler; nokta eme deneylerinde kullanlmak zere preslenen
ubuk numuneler ve makro sertlik, mikro sertlik ve mikroyap almalar iin kontrol numunesi olarak preslenen
502

pelet numunelerdir. 16 mm apl pelet numunelerde 8 gr toz kullanlrken ubuk numunelerde yaklak olarak 17 gr
toz kullanlmtr. Pelet numunelerden er tane, ubuk numunelerden TS 4222 EN ISO 3325 standartlarna uygun
olarak beer tane hazrlanmtr.
Preslenen numunelerin sinterleme ilemleri ve sinterleme ile sertletirme ilemleri Tozmetal firmasndaki frnda
gerekletirilmitir. Sinterleme ilemlerinde sinterleme ortam olarak metan gaz kullanlmtr. Frnda; ilk olarak
700C de yalayc ve balayc giderme ilemi yaplm, daha sonra numuneler 1000Cye, 1050Cye ve
1120Cye kademeli olarak stlarak sinterleme ilemi gerekletirilmitir. Numuneler 1120Cde 20 dakika sre
ile sinterlenmilerdir. Sinterleme ileminden sonra yava soutma koullar 5 Hz olarak ayarlanm, sinterleme ile
sertletirme ilemleri ise orta hzda soutmada 15 Hz ve hzl soutmada ise 35 Hz olarak gerekletirilmitir. Frnn
bant hz 200 mm/dak. olup her bir evrim 1 saat 20 dakikada tamamlanmtr.
Sinterleme ilemlerinden sonra numunelerin apraz krlma dayanmlar, makrosertlik ve mikrosertlik deerleri
belirlenmitir. apraz krlma dayanm deerleri 5 tonluk Instron ekme-basma cihaznda TS 4222 EN ISO 3325
standartlarna uygun olarak gerekletirilmitir.
Basma hz olarak 1 mm/dak. seilmi, numune boyutlar; 31,8x12,8x6 mm olarak belirlenmitir. Makro sertlik
lmleri Wilson-Wolpert cihaznda Brinell yntemi ile (HB), mikrosertlik lmleri Buehler cihaznda Vickers
yntemi ile (HV0,1) yaplmtr. Mikroyap almalarnda dalayc zeltisi olarak %3lk nital zeltisi kullanlmtr.
Sinterlenmi numunelerin bir blm karbonitrrleme ikincil sl ilemine tabi tutulmutur. Karbonitrrleme ilemi
850Cde, C miktarnn 0,65 ve NH3 miktarnn 0,5 olduu durumda 120 dakika sre ile gerekletirilmi, sonraki
aamada scaklk 810C ye drlm ve numunelere 30 dakika sre ile karbon ve amonyak nfuz ettirilmitir. Son
aamada, numuneler 100Cde bulunan ya banyosunda soutulmu ve 85C de ykama ilemi gerekletirilerek
ilem tamamlanmtr.
3.DENEYSEL SONULAR ve TARTIMA
3.1.Mekanik zellikler
Sinterlenmi, sinterleme ile sertletirilmi, ve ikincil sl ilem uygulanm numunelerin mekanik zellikleri izelge
2 de verilmitir. Sinterlenmi numunelerin sertlik deeri 144 HB olarak llmtr. Sinterleme ileminden sonra
iki farkl soutma hznda yaplan sinterleme ile sertletirme ilemi sertlik deerlerinde az bir arta yol am ve
numunelerin sertlik deerleri orta hzda yaplan soutma ilemi iin 160 HB, yksek hzda yaplan soutma ilemi iin
167 HB olarak llmtr. Orta ve yksek hzda yaplan sinterleme ile sertletirme ileminde sertlik deerindeki
artn az olmas Fe-1,5Cu-0,62C alam iin soutma hznn yeterli olmadn ve buna bal olarak martensit faz
oluumunun gereklemediini gstermektedir.
Sinterleme ileminden sonra yaplan ikincil sl ilem ile (karbonitrrleme), numunenin sertlii artm ve sertlik deeri
246 HB olarak llmtr. Sertlik deerindeki artn nedeni karbonitrrleme ilemi srasnda numune yzeyinde
meydana gelen bileim deiimi ve su verme ilemi sonrasnda numune kesiti boyunca oluan martensit fazdr.
kincil sl ilem uygulanm numunenin kesit boyunca mikrosertlik deiimi ekil 1de verilmitir.
izelge 2. Sinterlenmi ve sinterleme ile sertletirilmi numunelerin mekanik zellikleri.
Numune
(Fe-%2Cu-%1,5Mo-%0,7C)
Makrosertlik
(HB)
apraz Krlma Dayanm (MPa)
Sinterleme (1120C, 20dak.)
1443
94326
Sinterleme (1120C, 20dak.) ve

orta hzda soutma
1604
91838

yksek hzda soutma
1673
97832

+ ikincil sl ilem
24658
93236
503

Kenar blgelerde soutma hznn yksek olmasna ve martensit faznn oluumuna bal olarak yksek sertlik
deerleri (700 HV0,1) elde edilirken, orta blgede sertleebilirliin dk olmasna bal olarak dk sertlik
deerleri (350 HV0,1) elde edilmitir.
ekil 1. Sinterleme sonras ikinci sl ilem uygulanm numunenin kesiti boyunca mikro sertlik deiimi.
Numunelerin apraz krlma dayanm deerlerinin 920-980 MPa arasnda deitii gzlenmitir (izelge 2). Fe-Cu
alamlar zerine yaplan bir almada, 1150Cde amonyak gaz altnda 60 dakika sre ile sinterlenen Fe-2Cu
alamnn sinterlenmi dayanm deeri 420 MPa olarak llmtr [7]. Fe-2Cu-0,6P alam zerine yaplan bir
almada numuneler 1120Cde endogaz altnda sinterlenmi ve numunelerin apraz krlma dayanm deerleri 689
MPa olarak llmtr [8]. Bu tr alamlar zerine yaplan dier bir almada Fe-3Cu-0,3C-0,28P alamnn
sinterlenmi dayanm deeri 880 MPa olarak llm ve C miktarnn artna bal olarak dayanm deerinin
artt belirlenmitir [9].
3.2.Mikroyap ncelemeleri
ekil 2de sinterlenmi numunenin optik mikroskop ve taramal elektron mikroskop grntleri verilmitir. Mikroyap
tektoid ncesi oluan ferrit fazndan (ak faz) ve ince perlitten olumaktadr. Sinterleme ileminden sonra yksek
hzda soutulan numunenin optik ve taramal elektron mikroskop grntleri ekil 3te verilmitir. Mikroyap yava
ve orta hzda soutulan numune mikroyaplarna benzer ekilde ferrit (ak faz) ve ince perlitten olumaktadr.
Mikroyapda soutma hznn artmasna bal olarak ferrit miktar azald, ince perlit miktarnn ise artt
gzlenmitir.
ekil 2. 1120C de metan gaz ortamnda 20 dakika sinterlenen ve yava soutulan numunenin ferrit ve perlit
ieren mikroyaplar.
504

ekil 3. 1120C de metan gaz ortamnda 20 dakika sinterlenen ve yksek hzda soutulan numunenin ferrit ve
perlit ieren mikroyaplar.(a) 100x, (b) 3000x
Sinterleme ileminden sonra yaplan ikincil sl ilem numunenin sertlik deerinde arta yol amtr. Bunun
nedeni karbonitrrleme ilemi ile numunenin yzey blgesinde salanan bileim deiimi ve karbonitrrleme
ileminden sonra yaplan hzl soutma ilemine bal olarak martensit faznn oluumudur. Numunenin dalanm
mikroyapsndan elde edilen mikroyap grntleri ekil 4te verilmitir. ekil 4.ada verilen optik grnts sl
ilem sonrasnda karbonitrrleme ilemi ile oluturulan sertletirme derinliini, ekil 4.bde verilen optik mikroskop
grnts martensit mikroyapsn gstermektedir.
ekil 4. 1120C de 20 dakika sinterlendikten sonra sl ilem uygulanm numunelerin mikroyap grntleri. (a)
100x , (b) 1000x
4.SONULAR
Bu almada demir esasl Fe-%1,5Cu-%0,62C toz alamnda sinterleme ile sertletirme ileminin mekanik
zelliklere etkisi incelenmitir. ki farkl soutma hznda yaplan sinterleme ile sertletirme ileminin, sinterleme
sonrasnda yaplan ikincil sl ileme kyasla istenilen dzeyde sertlik artna yol amad belirlenmitir.
TEEKKR
Bu alma TOBB Ekonomi ve Teknoloji niversitesi ve Tozmetal A. firmasnn katklar ile gerekletirilmitir.
Taramal elektron mikroskop almasndaki katklarndan tr Cengiz Tan ve Serkan Ylmaza teekkr ederiz.
5.KAYNAKLAR
[1] Hatami S., Malakizadi A., Nyborg L., Wallin D., Critical aspect of sinter-hardening of prealloyed Cr-Mo steel,
Journal of Materials Processing Technology 2010 1180-1189.
505

[2] James W. B., What is Sinter Hardening, International Conference on Powder Metallurgy & Particulate
Materials, May 31-June 4, 1998, Las Vegas, Nevada, USA.
[3] Rutz H.G., Graham A.H., Davala A.B., Sinter-Hardening P/M Steels, International Conference on Powder
Metallurgy & Particulate Materials, June 29-July 2, 1997, Chicago, IL USA.
[4] Blais C., Serafini Jr. R. E., LEsperance G., Effect of Hydrojen Concentration in Cooling Zone on Sinter
Hardening, International Journal of Powder Metallurgy, Volume:41, No::4, pp. 33-41, 2005.
[5] Staffelini G., Fontanari V., Hafez A., Benedetti M., Tensile and Fatigue Behaviour of Sinter Hardened Fe-1.5Mo2Cu-0.6C Steels, Powder Metallurgy, Volume:52, No:4, pp. 298-303, 2009.
[6] etinkaya ., Karbon Katkl Alaml Demir Tozu Peletlerinin Sinterleme Sonras zellikleri, Yksek Lisans
Tezi, stanbul niversitesi F.B.E., 2005.
[7] Phadke B., Relationship Between Transverse Rupture Strength and Hardness of P/M Fe-Cu Alloys, The
International Journal of Powder Metallurgy and Powder Technology, Volume: 17, No:1, pp.37-43, 1981.
[8] Avar E., Durlu N., Ata A., Bozac C., zdural H., Demir Esasl Toz Metal Paralarn Sinterleme ile Birletirilmesi,
Gazi niversitesi Mhendislik-Mimarlk Fakltesi Dergisi, Volume:25, No:4, 713-718, 2010.
[9] Kohno T., Koczak M.J., Rajagopalan V., Nishino Y., Sintering Improvements in Strength and Dimensional Control
Utilizing Eutectic Phosphide Additions in Iron-Copper-Carbon Alloys, Modern Developments in Powder
Metallurgy, Volume 15, pp 521-540, 1985.
506

CH4 ATMOSFERNDE NANOKRSTAL NKEL OKST TOZUNUN

ZOTERMAL NDRGENMES
Melek CUMBUL ALTAY, erafettin EROLU
stanbul niversitesi, Mhendislik Fakltesi, Metalurji ve Malzeme Mhendislii
Blm, 34320, Avclar, stanbul, mcumbul@istanbul.edu.tr, seref@istanbul.edu.tr
ZET
Nanokristal nikel oksit tozunun reaksiyon davran farkl scaklk (1000-1300 K) ve sre iin saf metan altnda
allmtr. Nikel oksit toz ieriinin tanmlanmasnda DTA/DSC-TG, FTIR ve XRD tekniklerinden yararlanlmtr.
Nikel oksit tozunun sadece NiO fazn ierdii XRD analiz ile ortaya konulmutur. Enstrmantal analiz, az miktarda
Ni(OH)2xH2O faznn da orijinal nikel oksit tozda mevcut olduunu gstermitir. Arlk lmleri, Ni:O orannn
2:3 olduunu belirtmitir. Oksit tozu 1200 K de 5 dak iinde saf metan tarafndan Ni e indirgenmektedir. Artan scaklk
ve sreyle serbest C da olumaktadr. Bu sonular, yksek scaklklarda (1100-1300 K) termodinamik analiz sonularyla kalitatif olarak uyum iinde bulunmutur.
Anahtar Kelimeler: Nanokristal toz, Nikel oksit, Metan, ndirgenme
ISOTHERMAL REDUCTION OF NANOCRYSTALLINE NICKEL OXIDE

POWDER UNDER CH4 ATMOSPHERE
ABSTRACT
Reaction behavior of nanocrystalline nickel oxide powder was studied under pure CH4 atmosphere at different temperatures (1000-1300 K) and time. DTA/DSC-TG, FTIR and XRD techniques were employed for the determination
of contents of nickel oxide powder. Nickel oxide powder consisted of only NiO phase as revealed by XRD. Instrumental analysis showed that a small amount of Ni(OH)2xH2O phase is also present in the original powder. Weight
measurements indicated that the ratio of Ni to O is 2:3. Oxide powder was reduced to Ni at 1200 K within 5 min
under pure CH4 atmosphere. Free C was also observed with increasing temperature and time. These results were
found to be qualitatively in agreement with those of thermodynamic analysis at high temperatures (1100-1300 K).
Keywords: Nanocrystalline powder, Nickel oxide, Methane, Reduction
1. GR
Nano malzemeler, yeni malzemelerin bir tr olarak, geleneksel bulk (yn) malzemelere gre boyut etkisi nedeniyle stn fiziksel ve kimyasal zellikler sergilemekte ve birok alanda geni potansiyel uygulama alanna
sahip olmaktadr. 1990 lardan beri nano lekli bilim ve teknoloji, kimyasal g kaynaklar alanna artan bir ilgiyle
odaklanmtr [1]. Gei metal oksiti olan nikel oksit (NiO) ise NaCl tipi antiferromanyetik yar iletken zellie sahip
olmasndan dolay birok aratrmann konusu olmutur. NiO in dikkat eken zellikleri; yksek dayankllk ve
elektrokimyasal kararllk, dk malzeme maliyeti, periyodik karallk ve geni yaylma optik younluu asndan
umut verici iyon depolama malzeme olmas ve eitli retim tekniklerine olanak salamasdr. NiO, solar termal
emici, fotoelektroliz ve elektrokromik cihazlarda katalizr olarak potansiyel kullanm alanna sahiptir [2]. Ayrca NiO,
karbon nanotp (KNT) sentezinde katalizr hammaddesi olarak da kullanlmaktadr [3].
KNT sentezi iin ark dearj, lazer kazma ve kimyasal buhar biriktirme (KBB) yntemleri en sk kullanlan yntemlerdir [4]. Ark dearj ve lazer kazma yntemleri, yksek scaklklarda kat karbon kaynaklarnn buharlamasyla
507

oluan karbon atomlarnn younlamas, KBB yntemi ise genellikle hidrokarbon gazn (C2H2, CH4, C2H4 vs.)
katalizr partikllerin yzeyinde paralanaca reaksiyon odasna tanmas temeline dayanmaktadr [5, 6]. KNT
morfolojilerinin sentez srasnda katalizr boyutu ve ekliyle ilikili olduu rapor edilmitir. Katalizr olarak Fe, Co ve
Ni gibi gei metal elementleri KNT lerin bymesinde nemli rol oynamaktadr [6].
KNT sentezinde katalizr olarak kullanlan gei metal oksit tozunun karbon bytlmesindeki katalitik etkisinin
belirlenmesinde hidrokarbon gaz atmosferi altndaki indirgenme davrannn anlalmas byk nem tamaktadr.
Bu almada nanokristal nikel oksit tozunun reaksiyon davran farkl scaklk ve sre iin saf metan altnda izotermal
artlarda incelenmitir. Nikel oksit toz ieriinin tanmlanmasnda birok farkl malzeme karakterizasyon tekniklerinden yararlanlmtr. Ayrca oksit tozun reaksiyon davrannn daha iyi anlalmasna ve indirgenme artlarnn
ngrlmesine yardmc olmas iin NiO-CH4 sisteminde termodinamik analiz de yaplmtr.
2. MALZEME VE YNTEM
Mevcut almada kullanlan deney dzenei (ekil 1) esas olarak SiC stc elementli scak cidarl frn, kuvars tp
(20 mm apnda) ve gaz ak lerlerden olumaktadr. Deneysel almada katalizr hammaddesi olarak 10-20 nm
boyutlarnda % 99,8 safiyette nikel oksit tozu kullanlmtr. Deney ncesi oksit tozu, nem gidermek amacyla 373
K de 15 dak sreyle etvde tutulmutur. zotermal artlarda indirgeme almalar iin ~0,3728 g nikel oksit tozu
almina kaykk ierisinde frnn scak blgesine yerletirilmitir. Daha sonra frn Ar (%99,999) atmosferi altnda
reaksiyon scaklna stlmtr. stenilen scakla eriildiinde saf CH4 (% 99,5) belirlenen gaz ak hz3nda ve
srede sistemden geirilmitir. Reaksiyon sonrasnda tm numuneler,
42,5 cm /dak lk Ar ak debisinde oda scaklna soutulmutur.. Reaksiyon sonras elde edilen rnn arl llmtr. Reaksiyonlarn geliimini anlamak iin rn/giren (balang) arlk oranlar hesaplanarak grafik eklinde
gsterilmitir. Arlk lmleri, 0.0001 g hassasiyetli elektronik hassas teraziyle (Sartorius) yaplmtr. ndirgenme deneyleri 1000-1300 K scaklk aralnda, deiik sre (0-45 dak) ve metan gaz ak (0-70 cm3/dak) artlarnda
allmtr.
ekil 1. Kimyasal buhar biriktirme reaktrnn ematik grnm.

almada kullanlan balang tozu, X nlar difraksiyon analizi (Rigaku D/Max- 2200/PC), Fourier dnml kzltesi spektrometresi (FTIR; Bruker IFS 66/S), termal analiz (DSC/DTA-TG; TA SDT Q600) ve Yksek znrlkl
Geirim Elektron Mikroskobu (HR-TEM; Jeol 2100) kullanlarak karakterize edilmitir. HR-TEM analizinde elektron
difraksiyon paterni ekilmitir. Patern difraksiyon halka oranlar kullanlarak zlmtr. Balang tozunun kristal
boyutu elde edilen XRD paterninden Denklem 1 de verilmi olan Scherrrer forml ile hesaplanmtr.
(1)
Burada, t = ortalama kristal boyutu, = dalga boyu (0,15418 nm), = yar ykseklikteki pik genilii, = difraksiyon asdr.
508

Deneysel almalar neticesinde elde edilen rnlerin faz analizleri XRD yntemiyle, morfolojik incelemeler ise
Taramal Elektron Mikroskobu (SEM Jeol 5600, FEG-SEM Jeol 6335F) kullanlarak gerekletirilmitir. Ayrca,
NiO-CH4 sisteminde termodinamik hesaplamalar serbest enerji minimizasyon yntemiyle [7] 700-1300 K scaklk
aralnda yaplmtr. 700-1000 K iin 71 ve 1100-1300 K iin ise 41 gaz faz bileeni hesaplamalarda kullanlmtr. Bu
sistemde en nemli gaz bileenleri CO, CO2, CH4 ve H2 dir. Kat faz iin 700, 800 ve 900-1300 K de srasyla 6 (C,
Ni, Ni3C, NiO, NiCO3, Ni(CO)4), 4 (C, Ni, Ni3C, NiO) ve 3 (C, Ni, NiO) bileen gz nne alnmtr.
3. BULGULAR
3.1. Oksit tozun karakterizasyonu
Nikel oksit tozunun HR-TEM grnts, elektron difraksiyon paterni ve XRD paterni ekil 2 (a-c) de gsterilmektedir.
ekil 2. Balang oksit tozuna ait a) HR-TEM grnts, b) elektron difraksiyon ve c) XRD paternleri.
Toz, genellikle kresele yakn bir morfolojiye sahip olup llen partikl boyutu ortalama 126 nm dir. Halka
eklindeki difraksiyon paterni, tozun ok kristalli karakterini yanstmaktadr. ekil 2 b de, srasyla merkezden darya doru halkalarn (111), (200) ve (220) dzlemlerine ait olduu tespit edilmitir. Bu sonu NiO in YMK yapda
olduunu gstermektedir. ekil 2 c de verilen tozun XRD paterni YMK yapy teyit etmektedir. Paternden grld
zere difraksiyon piklerinin iddetleri ve difraksiyon alar, NiO in yaynlanm izgileriyle uyum iindedir. Ayrca
toza ait iddetli piklerin yar ykseklikteki genilikleri kullanlarak kristal (tane) boyutu Denklem 1 ile 18 nm olarak
hesaplanmtr. Bu deer retici firma tarafndan rapor edilen ve HR-TEM ile llen deerlere yakndr. Dolaysyla,
partikllerin tek (mono) kristal yapda olduu anlalmtr.
Nikel oksit tozuna ait argon atmosferi altnda elde edilen DSC/DTA-TG diyagramlar ile FTIR analiz sonular ekil 3
(a-c) de verilmitir. ekil 3a da verilen diyagramdan ~380 K de tozun bnyesinden nemin tamamen ayrld endotermik DTA ve DSC piklerinden anlalmaktadr. TG erisinden tozun yaklak olarak % 2,5 nem ierdii belirlenmitir.
Artan scaklkla 520 K ve 576 K de iki endotermik pik gzlenmektedir.
Literatr aratrmas, bu piklerin Ni(OH)2xH2O bileii ile ilikili olduunu gstermektedir [8-11]. Deneysel almada kullanlan tozun az miktarda bu faz ierdii tahmin edilmektedir. ki endotermik pikten birincisinin bileikte bulunan
yapsal suyun uzaklamasyla, ikincisinin ise bileiin Ni(OH)2 nin NiO e dnmesiyle ortaya kt sonucuna
varlmtr. Ayrca, 710 K de grlen kk ekzotermik pikin yapda olmas muhtemel amorf yapnn kristallemesiyle ortaya ktna inanlmaktadr. 1150 K de DSC erisinde daha belirgin grlen geni endotermik pik, NiO in Ar atmosferi
altnda ok az miktarda Ni e dnmesiyle aklanmaktadr.
Bu duruma tekabl eden TGA erisinde dk oranda artan scaklkla arlkta azalma olmakta olup eriilen nihai
arlk deiimi % 88,5 tir. lerideki blmde gsterilecei zere arlk kayb ve XRD analizleri-1bu sonucu desteklemektedir. ekil 3 b de verilen orta-IR spektrumunda 3670-3330 cm da-l1ga saylar arasndaki geni bandn suya ve
Ni(OH)2 e [1,2,8,12-15], ve 1976 cm deki kk keskin bandlarn ise ATR kr-istaline (elmas) [16] ait olduu tespit
edilmitir. Ayrca, 1612 [1,2,8,14] ve 660 cm 1 deki bandlarn su ve Ni(OH)2 den [12-14] kayn-akland tahmin edilmektedir. Dier Ni(OH)2 bandlarnn 1432, 1360 [14] ve 560 cm 1 [11,13,17,18] dalga saylarnda bulunduu tespit
edilmitir. Orta-IR spektrumunda 460 cm- de ortaya kan bandn NiO e ait olduu b1elirlenmitir [1,2,8,13,19,20].
ekil 3 c de verilen uzak IR spektrumunda ise 395 cm- deki geni band, nano kristal NiO ten kaynaklanmaktadr
[17,18].
509

ekil 3. a) Nikel oksit tozuna ait Ar atmosferi altnda elde edilen DSC/DTA-TG diyagramlar b)orta IR ve c) uzak IR
blgesinde ekilen FTIR diyagramlar.
3.2. CH4 atmosferlerinde oksit tozunun izotermal indirgenmesinde scaklk ve srenin toz arlk oranlarna
etkisi
Sabit CH4 gaz ak hznda (13,4 cm3/dak) izotermal artlarda 1000-1300 K scaklk aralnda yaplan deneyler
sonucu elde edilen toz arlk oranlarnn reaksiyon sresiyle deiimi ile 1000 ve 1200 K iin srasyla 15 ve 7,5
dak reaksiyon sresinde CH4 gaz ak hznn arlk oranlarna etkisi ekil 4 (a-b) de verilmitir. ekil 4 a da grld zere 1000 K de arlk zamanla azalmakta ve 45 dak iinde % 71 deerindeki yatay izgiye yaklamaktadr. 1100 K de arlk kayb daha ksa srede gereklemekte ve yaklak 17,5 dak sonra ok az arlk kazanc
grlmektedir. 1200 ve 1300 K de ise arlk oran-zaman erileri arlkta azalmay takip eden art olduunu
gstermektedir. Ancak, 1300 K de arlk oranlar 1200 K e kyasla daha dk seviyelerde bulunmaktadr. Bu scaklklarda (1200-1300 K) arlk kayb dk scaklklara kyasla daha hzl olmaktadr. ekil 4 b de grld zere
1000 K de arlk hemen hemen dorusal bir ekilde CH4 ak hzyla azalmaktadr. 1200 K de ise arlktaki azalmay
art izlemektedir.
ekil 4. a) 1000-1300 K scaklk aralnda reaksiyon sresinin toz arlk oranlarna etkisi, b) CH4 ak hznn 1
000 K de 15 dak ve 1200 K de 7,5 dak sresi sonunda arlk oranna etkisi.
3.3. rnlerin X-nlar difraksiyonu ile faz analizi
ekil 5 (a-d), oksitin deiik srelerde CH4 ile izotermal reaksiyonu sonucu elde edilen rnlere ait XRD paternlerini
srasyla 1000, 1100, 1200 ve 1300 K iin gstermektedir.
510

ekil 5. 13,4 cm3/dak CH4 ak hznda, deiik reaksiyon srelerinde; a) 1000 K, b) 1100 K, c) 1200 K ve d) 1300 K
de elde edilen rnlerin XRD paternleri.
1000 K deki paternlerden balangta numunenin NiO ve eser miktarda Ni fazlarn ierdii, artan reaksiyon sresiyle Ni pik iddetlerinin ykseldii ve NiO e ait olanlarn ise azald grlmektedir. Ayrca, 45 dak sonunda Ni in yannda az
miktarda oksit faz bulunmaktadr. 1100 K de ise 20 dak sonunda oksit tamamen Ni e indirgenerek tek faz olumaktadr.
1200 K de daha ksa srede (7,5 dak) indirgenme tamamlanmaktadr. Daha yksek scaklkta (1300 K) 5 dak sonra
Ni ve NiO fazlar yannda eser miktarda C faz (ekilde gsterilen paternde belirgin deil) grlmektedir. 12,5 dak
sonra ise oksit tamamen Ni fazna dnmektedir. Sre arttka C (002) pik iddeti de artmaktadr. ekil 6, 1200 K
de, 13,4 ve 70 cm3/dak CH4 gaz ak hzlarnda, 7,5 dak reaksiyon sresinde elde edilen rnlere ait XRD paternlerini gstermektedir. Dk gaz ak hznda sadece Ni in, yksek CH4 gaz aknda ise Ni in yannda serbest C
un bulunduu paternlerden grlmektedir.
ekil 6. Deiik CH4 ak hznda elde e3dilen rnlere ait XRD paternleri. artlar: a) 13,4 cm3/dak, b) 70 cm /dak
CH4, 1200 K, 7,5 dak.
3.4. rnlerin morfolojlerinin incelenmesi
CH4 atmosferinde (13,4 cm3/dak) 20 dak lk reaksiyon sonunda 1000 ve 1200 K de elde edilen numunelerin SEM
grntleri srasyla ekil 7 (a-b) de gsterilmektedir. 1000 K de morfoloji, ortalama boyutu 6015 nm olan partikllerden olumaktadr. 1200 K de ise partikl boyutunda biraz art olmakta (ortalama boyut 7916 nm) ve top eklinde
yaplar bulunmaktadr.
ekil 7. SEM grntleri. 13,4 cm3/dak CH4 gaz ak hz, 20 dak srede, a) 1000 K, b) 1200 K de elde edilen rnlere ait morfolojiler.
511

3.5. Termodinamik analiz

Ar altnda stma sonrasnda rnn esas itibaryla NiO ten olutuu tespit edilmitir. CH4 gaz sisteme verilmeden
nce Ar altnda stma yapldndan termodinamik hesaplamalarda Ni:O oran 1:1 alnmtr. NiO-CH4 sistemi iin yaplan termodinamik hesaplamalar sonucunda elde edilen denge kat hal diyagram, denge durumunda oluan rnlerin
(kat ve gaz) miktarlar scaklk (700-1300 K) ve CH4 mol kesrine (nCH4/(nNiO+nCH4) bal olarak ifade ekil 8
(a-c) de grafikler halinde verilmektedir.
ekil 8 a dan da grld zere 700 ile 1300 K aralnda NiO+Ni, Ni, Ni+C olmak zere 3 faz alan mevcuttur.
NiO+Ni faz alan, allan scaklklarda 0-0,2 CH4 mol kesri aralnda bulunmaktadr. CH4 mol kesri 0,2 den yksek
olduunda, Ni tek faz blgesinin olutuu ve artan scaklkla Ni blgesinin geniledii ekilden grlmektedir. rnein, 700 ve 1300 K iin tek faz Ni blgesinin snrlar srasyla 0,2- 0,3 ve 0,2-0,5 CH4 mol kesir aralklarndadr. Bu
snrlarn stnde Ni ile beraber serbest C da oluarak Ni+C faz alan ortaya kmaktadr. Bu alan, 1000 K in altndaki
scaklklarda genilemektedir. ekil 8 b den grld zere allan scaklk aralnda artan CH4 mol miktar ile
NiO miktar azalmakta, 0,2 mol kesrinde Ni ierii % 100 e ulamaktadr. Ni+C faz alannda tm scaklklarda CH4 mol
kesri arttka Ni miktar azalmakta ve serbest C miktar artmaktadr. Ancak, 700 K de C faz 1300 K e kyasla daha
dk CH4 mol kesrinde (0,3) ortaya kmaktadr. ekil 8 c de 700-1300 K de, H2O, CO2, H2, CO ve CH4 sistemde
bulunan nemli gaz bileenleri olup ksm basnlarnn nCH4/(nNiO+nCH4) ile deiimi gsterilmitir. Grafikte gsterilmemi olan miktar az (<10-5 atm) olan gaz bileenler arasnda CH2O2, Ni(OH)2, HO, H, H2CO, CH4O, C2H4
ve C2H6 bulunmaktadr.
ekil 8. a) Scaklk ve CH4 mol kesrine bal olarak denge kat hal diyagram, b) CH4 mol kesrinin kat rn % mol
miktarlarna etkisi, c) rnlerin ksm basnlarnn CH4 mol kesri ile deiimi
rnlerin oluumu iin olas reaksiyonlar kat ve gaz faz bileimlerindeki deiimin incelenmesiyle aklanabilir.
Dk CH4 mol kesirlerinde, Ni+NiO faz alannda, H2O ve CO2 ksmi basnlar H2 ve CO te kyasla daha yksek
olup artan CH4 mol kesriyle miktarlar kademeli bir ekilde azalmaktadr. Buna karlk H2 ve CO ksm basnlar
artmaktadr. Bu durumda oluabilecek nemli reaksiyonlar srasyla dk ve yksek CH4 mol kesirleri iin Denklem
2 ve 3 ile verilebilir.
(2)
(3)
512

Bu reaksiyonlara ilaveten Denklem 4, 5 ve 6 da verilmi olan reaksiyonlarn ortaya kmas muhtemeldir. CH4 ile
H2O ve CO2 arasndaki reaksiyonlar (Denklem 5 ve 6) CO ve H2 miktarlarnn artmasna yol aabilir.
(4)
(5)
(6)
C oluumu iin reaksiyonlar Denklem 4 (CH4 n paralanmas) ve 7 ile ifade edilebilir. Denklem 7 ile verilen Boudouard reaksiyonu 1000 K in altndaki scaklklarda C oluumuna neden olmaktadr. 1000 K zerinde ise reaksiyon
tersine dnerek (CO2, C la reaksiyona girerek) CO oluumuna yol amaktadr. Bunun sonucu olarak kat hal
diyagramnda Ni+C faz alan artan scaklkla daralmakta, yksek scaklklarda ( 1000 K) serbest C sadece CH4 n sl
paralanmasyla olumaktadr.

(7)
Yukarda verilen bilgiler nda NiO-CH4 sisteminde Ni+C oluumu iin genel reaksiyonlar Denklem 8 ve 9 ile
ifade edilebilir.
(8)

(9)
Termodinamik analiz, artan CH4 mol kesriyle NiONiNi+C dnmnn olacan ngrmektedir.
4. TARTIMA
CH4 atmosferi altnda izortermal artlarda oksit tozunda gerekleen arlk deiimleri, esas itibaryla balang tozunun tamamnda Ni:O orann 1:1 olmadn, NiO faz yannda Ni2O3, Ni(OH)2 gibi dier fazlar da ierebileceini
gstermitir. Bahsedilen ilave fazlar X-n difraksiyonunda deiik nedenlerden (amorf yap, faz miktarnn az olmas) tr tespit edilememitir. Ayrca, Ar atmosferinde balangta siyah renkte olan orijinal tozun, arlk orannn
~% 90 olduunda, ak yeile (NiO in tipik rengine) dnmesi bileimde deiimin (oksijen miktarnn azalmas)
olduunun iaretidir. Teorik olarak Ni:O orannn 2:3 ten 1:1 e dt toz arlk oran (% 91,3) grafiklerinde yatay
referans izgisi olarak gsterilmitir. Deneysel sonucun bu deere yakn olmas, balang tozunun oksijence daha
zengin olduunu gstermektedir. Bu gzlemler balang tozunda Ni:O orannn 2:3 olduuna iaret etmektedir.
Ayrca, DTA-DSC-TG ve FTIR analizleri bu sonucu desteklemektedir. Deneysel artlar, kat hal denge diyagramnda
tm scaklklar iin yksek CH4 mol kesirlerine (1 e yakn) tekabl etmektedir. Diyagrama gre denge durumunda
rnlerin Ni+C fazlarndan olumas gerekirken deneysel sonular, 1200 K in altndaki scaklklarda serbest C un
olumadn gstermektedir. Bu durum, dk scaklklarda CH4 n yeteri kadar paralanmadn, dolaysyla
serbest C olumadn gstermektedir. Bu scaklklarda kinetik faktrler nemli rol oynamaktadr. 1200 ve 1300 K
de ise CH4 n paralanma derecesi artarak rnlerde Ni yannda serbest C da grlmektedir. Yksek scaklklarda
kinetik faktrler nemini yitirmekte ve sistem termodinamik dengeye yaklamaktadr. Termodinamik ngrler, artan
CH4 miktaryla NiO tozundaki deiimleri srasyla NiONiNi+C eklinde olduunu gstermekte olup 1200-1300
K deki deneysel sonularla kalitatif olarak uyum iindedir. XRD analiz sonular, arlk oran verilerini dorulamaktadr. rnein, 1300 K de zamanla NiO faz Ni e kademeli olarak dnmekte, artan reaksiyon sresiyle Ni faznn
yannda bulunan serbest C a ait (002) pikinin iddeti (C miktar) artmaktadr.
5. SONU
Nanokristal nikel oksit tozunun reaksiyon davran farkl scaklk (1000-1300 K) ve sre iin saf metan altnda
incelenmitir. CH4, atmosferi altnda scaklk ve sreye bal olarak arlk oranlarndaki deiimler oksit tozunun
oksijence daha zengin olduunu
(Ni:O=1:1 oranndan daha yksek), muhtemelen bu orann 2:3 olduunu gstermitir. FTIR ve DTA/DSC-TG analizleri bu sonucu desteklemekte olup yapda NiO in yannda az miktarda Ni(OH)2xH2O faznn bulunduu tahmin
edilmektedir. Termodinamik ngrler, artan CH4 miktaryla NiO tozundaki deiimleri srasyla NiONiNi+C
eklinde olduunu gstermekte olup 1200-1300 K deki XRD ve arlk oran verileriyle kalitatif olarak uyum iindedir.
NiO-CH4 sisteminde nemli reaksiyonun; NiO(k)+2CH4 Ni(k)+C(k)+CO+4H2 eklinde olduu ngrlmektedir.
513

TEEKKR
Bu alma, ..Aratrma Projeleri Birimi tarafndan 1459 numaras ile desteklenen proje ile M. C. Altay n doktora
tezinin bir blmdr.
KAYNAKLAR
1. Xiao-Yan, G., Jian-Cheng, D., Preparation and Electrochemical Performance of Nano-Scale Nickel Hydroxide
with Different Shapes, Materials Letters, 61, 621-625, 2007.
2. Patil, P. S., Kadam, L. D., Preparation and Characterization of Spray Pyrolyzed Nickel Oxide (NiO) Thin Films,
Applied Surface Science, 199, 211-221, 2002.
3. Bououdina, M., Grant, D., Walker, G., Effect Of Processing Conditions On Unsupported Ni-Based Catalysts
For Graphitic-Nanofibre Formation, Carbon, 43 1286-1292, 2005.
4.Kuchibhatla, S. V. N. T., Karakoti, A. S., Bera, D., Seal, S., One Dimensional Nanostructured Materials, Progress in Materials Science, 52, 699-913, 2007.
5. Yang, P., The Chemistry of Nanostructured Materials, World scientific publishing, New Jersey, U.S.A.,
2003.
514

SNEK METALLERN TLMESNDE EEKSENL AISAL PRESLEME

KULLANIMI LE NCE TOZ RETM
Glhan AKMAK ve Tayfur ZTRK
Orta Dou Teknik niversitesi, Mhendislik Fakltesi, Metalurji ve Malzeme Mhendislii Blm, 06800, Ankara
ozturk@metu.edu.tr
zet
Snek metallerde ince toz retimi kuru tmede topaklama nedeni ile ou kez mmkn olmamaktadr. Her ne
kadar dk scaklklarda tme ve/veya slak tme belirli oranlarda baarl olsa da snek metal ve alamlardan ince toz retimi skntl bir sretir. Bu alma Mg tozlarnn tlmesini konu almakta ve etkin inceltme
amal olarak iki yntemi deerlendirmektedir. Bu yntemler MgH2 ilavesi ile tme ve e kanall asal preslemeyi
takiben tmedir. alma her iki yntemin de baarl sonular verdiini gstermekle beraber e kanall asal
presleme tm snek tozlara uygulanabilir olmas nitelii ile n plana kmaktadr. nerilen yntem snek tozlarn
e kanall asal prese beslenmesi ve birka paso preslemeyi takiben sertlemi metalin mekanik olarak tlmesidir.
Anahtar Kelimeler: Mekanik tme, Katkl tme, E Kanall Asal Presleme, Parack Boyutu, Hcre Bykl.
equal channel angular PRESSING AS an a ad n the mllng

of ductle powders
ABSTRACT
Mechanical milling of ductile metals and alloys into fine powders are difficult to achieve due to particle agglomeration. Even though cyrogenic milling and/or wet milling can lead to substantial reduction of particle size, the production of fine powders from ductile metals is a difficult process. The current study deals with the milling of Mg powder
and examines processing methods that would yield an efficient size reduction. Two methods were investigated i.e.
milling with MgH2 addition, and milling the powders pre-deformed via equal channel angular pressing(ECAP). The
study shows that both methods are successful in imparting a substantial size reduction but preprocessing of powders via equal channel angular pressing has more applicability. In this method, metal powders may be subjected to
several passes of equal channel angular pressing followed by mechanical milling.
Keywords: Mechanical Milling, Milling with Additives, Equal Channel Angular Pressing(ECAP), Particle Size, Coherently Diffracting Volume,
1. GR
Toz boyutlar her ne kadar toz retim aamasnda ilgili parametrelerin kontrol ile denetim altna alnabilse de,
elde edilen boyutlar ou uygulama iin iri kalmakta, bu da retim sonras parack inceltme srelerini gerekli
klmaktadr. nceltme, genellikle mekanik tme ile gerekletirilmektedir. Bu ilem, seramik ve intermetalikler gibi
krlgan tozlarda baarl sonular vermekte ve -kuru halde gerekletirilmeleri halinde bile- mikron alt tozlarn eldesi mmkn olabilmektedir. Bu durum snek tozlarda farkllk gstermekte, sneklik nedeni ile paracklar ufalanma
yerine arpma srasnda yer yer yapmakta ve aglomere olmaktadr[1]. Bu nedenle snek tozlar ou kez sv
515

bir ortam iinde tlmektedir[2]. Sv ortamn kullanm her uygulama iin uygun dmemekte, bu durum alternatif yntemlerin kullanmn gerekli klmaktadr. Bu yntemler malzeme snekliliini azaltma amal olup, bunun
nispeten yaygn uygulamas tmenin dk scaklklarda yaplmasdr[3]. Hidrr oluturan metallerde tmenin
hidrojen atmosferi altnda yaplmas gene yaygn bir uygulamadr[4]. Bavurulabilecek dier bir yntem tozlara
uygun katklar yaplarak snekliinin azaltlmasdr. Oksit[5], karbr[6] veya florrler[7] bu ama iin yaygnca kullanlan ilavelerdir.
nce toz eldesi Mg ve Mg esasl alamlarda nem arz eden bir husustur. Bu durum zellikle hidrojen depolama
asndan bir gereklilik olmakta ve sorunun nitelii gerei ilemin kuru olarak gerekletirilmesi gerekmektedir. Bu
almada magnezyumun tlmesinde iki yeni yntem deerlendirilmitir. Bunlar, katk maddesi olarak MgH2
ilavesi ile tme ve e kanall asal preslemeyi takiben tme eklindedir.
2. DENEYSEL YNTEM
Bu almada kullanlan Mg tozu (Alfa Aesar) % 99,8 saflkta ve parack bykl ortalama 45,7 m dir. Yaplan
almada ou deney saf Mg tozu ile gerekletirilmitir. Katkl karmlar Mgye MgH2(Goldschmidt) ilavesi ile
hazrlanmtr.
tme ilemleri gezegensel deirmende (Fritsch-Pulverisette 7 Premium Line) argon gaz altnda yaplmtr.
tme ilemleri paslanmaz elik hazne ierisinde 15 mm apnda paslanmaz elik toplar kullanlmak sureti ile gerekletirilmitir. Top/toz oran 10:1 olarak seilmi ve cihaz 700 rpm hzda altrlmtr. tme her yarm saatte
yarm saatlik srelerle durdurulmu ve bu ekilde ortamn snmas kontrol altnda tutulmutur.
E kanall asal pres ilemi iin kullanlan kalp ematik olarak ekil 1 de verilmektedir. Tozlarn kalp boluuna
beslenebilmesi iin tozlar nce bakr bir blok ierisine yerletirilmitir. Bu amala 14x14 mm boyutlarndaki bloun
orta ekseni 8 mm apnda delinmi ve bu delik toz konduktan sonra bakr bir tpa yardmyla kapatlmtr.
Verilen geometride kalp ke as =90 (d ke =20) olup numunenin kalptan geirilii gerek gerinme
olarak =1 e denk gelmektedir[8]. Her bir gei sonras numune dikey ekseni boyunca 90 evirilerek kanala tekrar
beslenmitir.
ekil 1. E kanall asal pres kalbnn ematik grnm (=90 ve =20)

lem gren tozlarda parack boyutu, tarama elektron mikroskop grntleri zerinde lm almak veya lazer
parack boyut lm ile tespit edilmitir. Mgnin su ile reaksiyona girmesi nedeni ile lazer ile lmde tozlar etanol
iinde datlmtr. Paracklarda, uyumlu krnm salayan hacim dier bir ifade ile hcre bykl X-nlar
krnm ile tespit edilmitir. Bu amala veri, CuK kullanlmak sureti ile 20<2<90 aralnda toplanmtr. Veriler
adml tarama modunda 0.02 lik aralklarla 3 s sre ile toplanmtr.
516

ekil 2. MgH2 ilaveli tme ile Mg de elde edilen toz yaps (a)Mg (b)Mg-%5 MgH2 (c) Mg-%10 MgH2
(d) Mg-%30 MgH2
3. BULGU VE DEERLENDRME
Bu blmde nce MgH2 ilaveli tme ele alnacak, takibende e kanall asal presleme sonras tme deerlendirilecektir.
MgH2 ilavesi ile tme MgH2 ilaveli tme iin Mg tozlarna hacimce % 5, % 10 ve % 30 MgH2 ilave edilmitir.
Her bir deney iin toplam 10 gr toz kullanlm ve tme argon atmosferi altnda gerekletirilmitir. 3 saat tme
sonras elde edilen toz byklkleri ekil 2 de verilmektedir. Tespit edilen SEM grntleri zerinde yaplan lmler sonucu elde edilen parack byklkleri izelge 1 de verilmektedir. Grlecei zere MgH2 ilaveli tme
ilavesiz tmeye oranla daha kk deerler vermektedir. lavesiz tme ile elde edilen parack bykl
ortalama 80 m iken bu deer % 5-10 MgH2 ilavesi ile 20 civarna dmekte ilave miktarnn % 30 a kartlmas ile
ortalama byklk 11 m e dmektedir. X nlar krnm yntemi ile tespit edilen hcre byklkleri izelge 1 e
dahil edilmitir. Benzer ekilde, artan MgH2 ilavesi ile parac oluturan hcreler klmekte, ancak bu klme
parack boyutuna gre daha tedrici kalmaktadr.
izelge 1. MgH2 katks ile tlen Mg de parack boyutu ve hcre bykl
Numune
Mg
Mg-5%
MgH2
Mg-10%
MgH2
Mg-30%
MgH2
Parack bykl
(m)
79,43
26.85
22.16
11.19
42.33
30.36
24.57
Hcre bykl (nm)

79.7
E kanall asal presleme kullanm ile tme Bakr blok iersine yerletirilen Mg tozlar ekil 1de gsterilen
kalp kullanlmak sureti ile 4 kez kalptan geirilmitir. Mg tozlarnda bu ilem sonras tespit edilen SEM grntleri
ekil 3de verilmektedir. Grlecei zere bu ilem sonucu tozlar konsolide olmakta ve yekparelemektedir. Drt
paso sonras yekpare halde bakr bloktan kartlan numune havanda krlm ve takiben tme ilemine tabi
tutulmutur.
517

ekil 3. E kanall asal presleme yntemi ile deforme edilmi Mg tozlarnda yap. a) balang mikroyaps
(b) Presleme sonras yap (kayma dzlemi kesidi)
Presleme sonras tlen tozlarn yaps ekil 4de verilmektedir. Grlecei zere tme ile elde edilen yaplar
magnezyumun dorudan tlmesi ile elde edilen yapdan -baknz ekil 2(a)- bir hayli incedir. Tozlar artan tme sresi ile tedrici bir incelme gstermektedirler. ki saat sonras ortalama 40 m olan toz boyutu 5 saatlik sre
sonunda 26 m e inmektedir.
Yukarda verilen sonular magnezyumun gerek MgH2 ilavesi gerekse e kanall asal presleme ile daha etkin tarzda tlebileceini gstermektedir. Nitekim tek bana kuru olarak tlen Mg, 5 saat sonunda yaklak 70 m lik
paracklar verirken MgH2 ilaveli tme % 5-10 mertebelik ilavelerde 20-30 m lik paracklar (%30 lk ilavede 11
m), e kanall asal preslemede ise benzer srede 26 m lik paracklar vermektedir.Burada belirtilmesi gereken
bir husus katknn MgH2 olmas nedeni ile burada bir hacim kaybnn olmaddr. Tozlarn dehidrrlenmesi ile tm
yap Mgye dnecektir. Bu durum hidrr oluturan metallerin katkl tme ile baarl tarzda tlebileceini
gstermektedir.
ekil 4. E kanall asal presleme sonras tlen Mg tozlarnda mikroyap. (a) 0,5 s (b) 1 s (c)2 s
(d) 5 s tme.
E kanall asal presleme ile tme, metal hidrr katkl tmeden farkl olarak tm metallere ve alamlara
uygulanabilir bir sretir. Bu nedenle ayr bir neme sahiptir. Bu ilem sonras elde edilen etkin incelme byk bir
ihtimalle ilemin sebep olduu gerinme sertlemesinden dier bir ifade ile sneklik azalmasndan kaynaklanmakta-
518

dr. E kanall asal presleme ile malzemelerin hzla sertletii ve bu sertlemenin byk oranda ilk paso srasnda
gerekletii bilinmektedir[9]. E kanall asal preslemenin dier bir stnl tmenin aksine malzeme yzey
alannda artn bu ilemde snrl kalmasdr. Bu durum atmosferden etkilenen tozlarn ilenmesinde bir stnlk
salamakta, tozlar atmosfer kontrolsz ortamda ilenebilmektedir. Bu koullarda nerilen yaklam tozlarn atmosfer kontrolsz olarak e kanall asal kalpta birka paso preslenmesi ve takiben atmosfer kontroll bir ortamda
ksa srelerle tlmesidir[10].
3. SONU
Mg tozlarnn inceltilmesini konu alan bu almada MgH2 ilavesi ile tme ve e kanall asal preslemeyi takiben
tme yntemleri deerlendirilmitir. alma her iki yntemin de baarl sonular verdiini gstermi ve
1- MgH2 nin 1/3 hacim oranlk ilavesi ile yaplan 3 saatlik tme sonunda parack byklnn 11,2 m indirilebildiini
2- Ekanall asal presleme ile tozlarn deforme edilmesi durumunda tozlarn nce yekpareletii, takiben yaplan
tmede ise etkin bir incelme gsterdii tespit edilmitir. Magnezyumun dorudan tlmesi durumunda elde
edilen parack byklnn 5 saat sonunda 70 m olduu dikkate alndnda yukarda verilen deerler tozlarda
ciddi bir incelmeye iaret etmektedir. MgH2 katk miktarnn yksek olmas katkl tmenin ancak hidrr oluturan
metaller iin uygulanabilir bir yntem olduu anlamndadr. Bu durum ekanall asal preselemeyi yntem olarak
nplana kartmaktadr.
KAYNAKLAR
1. Suryanarayana, C. Mechanical alloying and milling, Progress in Materials Science , Vol.46,1,2001
2. Arias, A.,The Role of Chemical Reactions in the Mechanism of Comminution of Ductile Metals into Ultrafine
Powders by Grinding NASA technical Note, 1968
3. Song, M. Y., Kwon, S. N., Bobet, J-L,Park, H. R. Enhancement of hydrogen-storage properties of Mg by reactive mechanical grinding with oxide, metallic element(s), and hydride-forming element Ceramics International,
vol. 37, 897-902, 2011
4. Bobet, J.-L., Akiba, E., Darriet, B., Study of Mg-M(M=Co,Ni, and Fe) mixture elaborated by reactive mechanical
alloying: hydrogen sorption properties International Journal of Hydrogen Energy, Vol. 26, . 493-501, 2001
5. Friedrichs, O., Klassen, T., Sanchez-Lopez, J.C., Bormann, R., Fernandez, A. Hydrogen sorption improvement of nanocrystalline MgH2 by Nb2O5 nanoparticles Scripta Materialia 54/7, 473,2006
6. Gvendiren, M., Baybr, E., ztrk, T., Effects of additives on mechanical milling and hydrogenation of magnesium powders International Journal of Hydrogen Energy, vol. 29, 491, 2004
7. Deledd, S., Borissov, A., Poinsignon C., Bott W.J., Dornheim, M., Klassen, T., H-sorption in MgH2 nanocomposites containing Fe or Ni with uorin , Journal of Alloys and Compounds , vol. 404/406, 409412, 2005
8. Valiev, R., Islamgaliev, R.K., Alexandrov, I.V., Bulk nanostructured materials from severe plastic deformation,
Progress in Materials Science , vol. 45, 103-189,2000
9. Valiev, R., Langdon, T.G., Principles of equal channel angular pressing as a processing tool for grain refinement, Progress in Materilas Science ,vol. 51, 881, 2006,
10. akmak, G., ztrk, T., ECAP processing and mechanical milling of Mg and MgTi powders: a comparative
study, Journal of Materials Science , vol. 46, 5559-5567, 2011
519

Sv Fazl sinterlenen W-Ni-Cu alamlarnda soutma hznn

mekanik zelliklere etkisi
N. Kaan ALIKAN*, Nuri DURLU**, A. akir BOR***
*TBTAK-SAGE, Metal ve Seramik Malzemeler Birimi, PK 16, Mamak, Ankara,
** TOBB, Ekonomi ve Teknoloji niversitesi, Makina Mh Bl., 06560, Ankara,
***Orta Dou Teknik niversitesi, Metalurji ve Malzeme Mh. Bl., Ankara
ZET
Tungsten ar alamlar sv fazl sinterleme teknikleri kullanlarak retilen iki fazl kompozit malzemelerdir. Bu
almada sv fazl sinterlenen 90W-7Ni-3Cu ve 90W-3Ni-7Cu alamlarnda sinterleme ileminden sonra yaplan
soutma ilemi hznn mekanik zelliklere etkisi incelenmitir. Numuneler souk izostatik presleme ile 300 MPa
basn altnda preslenmi ve 1430Cde hidrojen ve argon altnda 30 dakika sre ile sinterlenmitir. Sinterleme ileminden sonra numuneler iki farkl soutma hznda soutulmutur. Numunelerin mikroyaplar ve mekanik zellikleri
incelenmitir. Sv fazl sinterlenen 90W-7Ni-3Cu alamnn ekme dayanmnn ve % uzamasnn 90W-3Ni-7Cu
alamna kyasla daha iyi olduu belirlenmitir. 90W-7Ni-3Cu alamnda sinterleme sonrasndaki soutma hznn
yava olmasna bal olarak ekme dayanmnn ve % uzamann artt, 90W-3Ni-7Cu alamnda ise yava soutma koullarnda ekme dayanmnn dt ve snekliin artt belirlenmitir.
Anahtar Kelimeler: Tungsten ar alamlar, sv fazl sinterleme, W-Ni-Cu, mekanik zellikler, soutma hz
EFFECT OF coolng rate ON The MECHANICAL PROPERTIES OF

lqud phase sntered W-N-cu Alloys
ABSTRACT
Tungsten based alloys are two phase composite materials manufactured by liquid phase sintering technique. In
this study, the effect of cooling rate after liquid phase sintering was investigated in 90W-7Ni-3Cu and 90W-3Ni7Cu alloys. Samples were cold isostatically pressed under 300 MPa and sintered at 1430C for 30 minutes under
hydrogen and argon. After liquid phase sintering the samples were cooled at two different cooling rates. The mechanical properties of the samples were determined, and the microstructures were investigated. The mechanical
properties of the 90W-7Ni-3Cu alloy was found to be better than the 90W-3Ni-7Cu alloy. In the 90W-7Ni-3Cu alloy,
with the slower cooling rate after sintering, an increase in tensile strength and % elongation was observed. On the
other hand, in the 90W-3Ni-7Cu alloy, slower cooling rate led to a decrease in tensile strength and an increase in
% elongation.
Key Words : Tungsten heavy alloys, liquid phase sintering, W-Ni-Cu, mechanical properties, cooling rates
1. GR
Tungsten ar alamlar sv fazl sinterleme teknii ile retilen iki fazl metal matriks kompozitleridir. Tungsten ar
alamlarnn sahip olduklar yksek younluk, yksek ekme dayanm, yksek sneklik ve iyi korozyon zellikleri,
bu tr alamlarn zellikle savunma sanayisine ynelik uygulamalarda yaygn kullanmna yol amtr. Tungsten ar alamlarnda en youn olarak kullanlan l alam sistemleri W-Ni-Fe ve W-Ni-Cudr. Yaklak ola-
520

rak %90-%98 arlk oranlarndaki Wnin, belirli oranlardaki Ni-Fe veya Ni-Cu balayc faz bileimleri ile birlikte
1410C1500C aralndaki scaklklarda koruyucu ortam altnda sv fazl sinterlenmesi, yksek younlua ve
mekanik zelliklere sahip alamlarn retimini salamaktadr. Sinterleme sonras oluan iki fazl mikroyapda yksek oranda hacim merkez kp kristal yapl W faz, ve balayc faz (veya matriks) olarak kullanlan yzey merkez
kp kristal yapl Ni-Fe-W veya Ni-Cu-W kat zelti faz bulunmaktadr.
Tungsten ar alamlarnn sv fazl sinterlenmesi ile ilgili ilk alma 1930lu yllarda W-Ni-Cu l alam sisteminde yaplmtr [1]. Ancak W-Ni-Cu alam sisteminin istenilen mekanik zellikleri salayamamas nedeni ile, 1950li
yllarda daha iyi mekanik zellikler salayan W-Ni-Fe sistemi yaygn bir ekilde kullanlmaya balanmtr. Gnmzde W-Ni-Cu l alam sistemindeki tungsten ar alamlar manyetik geirgenliinin dk olmas nedeni ile
manyetik alan etkilenmeyen uygulamalarda yaygn olarak kullanlmaktadr [2].
W-Ni-Cu ve W-Ni-Fe sistemlerindeki ar alamlarn mekanik zelliklerinin incelendii almalarda, 90W-6Ni-4Cu
alamnn ekme dayanm 600 MPa, uzama ise %3 olarak [3], 90W-7Ni-3Cu alamnn ekme dayanmnn ise
770 MPa ve uzamann ise %0,5 ile %6 arasnda deitii gzlenmitir [4]. 90W-6Ni-4Cu alamnn sv fazl sinterleme ilemi 1425Cde 1 saat sre ile hidrojen altnda yaplm ve daha sonra numuneler hzl bir ekilde oda
scaklna soutulmu [3], 90W-7Ni-3Cu alamnda ise sv fazl sinterleme ilemi 1410Cde hidrojen altnda
yapldktan sonra numuneler frnda soutulmutur [4].
90W-7Ni-3Cu alamnda yaplan detayl mikroyap incelemelerinde herhangi bir intermetalik faz oluumuna rastlanmam, ancak Auger elektron spektroskopisi ile yaplan incelemelerde tungsten ile matriks arayzeyinde gzlenen P ve S birikintilerinin gevreklemeye yol aarak dk % uzama deerlerine yol at ifade edilmitir [4].
Hidrojen altnda 1420Cde 1 saat sre ile sinterlenen ve frnda soutulan 90,4W-7,2Ni-2,4Cu alamnda yaplan
detayl transmisyon elektron mikroskop almalarnda frnda soutulan numunelerde herhangi bir intermetalik faz
oluumuna rastlanmam, ancak 1350Cde bir saat tavlandktan sonra su verilen numunelerde tungsten ve matriks
arasndaki snrlarda intermetalik faz oluumlar gzlenmitir [5]. Transmisyon elektron mikroskop almalar fazlar
arasnda ince bir film olarak oluan bu fazn Ni4W faz olduunu gstermitir.
W-Ni-Cu l sisteminde balayc faz bileimindeki Ni:Cu orannn 7:3 olarak, ve balayc faz miktarnn %5 ile
%25 arasnda seildii bir almada, 1300C ve 1350Cde yaplan sv fazl sinterleme ilemi sonrasnda, balayc faz miktarndaki arta ve sinterleme sresindeki arta bal olarak W paracklarnn byklnn ve bitiikliin
azald gzlenmitir [6]. W-Ni-Cu l sisteminde daha yksek oranlarda W ( > %92,5) ve balayc faz iindeki
Ni:Cu orann yksek olduu (>2,5) ar alamlarda yaplan almalarda, numunelerin ekme dayanmlarnn 660
ile 701 MPa arasnda, % uzamalarnn ise 3 ile 6 arasnda olduu gzlenmitir [7,8].
W-Ni-Cu sistemindeki ar alamlarnn performans toz zelliklerinden, alam iindeki tungsten miktar ve balayc faz bileiminden, sv fazl sinterleme ortam ve sresinden, ve sinterleme ilemi sonrasndaki soutma hzna
bal olarak oluan mikroyapdan etkilenmektedir. Bu almada sv fazl sinterlenen 90W-7Ni-3Cu ve 90W-3Ni7Cu alamlarnda, sinterleme sonras iki farkl hzda yaplan soutma ileminin mekanik zelliklere etkisi incelenmitir.
2. DENEYSEL YNTEM
Deneysel almalarda kullanlan Cu, Ni ve W metal tozlarnn zellikleri izelge 1de verilmitir. Tozlarn ortalama
tane byklkleri lazer tane bykl analiz cihaz (Model: Malvern Mastersizer 2000) ile llmtr. Tozlarn
parack ekli taramal elektron mikroskop ile incelenmi ve ekil 1de verilmitir.
izelge 1. almada kullanlan metal tozlarn zellikleri.
Toz
retici
Cu
AEE
Ni
AEE
W
Eurotungstene
Saflk
99.9+
99.9+
99.9+
Toz ekli
Kresel
Kresel
Poligonal
D10(m)
3.1
5.2
1.7
D50(m)
6.5
9.1
4.2
D90(m)
12.3
16.1
10.3
521

Elementel metal tozlarndan yaklak olarak 3 kg olarak hazrlanan 90W-7Ni-3Cu ve 90W-3Ni-7Cu toz karmlar
Turbula kartrcda (Model: T2F Glenn Mills) dakikada 67 devir ile 45 dakika sre ile kartrlmlardr. Toz karmlarnn ekillendirilmesinde polimerik kalplar kullanlm ve numuneler souk izostatik presleme cihaznda
(Model: Flow Autoclave Engineers CIP 42260) yaklak 15 saniye boyunca 300 MPa basn altnda sktrlarak
ekillendirilmilerdir. ekillendirilen W-Ni-Cu alamlarn ya numunelerinin yaklak %65 teorik younlua ulatklar belirlenmitir.
ekil 1. almada kullanlan Cu, Ni ve W metal tozlarnn taramal elektron mikroskop grntleri.
Sinterleme almalar yksek saflkta hidrojen gaz altnda (ilenme noktas = - 60C), 1430Cde atmosfer kontroll frn (Linn HT-1800) kullanlarak gerekletirilmitir. Sinterleme dngs u ekilde uygulanmtr : 9C/dakika
stma hz ile 1000Cye stma, saf H2 altnda 1000Cde 30 dakika oksit indirgeme, 3C/dakika stma hz ile
1430Cye stma, 1430Cde 20 dakika sre ile H2 altnda ve 10 dakika sre ile argon altnda sinterlemenin ardndan
iki farkl hzda soutma. Yava olarak yaplan soutma ileminde numuneler 1430Cden 1130Cye kadar 2,6C/
dak. hznda soutulduktan sonra frnda soutulmaya braklm, daha hzl olarak yaplan soutma ileminde ise
numuneler 1430Cden 1330Cye 2,8C/dak. hznda soutulduktan sonra frnda soutulmaya braklmtr.
Sinterlenen numunelerin mekanik zelliklerini belirleme almalarnda kullanlmak zere ekme testi ubuu ve
sertlik, younluk lm ve iyap incelemeleri iin ise kk numune retimi yaplmtr. ekme deneyinde kullanlan numuneler uluslararas standarda uygun ekilde (ISO 6892) hazrlanmtr. ekme testi (Model: 3369 Instron)
0.5mm/dakika ekme hznda gerekletirilmitir. ekme testi sonular 3 adet numunenin ortalamas alnarak verilmitir.
Alam numunelerinin iyaps geleneksel metalografi yntemleri ile incelenmitir. yap incelemeleri iin hazrlanan numuneler literatrde nerilen Murakami zeltisi (10 g K3Fe(CN)6, 10g NaOH, ve 100 ml saf H2O) ile dalanmtr. Numunelerin iyap incelemeleri nokta sayma yntemi kullanlarak optik mikroskop grntleri zerinden
gerekletirilmitir. Fazlarn hacimce miktarnn belirleme almalar ASTM E562 standardnn uygulanmas ile
gerekletirilmitir. Tungsten bitiiklik deeri ise optik mikroskop grntleri zerine 10x10cmlik ve 1cm aralkl
matrislerin izilmesiyle her bir izgiye den W-W balantsnn saylmasyla gerekletirilmitir.
Bitiiklik deerinin hesaplanmasnda kullanlan basit denklem u ekildedir [9].
NWW = izgi bana den W-W balant says

NWM = izgi bana den W-balayc faz balant says
Sinterlenmi numunelerin younluk lmleri hassas terazi kullanlarak Arimet prensibi ile gerekletirilmitir. Younluk lmlerinde sv olarak ksilen (younluk 0.86g/cm3) kullanlmtr. W-Ni-Cu alamlarndaki faz dnm scaklklar DSC cihaz (Model: Setaram Setsys Evolution) kullanlarak belirlenmitir. DSC cihaznda argon atmosferi
altnda yaplan lmlerde stma ve soutma hz olarak 10C/dakika kullanlmtr.
Sv fazl sinterlenmi ve farkl hzlarda soutulmu numunelerin optik mikroskop grntleri ekil 2de verilmitir.
Alamlarn mikroyaplar, kresel W tanelerinden, ve Ni-Cu-W balayc fazndan (veya matriks faz) olumaktadr.
Parlatlm numune yzeylerinde yaplan optik mikroskop incelemelerinde gzenek miktarnn ok az (<%1) olduu
ve younluk lmlerinde de btn numunelerin younluunun %99 teorik younluk civarnda olduu belirlenmitir.
522

ekil 2. Sv fazl sinterlenmi numunelerin optik mikroskop grntleri. (a) 90W-7Ni-3Cu, yava soutma,
(b) 90W-7Ni-3Cu, hzl soutma (c) 90W-3Ni-7Cu, yava soutma, (d) 90W-3Ni-7Cu, hzl soutma.
ekil 2de verilen optik mikroskop grntlerinde sv fazl sinterlenmi 90W-7Ni-3Cu alamndaki W tanelerinin,
90W-3Ni-7Cu numunelerindeki W tanelerine kyasla daha byk olduu grlmektedir. Optik mikroskop grntleri zerinde yaplan W tane bykl lmlerinde, ortalama W tane byklkleri yava ve hzl soutulmu
90W-7Ni-3Cu alamlar iin 22,55 mikron ve 214 mikron, yava ve hzl soutulmu 90W-3Ni-7Cu alamlar iin
ise 163 mikron ve 164 mikron olarak llm ve soutma hznn mikroyapdaki ortalama W tane byklne
nemli bir etkisinin olmad belirlenmitir. Optik mikroskop grntlerinden, grnt yazlm ile yaplan mikroyap
incelemelerinde, sinterlenmi numunelerdeki toplam balayc faz miktarnn 90W-7Ni-3Cu alamnda yaklak olarak %18, 90W-3Ni-7Cu alamnda ise %10 olduu belirlenmi ve soutma hznn balayc faz miktarnda nemli
bir deiime yol amad gzlenmitir.
Balayc faz iindeki Ni:Cu orannn artmasna bal olarak W tane bykl ve balayc faz miktar artmtr.
Bu artlarn nedeni Wnin 7Ni-3Cu balayc faz iindeki znrllnn, 3Ni-7Cu balayc faz iindeki W znrlne kyasla daha fazla olmasdr [10]. Sv fazl sinterleme ileminin baar ile gereklemesi iin yksek
miktarda kat fazn sv faz ierisinde znmesi gerekmektedir. Kat fazn sv faz ierisindeki znrlnn
artmas ile sv faz miktar artmakta, slatma as dmekte ve znme-yeniden kelme aamasnn ok hzl
gereklemesi nedeni ile son iyapdaki kat fazn bykl artmaktadr [9].
DSC almalar ile sv fazl sinterlenmi ve farkl soutma hzlarnda soutulmu numunelerin faz dnm scaklklar belirlenmitir. Yaplan DSC deneylerinin stma erilerinden balayc faz iindeki Ni:Cu orannn 7:3 olduu
numunede katgen scakl yaklak olarak 1387C svgen scakl ise 1426C olarak belirlenmitir. Balayc faz
iindeki Ni:Cu orannn 3:7 olduu durumda ise, katgen scakl 1188C, svgen scakl ise 1262C olarak llmtr. Bakr-nikel ikili faz diyagram incelendiinde, Ni:Cu orannn 7:3 olduu durumda svgen scakl 1375C,
Ni-Cu orannn 3:7 olduu durumda ise svgen scakl 1245Cdir [11]. 90W-7Ni-3Cu numunesinde gzlenen
svgen scakl 1426Cdir ve bu bileimdeki 7Ni-3Cu alamnn svgen scaklndan yaklak olarak 51C zerindedir. 90W-3Ni-7Cu alamnda ise Ni-Cu-W kat zeltisinin svgen scakl ile 3Ni-7Cu ikili alamn svgen
scaklklar arasnda yaklak olarak 17Clik bir fark bulunmaktadr. Her iki alamda da Wnin balayc faz iinde
znmesi, svgen erilerinde arta yol amtr. Ancak 90W-7Ni-3Cu alamnda balayc faz iindeki W znrl, 90W-3Ni-7Cu alamndaki balayc faza gre daha fazla olduu iin, l alamn svgen scaklndaki
art daha fazla olmutur [10].
Sv fazl sinterlenen ve farkl soutma hzlarnda soutulan 90W-7Ni-3Cu ve 90W-3Ni-7Cu ar alamlarnn optik
mikroskop grntleri zerinden yaplan mikroyap incelemeleri ile bitiiklik deerleri belirlenmitir. 90W-7Ni-3Cu
alamndaki bitiiklik deerleri yava soutmada 0,37 ve hzl soutma da 0,46 olarak, 90W-3Ni-7Cu alamnda
ise bitiiklik deeri yava soutmada 0,64 hzl soutmada ise 0,67 olarak llmtr. W-Ni-Cu alamlarnda llen bitiiklik deerleri mekanik zellikler asndan 90W-7Ni-3Cu alamnn 90W-3Ni-7Cu numunesine gre daha
523

iyi mekanik zelliklere sahip olabileceini ve bu alamlarda yava soutma hzlarnn daha iyi mekanik zellikler
vereceini gstermektedir. Sv fazl sinterlendikten sonra farkl hzlarda soutulmu numunelerin mekanik zellikleri izelge 2de verilmitir. Sinterlenmi numuneler arasnda en yksek ekme dayanm (776 MPa) ve uzama deeri (%9,2) yava soutulmu 90W-7Ni-3Cu numunesinde gzlenmitir. Bu numunede soutma hznn artrlmas
ekme dayanm deerinde ve % uzama deerinde dmeye yol amtr. 90W-7Ni-3Cu numunesinde
izelge 2. Sv fazl sinterlenmi ve farkl soutma hzlarnda soutulmu 90W-7Ni-3Cu ve 90W-3Ni-7Cu
alamlarnn mekanik zellikleri.
Numune
90W-7Ni-3Cu a
90W-7Ni-3Cu b
90W-3Ni-7Cu a
90W-3Ni-7Cu b
ekme Dayanm (MPa)
Uzama (%)
77614
74312
6811
7136
9.21.8
7.51.5
4.80.4
3.80.5
1430Cden 1100Cye argon altnda 2,6C/dak. hznda soutmann ardndan frnda soutma b1430Cden
1365Cye argon altnda 2,6C/dak. hznda soutmann ardndan frnda soutmafarkl soutma hzlarnda elde
edilen ekme dayanm deerleri Edmonds ve Jones tarafndan ayn alam sistemi iin yaplan bir almadaki
deerler ile benzerlik gstermektedir [4]. Ancak almamzda bu alam iin iki farkl soutma hznda daha yksek
% uzama deerleri elde edilmitir. ki farkl hzda soutulmu 90W-3Ni-7Cu alamlarnn ekme dayanm ve %
uzama deerleri 90W-7Ni-3Cu alamlarna kyasla daha dktr. Bunun nedeni dk Ni:Cu oranlarnda, Wnin
balayc faz iindeki znrlnn dk olmas ve buna bal olarak balayc faz dayanmnn azalmasdr. Bu
etkinin yansra, 90W-3Ni-7Cu alamnda bulunan balayc faz miktarnn daha az olmas (yaklak olarak %10)
yksek bitiiklik deerlerine yol amakta ve bu alam sisteminde ekme dayanmnn ve % uzamann dmesine
yol amaktadr.
4.SONULAR
Bu almada 1430Cde hidrojen ve argon altnda yarm saat sre ile sv fazl sinterlenen ve yksek younlua
ulalan 90W-7Ni-3Cu ve 90W-Ni3-Cu7 ar alamlarnda sinterleme ileminden sonra iki farkl hzda yaplan soutma ileminin mikroyapya ve mekanik zelliklere etkisi incelenmitir. alma sonucunda 90W-7Ni-3Cu alamnn ekme dayanmnn ve % uzamasnn 90W-3Ni-7Cu alamna gre daha yksek olduu belirlenmitir. 90W7Ni-3Cu alamnda sinterleme sonrasndaki soutma hznn yava olmasna bal olarak ekme dayanmnn ve
% uzamann artt, 90W-3Ni-7Cu alamnda ise yava soutma koullarnda ekme dayanmnn dt ve %
uzamann artt belirlenmitir.
5.KAYNAKLAR
[1] Price G.H.S., Smithells C.J. ve Williams S.V., Sintered Alloys. Part . CopperNickel-Tungsten Alloys Sintered with a Liquid Phase Present, Journal Institute Metals, Vol. 62, pp. 239-264, 1938.
[2] Caldwell S.G., Heat Treatment of Tungsten Heavy Alloys, International Journal of Powder Metallurgy, Vol.
39, No:7, pp. 43-51, 2003.
[3] Kuzmick J.F., Development of Ductile Tunsten-Base Heavy-Metal Alloys, Modern Developments in Powder
Metallurgy, Vol.3, pp.166-171, 1966.
[4] Edmonds D.V., Jones P.N., Interfacial Embrittlement in Liquid-Phase Sintered Tungsten Heavy Alloys, Metall.
Trans. A, Vol. 10A, No:3, pp. 289-295, 1979.
[5] Muddle B.C., Interphase Boundary Precipitation in Liquid Phase Sintered W-Ni-Fe and W-Ni-Cu Alloys, Metall.
Trans. A, Vol. 15A, No:6, pp. 1089-1098, 1984.
[6] Ramakrishnan K.N., Upadhyaya G.S., Effect of composition and sintering on the densification and microstructure of tungsten heavy alloys containing copper and nickel, J. Materials Science Letters, Vol.9, pp. 450-459,
1990.
[7] Das J., Kiran U.R., Chakraborty A., Prasad N.E., Hardness and tensile properties of tungsten based heavy
alloys prepared by liquid phase sintering technique, Int. J. Ref. Metals and Hard Materials, Vol.27, pp. 577583, 2009.
[8] Das J., Rao G.A., Pabi S.K., Microstructure and mechanical properties of tungsten heavy alloys, Materials
Science and Eng. A, Vol.527, pp.7841-7847, 2010.
[9] German R.M., Sintering Theory and Practice, John Wiley, Kanada, 1996.
[10] alkan N.K., Durlu N., Bor A.., Tungsten Esasl Ar Alamlarda Ni/Cu Orann Mekanik zelliklere Etkisi
yaynlanmak zere gnderildi, 2010.
[11 Okamoto H., Subramaniam P.R., Kacprzak L., Binary Phase Diagrams, Cilt 2, ASM International, Materials
Park, OH, 1990.
524

TOZ ENJEKSYON YNTEMYLE KALIPLANMI MgO TAKVYEL

ALMNANIN MEKANK ZELLKLERNN ARATIRILMASI
Ouz ERDEM*, brahim USLAN
*
Gazi niversitesi Mhendislik Fakltesi, Makine Mhendislii Blm, Ankara
oguz_erd@yahoo.com, iuslan@gazi.edu.tr
ZET
Bu almada MgO takviyeli ve takviyesiz almina tozlar toz enjeksiyon yntemiyle kalplanmtr. Balayc olarak
arlka %65 PEG8000 (polietilenglikol)+%30 PP (polipropilen)+%5 SA (stearik asit) kullanlmtr. Balangta
drt farkl oranda besleme stounun reolojik zellikleri incelenerek en iyi toz-balayc oran hacimce %53/%47
olarak bulunmutur. Bu karmdan oluan (MgO ilavesiz (takviyesiz) ve arlka %0,5, %1, %1,5 oranlarnda
MgO ieren) besleme stoklarnn reolojik zellikleri incelenmitir. Bu orana gre hazrlanan besleme stoklar
granl hale getirilmitir. Enjeksiyonda ekme ve eme numuneleri kalplanmtr. Kalplanan numunelere zc
ve sl balayc giderme (n sinterleme) ilemleri uygulanmtr. Yaplan sinterleme almalar sonucunda 1775 C
scaklk ve 8 saat sinterlenen numunelerde mekanik zellikler ktlemitir. 1775 C scaklk ve 6 saat sre optimum
sinterleme parametreleri olarak bulunmutur. En iyi mukavemet ve younluk deerleri ktlece %1 MgO takviyeli almina besleme stoklarnda elde edilmitir. SEM ile yaplan incelemelerde ktlece %1 MgO takviyeli numuneler daha
az gzenekli ve dzgn sinterlenmi grnm sergilemitir.
Anahtar Kelimeler: Toz enjeksiyon kalplama, Reoloji, Almina, Sinterleme.
INVESTIGATION OF MECHANICAL PROPERTIES OF POWDER INJECTION

MOULDED ALUMINA BY ADDING MgO
ABSTRACT
In this study, MgO added alumina and pure alumina powders were molded by powder injection molding method.
%65 PEG8000 (polyethyleneglycol)+%30 PP (polypropylene) + %5 SA (stearik asit) in weight was used as the binder.
First, the rheological properties of four different feedstocks were examined and the optimum powder/binder ratio
was determined as 53%/47% in volume. Rheological properties of feedstocks (pure and in weight for 0,5%, 1%,
1,5% MgO added alumina) which contain 53% alumina+ 47% binder in volume, were investigated. The feedstocks
prepared using this ratio, were granulated and then tensile and bending samples were molded by injection method.
Solvent and thermal (pre-sintering) debinding of these molded samples were carried out. As a result of sintering
investigations, the samples sintered in 1775 C for 8 hours had inferior mechanical properties. The temperature
of 1775 C and 6 hours of the holding time were determined as the optimum sintering parameters. The highest
strength and density values were obtained for 1% (wt.) MgO added alumina feedstocks. SEM analysis showed that
1% (wt.) MgO added alumina feedstock samples have less pore and those have good sintering.
Keywords: Powder injection moulding, Rheology, Alumina, Sintering.
1. GR
Toz Enjeksiyon Kalplama (TEK), ok ince taneli metal ve seramik tozlarn, termoplastik balayclarla
kartrlmas ve bu karma plastik enjeksiyon makinelerinde preslenerek ekil verme teknolojisidir. lem
aamalar; kartrma, granlleme, enjeksiyon kalplama, balayc ayrtrma ve sinterlemeden oluur [1]. kinci
Dnya Savandan sonra gelien teknolojilerin younluu dk, fiziksel ve kimyasal ortamlarda dayankl, y-
525

ksek scaklklarda da kullanlabilecek malzemelere olan ihtiyac aa karmasna bal olarak, metallerden daha
yksek scaklklarda kullanlabilen, sertlik ve anma direnci yksek seramik malzemeler ne kmtr [2]. Bugn
dnyada byk bir kullanm alanna sahip olan ileri mhendislik seramik malzemelerin banda mekanik, sl, optik,
elektrik, kimyasal ve nkleer zelliklerinden dolay almina ve almina bazl seramik malzemeler gelmektedir [3].
Alminann ekillendirilmesinde MgO ilavesinin alminadaki tane snr bymesini engelledii bilinmesine karn,
bugn halen birok aratrmac, MgO ilavesinin alminann tane bymesini yavalatmadaki roln ve tane yaps
zerindeki eitli mekanizmalar (ikinci faz, kat znme v.b) aratrmaktadr [4]. Alminann toz enjeksiyonla
kalplamasna ynelik almalar literatrde yaygn olmakla birlikte [5-20], MgO takviyeli alminann TEK yntemiyle
yaplm almalar snrldr [21-23].
Hwang ve arkadalar, aluminann enjeksiyon ile kalplanmasnda kullanlan balayc sistemine Mg bileikleri
katldnda sinterleme sonras %96 teorik younlua ulaldn ve Mg-stearatn homojen bir MgO dalm
saladn bildirmitir [21]. Vielma ve arkadalar polimer-mum esasl balayc sistemiyle gerekletirdikleri
alminann toz enjeksiyon yntemiyle kalplanmas almasnda en yksek younluk deerine (%99,6) 1600
Cde 2 saat sinterleme sonucu ulamlardr [22]. Ycel, herhangi bir ilave toz kullanmakszn %55 almina+%45
balayc sisteminden oluan besleme stou ile rettii numunelerde en iyi mekanik zellikleri 1800 C sinterleme
scaklnda elde ettiini bildirmitir [12].
2. DENEYSEL ALIMA
2.1. Malzemeler
Deneylerde kullanlan almina tozu Treibacher Schleifmittel firmas tarafndan retilen ALODUR WSK F500 fused
almina olup, %99,6 saflkta, 3,96 g/cm3 younlukta, 101,961 g/mol molekl arlnda ve 3,37 m ortalama boyuttadr.
Deneylerde takviye malzemesi olarak kullanlan magnezyum oksit tozu3 Merck Co. firmas tarafndan retilmitir.
Kullanlan MgOnun younluu 3,58 g/cm , molekl arl 40,30 g/mol, erime scakl 2800 C, kaynama scakl 3600
C ve ortalama boyutu 6,37 m dir. Balayc sistemi; enjeksiyon kalplama yaplacak MgO takviyeli ve takviyesiz almina
tozlarn sinterleme aamasna kadar bir arada tutacak olan iskelet balayc polipropilen (PP), kalplama esnasnda
ak kolaylatracak olan ana balayc PEG8000 ve toz-kalp aras yalayc (nemlendirici, kayganlatrc) etkis3i
olan stearik asit (SA)dan olumaktadr. Kullanlan PEG8000in younluu 1,204 g/cm ve erime scakl 60 C, PPnin
younluu 0,85 g/cm3 ve erime scakl 189 C, SAnn younluu 0,94 g/cm3 ve erime scakl 68 Cdir.
2.2. Klcal Reometre Deneyleri
Klcal reometre deneyleri iin drt farkl besleme stou oluturulmutur. Bunlar: hacimce %51 almina+%49
balayc, %53 almina+%47 balayc, %56 almina+%44 balayc ve %59 almina+%41 balaycdr. Besleme stoundaki balayc sistemi arlka %65 PEG8000, %30 PP ve %5 SAdan olumaktadr.
Deneylerde srasyla hacim olarak %51, 53, 56, 59 almina tozu oranl drt farkl besleme stounun 170, 180,
190, 200, 210 C scaklklarda 0,6 MPa ve 1 MPa basnlarda ASTM D1238 ve TS 1675 standartlarna gre reoloji
deneyleri yaplmtr.
2.3. Granlleme
Granlleme ilemi ift vidal Kraus-Maffei marka ekstrder ile yaplmtr. Ekstrderin silindir scakl 165 Cde ve 50
devir/dakda tm besleme stoklar granl edilmitir.
2.4. Toz Enjeksiyon Kalplama
Kalplama ilemi Gazi niversitesi Makina Mhendislii Blmnde bulunan ARBURG Allrounder 220S marka
enjeksiyon makinesinde gerekletirilmitir. Enjeksiyonda iki farkl tip (byk, kk) ekme numunesi ile tek tip
eme numunesi kalplanmtr. Bu numunelerin geometrileri ekil 1de, ham younluktaki boyut lleri ise izelge
1de grlmektedir.
2.5. Balayc Giderme
Bu almada kullanlan balayc sisteminden (%65 PEG8000, %30 PP, %5 SA) dolay iki aamada gerekletirilmitir.
lk aamada ana balayc PEG8000in suda znmesi, iskelet balayc PPnin ve yalayc SAnn suda znmemesinden faydalanarak PEG8000 uzaklatrlmtr. kinci aamada ise numuneleri sinterleme aamasna kadar
tayacak olan PP ve yalayc SA sinterlemenin ilk aamasnda s ile uzaklatrlmtr.
526

ekil 1. ekme ve nokta eme numunelerinin geometrileri

izelge 1. ekme ve eme numunelerinin ham younluktaki boyutlar
2.6. Sinterleme
Sinterleme ilemi Carbolite marka frnda gerekletirilmitir. Isl balayc giderme ileminden sonra frn 600 Cye
ulamtr. Sonra 10 C/dak ile 1200 Cye klm ve bu scaklkta 15 dak beklenmi daha sonra 15 C/dak ile farkl numunelerde (1650-1700-1720- 1740-1750-1775 C)ye klm ve burada 2-14 saat sre ile sinterleme ilemleri yaplmtr.
2.7. Sinterlenmi Paralarn % Bzlme ve Younluklarnn Tayini
ekme ve eme numunelerinin younluk ve % bzlme oranlar, TS 2305 ve TS EN 623-2 standartlarna uygun
olarak yaplmtr.
2.8. ekme ve Nokta Eme Deneyleri
ekme ve nokta eme deneyleri 5 kN kapasiteli bilgisayar kontroll Schimadzu marka ekme cihaz kullanlarak
gerekletirilmitir. ekme deneyleri TS ISO 15490 standart, eme deneyleri ise TS ENV 12789 standartlar esas
alnarak yaplmtr.
2.9. Taramal Elektron Mikroskop almalar
JEOL marka JSM-6060LV Taramal Elektron Mikroskobu (SEM) kullanlarak numunelerin sinterleme ncesi ve
sonras yapsal durumlar incelenmitir.
3.1. Klcal Reometre Sonular
Oluturulan drt farkl besleme stounun (hacimce %51 almina+ %49 balayc, %53 almina+%47 balayc,
%56 almina+%44 balayc ve %59 almina+%41 balayc) 0,6 MPa ve 1 MPa basn deerleri iin viskozitescaklk ve viskozite-kayma hz grafikleri deerlendirilerek besleme stoklarnn TEK ilemi iin uygunluu
aratrlmtr (ekil 2-5). Besleme stoklarnn reolojik zellikleri incelendiinde; hacimce %51 almina+%49
balayc karmnn reolojik zellikleri ilk bakta TEK ilemi iin uygun grnmektedir. Fakat bu karmn kayma
527

hz deerleri, dier karmlarn kayma hz deerlerine nazaran yksek olduundan; zellikle yksek kalplama
basnlarnda dk younluklu balaycya gre daha youn almina tozlarnn balaycdan ayrmasna neden
olabilecei, tam dolmama sorununa yol aabilecei dnlmtr. Ayrca TEK ilemi ile retilmi paralarda tam
younlua ulaabilmek iin mmkn olan azami kat ykleme oranna yaklalmaldr. Bu balamda hacimce %51
almina+%49 balayc karm tercih edilmemitir.
ekil 2. 0,6 MPa basnta karmlarn scaklk-viskozite grafii
ekil 3. 1 MPa basnta karmlarn scaklk-viskozite grafii
ekil 4. 0,6 MPa basnta karmlarn kayma hz-viskozite grafii
528

ekil 5. 1 MPa basnta karmlarn kayma hz-viskozite grafii

Besleme stoklarnn reoloji deneylerinde hacimce %56 almina+%44 balayc karmnn 170 Cde akmad ve
bundan sonraki scaklk deerlerindeki viskozite deerlerinin de TEK ilemi iin uygun olmad grlmtr. Buna
gre; bu karm iin kritik toz yk hacimsel olarak %56 alminadr. Dolaysyla besleme stoklarn olutururken
bu orann altndaki deerlerde oluturmann sorunsuz bir TEK ilemi iin gerekli olduu tespit edilmitir. Drt
farkl besleme stounun reolojik zellikleri incelendiinde TEK iin en uygun karmn hacimce %53 almina+%47
balayc olduuna karar verilmi ve MgO takviyesi bu orandaki karmlara yaplmtr. Burada almina ve MgOnun
younluk deerlerinin birbirine ok yakn olmas nedeniyle yaplacak MgO takviyesinin alminann reolojik zelliklerini
TEK ileminde sorun tekil edecek ekilde deitirmeyecei ngrlmtr. Bir baka deyile, takviyesiz almina
karm iin geerli olan en uygun orann, takviyeli almina karmlar iin de geerli olaca kabul edilmitir. Hacimce
%53 almina+ %47 balaycdan oluan farkl MgO takviyeli besleme stoklarnn 0,6 MPa ve 1 MPa basn
deerleri iin viskozite-scaklk ve viskozite-kayma hz grafikleri incelenerek TEK ilemi iin uygunluu aratrlmtr
(ekil 6-9).
ekil 6. 0,6 MPa basnta MgO takviyeli karmlarn scaklk-viskozite grafii
ekil 7. 1 MPa basnta MgO takviyeli karmlarn scaklk-viskozite grafii
ekil 8. 0,6 MPa basnta MgO takviyeli karmlarn kayma hz-viskozite grafii
529

Hacimce %53 almina+%47 balaycdan oluan takviyesiz, ktlece %0,5, %1 ve %1,5 MgO takviyeli besleme
stoklarnn, 0,6 ve 1 MPa basnlardaki scaklk-viskozite grafikleri incelendiinde viskozite deerlerinin tm besleme
stoklarnda 1000 Pa.snn altnda olduu ve TEK ilemi iin uygun olduklar rahatlkla grlebilir. Beslemestoklarnn
birbirlerine benzer ak zellii gstermesiyle, MgO takviyesinin reolojik zellikleri ok deitirmeyecei n grs
dorulanmtr.
ekil 9. 1 MPa basnta MgO takviyeli karmlarn kayma hz-viskozite grafii

3.2. Enjeksiyon Makinesinde Kalplama
Farkl enjeksiyon parametreleri sonucunda elde edilen baz numunelerde basn, scaklk, debi ve mal alma
miktarna bal olarak eksik dolum, apaklanma ve kme gzlenmitir. TEKde eksik dolum, apaklanma ve kme
istenmeyen durumlardandr. TEKde standart numune oluturma ancak uzun sren deneme-yanlmalar ile mmkn
klnmtr (izelge 2).
izelge 2. %53 almina+ %47 balayc ieren besleme stounun TEK ile kalplanmas
3.3. Balayc Giderme

Yaplan zcde balayc giderme denemelerinde en iyi sonu 60 C scaklktaki suda 24 saat bekleme sresinde
elde edilmitir. ekme ve eme numunelerine bu artlarda balayc giderme ilemi uygulanm sonra 50 Cde 5
saat kurutulmutur. Bu ilem sonunda PEG8000in, ekme numunelerinden ktlece %84, eme numunelerinden ise
ktlece %89u uzaklatrlmtr. Isl balayc giderme ilemi, sinterleme ileminin balangcnda gerekletirilmitir.
Isl balayc giderme ilemi ilk nce 210 Cye kadar 3 C/dak stma hzyla kma ve bu scaklkta 30 dak bekleme,
sonra 4 C/dak stma hzyla 480 Cye kma ve bu scaklkta 30 dak bekleme, daha sonra 5 C/dak stma hzyla
600 Cye kma ve bu scaklkta 15 dak bekleme olarak gerekletirilmitir. Bylece tamamlanan sl balayc
giderme ileminin (n sinterleme) ardndan numuneler frn iinden karlmadan sinterleme ilemine devam
edilmitir. Sinterlemenin balang aamas olarak planlanp uygulanan sl balayc giderme ileminde her hangi
bir soruna rastlanlmam ve sinterleme ilemi sonunda numuneler gayet dzgn kmtr.
3.4. Sinterleme
ncelikle optimum sinterleme parametrelerinin aratrlm daha sonra mevcut tane boyutu ve almina eiti iin en
uygun sinterleme artlar belirlendikten sonra bir defada ok sayda numune sinterlenmitir. Optimum sinterleme parametreleri belirlenirken ktlece %1 MgO takviyeli byk ve kk ekme numuneleri kullanlm ve sinterleme ilemi
sonunda numunelerin ekme mukavemetleri belirlenerek yorumlanmtr. Ktlece %1 MgO takviyeli numunelerin
kullanlmasnn sebebi, literatrde yaplm benzer bir almada [21] alminaya yaplan ktlece %1 MgO takviyesinin en iyi mekanik zellikleri gsterdii sonucudur. Optimum scaklk olarak 1775 Cnin tespitinden sonra optimum
sinterleme sresinin bulunmas iin bu scaklkta 2, 4, 6, 8 ve 10 saatlik sinterleme sreleri denenmitir. Sonulara
bakldnda 8 saat sinterleme sonras kk ekme numunelerinde ciddi derece arplma gzlemlenmi ancak
byk ekme numunelerinde bu sorunla karlalmamtr. 10 saatlik sinterleme ilemi sonras her iki tip numunede
de arplma gzlemlenmitir. 1775 Cde 6 saatte sinterlenmi byk ekme numunesinin mukavemet deeri ile
ayn scaklkta 8 saatte sinterlenmi byk ekme numunesinin mukavemet deerleri karlatrldnda, 8 saatlik
530

sinterleme ilemi sonras ekme mukavemetinde azalma grlmtr. Bunun nedenin yksek scaklklarda uzun sren sinterleme ilemi, tane bymesine yol amas olarak dnlmtr. Alminadaki anormal tane snr bymesinde MgO ilavesinin etkilerinin aratrld C. Park ve D. Yoonun almasnda [22] benzer sonular bulunmutur.
Sonu olarak en iyi deerler 1775 Cde 6 saatte sinterlenmi numunelerde elde edilmitir.
3.5. Mekanik Testler
Kk ve byk ekme numunelerinin 1775 C scaklkta 6 ve 8 saat bekleme srelerinde yaplan sinterleme
ilemi sonucunda deien ortalama mukavemet deerlerinin grafiksel gsterimleri ekil 10 ve 11de verilmitir.
Eme numunelerinin 1775 C scaklkta 6 ve 8 saat bekleme srelerinde yaplan sinterleme ilemi sonucunda
deien ortalama mukavemet deerlerin grafiksel gsterimleri ekil 12de verilmitir.
ekil 10. Kk ekme numunelerinin 1775 C scaklkta 6 ve 8 saat bekleme srelerindeki sinterleme ilemine gre
ortalama ekme mukavemetleri
ekil 11. Byk ekme numunelerinin 1775 C scaklkta 6 ve 8 saat bekleme srelerindeki sinterleme ilemine gre
ekil 12. Eme numunelerinin 1775 C scaklkta 6 ve 8 saat bekleme srelerindeki sinterleme ilemine gre
531

3.6. Sinterlenmi Paralarn % Bzlme ve Younluklar

Kk ekme numunelerinde en yksek younluk deeri ktlece %1 MgO takviyeli besleme stounda elde
edilmitir. Maksimum younluk deeri 3,44 g/cm3 ve %86,8 teorik younluk deeri elde edilmitir. Benzer durum
byk ekme numunelerinin younluk deerlerinde de grlmektedir. En yksek younluk deeri ktlece %1 MgO
takviyeli besleme stounda elde edilmitir. Maksimum younluk deeri 2,84 g/cm3 ve %71,7 teorik younluk deeri
elde edilmitir. Eme numunelerinde %1 MgO takviyeli besleme stounda 3,49 g/cm3 en yksek younluk ve %88,1
teorik younluk deeri elde edilmitir. Alminaya ktlece %0,5 MgO takviyesi younluk deerini artrmakta, MgO takviye miktar ktlece %1 olduunda ise younluk deerleri maksimum olmaktadr. Ancak MgO takviye miktar ktlece
%1,5 olduunda younluk deerlerinde d grlmektedir. Kk ekme numunelerinde %17,8 bzlme deeri,
byk ekme numunesinde %18,5 bzlme deeri ve eme numunelerinde %16,2 bzlme deeri elde edilmitir.
Bu almada toplam tip numune kullanlmtr. Bunlar byk ekme, kk ekme ve eme numuneleridir. Ham
numuneden balaycs giderilmi numuneye ve daha sonra sinterlenmi numuneye geii ile sinterlenmi numunelerdeki boyutsal daralma ekil 13de grlmektedir.
ekil 13. Numunelerdeki boyutsal daralma

3.7. Mikroskobik ncelemeler
Ham ve balaycs giderilmi takviyesiz alminaya ait ekme ve eme numunelerinin SEM grntleri ekil 14de
grlmektedir.
ekil 14. Ham ve balaycs giderilmi numuneler (a) Ham ekme numunesi
(b) Balaycs giderilmi ekme numunesi (c) Ham eme numunesi (d) Balaycs giderilmi eme numunesi
532

ekil 14 (a) ve (c)de grlecei zere ham numunelerde balayclar beyaz renkli blgelerde youn olarak grlmektedir. ekil 14 (b) ve (d)de ise balaycs giderilmi numunelerde beyaz blgelerin ciddi oranda azald grlmektedir.
3.7.1. ekme numuneleri
Drt farkl besleme stoundan hazrlanp 1775 Cde 6 saat sinterlenmi ekme numunelerinin krlma yzeylerine
ait SEM grntleri ekil 15de verilmitir.
ekil 15. %53 almina+ %47 balaycya sahip ekme numunesi krlma %5 yzeyleri (a) Takviyesiz numune:
48 MPa (b) %0,5 MgO takviyeli numune: 50,4 MPa (c) %1 MgO takviyeli numune: 69 MPa (d) %1,5
MgO takviyeli numune: 54,2 MPa
ekme numunelerinin SEM grntlerinden de grld gibi (ekil 15) almina tozlarnn en youn olduu,
baka bir ifadeyle gzeneklerin en az olduu %1 MgO takviyeli numune (ekil 15.c), ekme mukavemetinin yksek
olduu numunedir.
3.7.2. Eme numuneleri
Drt farkl besleme stoundan hazrlanp 1775 Cde 6 saat sinterlenmi eme numunelerinin SEM grntleri ekil
16da verilmitir.
533

ekil 16. %53 almina+ %47 balaycya sahip eme numunesi krlma % yzeyleri (a) Takviyesiz numune:
88,2 MPa (b) %0,5 MgO takviyeli numune: 110 MPa (c) %1 MgO takviyeli numune: 158 MPa (d) %1,5
MgO takviyeli numune: 144,1 MPa
Eme numunelerinin SEM grntlerinden de grld gibi (ekil 16) almina tozlarnn en youn olduu, baka
bir ifadeyle gzeneklerin en az olduu %1 MgO takviyeli numune (ekil 16.c.), ekme mukavemetinin yksek olduu
numunedir.
4. SONULAR
1. Kritik toz yk %56 almina olarak bulunmu ve en iyi toz-balayc oran hacimce %53 almina+ %47 balayc
olduu tespit edilmitir.
2. Granl haline getirilen besleme stoklaryla dzgn kalplama iin enjeksiyon parametreleri belirlenmitir. ekme
numuneleri iin 1150 bar enjeksiyon basnc, 17 cm3/s debi, 16 cm3 mal alma miktar ve 195 C ortalama
scaklkla kusursuz numuneler kalplanmtr. Eme numuneleri iin 900 bar enjeksiyon basnc, 17 cm3/s debi,
13,5 cm mal alma miktar ve 190 C ortalama scaklkla kusursuz numuneler kalplanmtr.
3. En iyi sinterleme parametreleri mukavemet deerleri esas alnarak: 1775 C sinterleme scakl ve 6 saat bekleme sresi olarak belirlenmitir.
4. Takviyesiz alminadan retilmi ekme numunelerinde, maksimum ekme mukavemeti 48 MPa iken ktlece
%1 MgO takviyeli alminadan retilmi numunelerin maksimum ekme mukavemeti 69 MPadr. Ayrca bu
almada ktlece %1 MgO takviyeli alminadan retilmi kk ekme numunelerinin ortalama ekme
mukavemeti 65,5 MPa iken Ycelin [12] almasnda ayn almina tozu ile 1800 Cde 10 dak sinterlenmi
kk ekme numunelerin ortalama ekme mukavemeti 56,51 MPadr. Bu sonulara gre alminaya ktlece
%1 MgO takviyesi yaplarak Ycelin [12] almasndaki ortalama ekme mukavemet deeri geilmitir.
5. Takviyesiz alminadan retilmi numunelerde, ortalama eme mukavemeti 86,8 MPa iken ktlece %1 MgO takviyeli alminadan retilmi numunelerde ortalama eme mukavemeti 155,8 MPadr. Ycelin [12] almasnda
alminadan retilmi eme numunelerinin ortalama eme mukavemeti 91,4 MPadr. Bu sonulara gre alminaya ktlece %1 MgO takviyesi yaplarak Ycelin [12] almasndaki maksimum eme mukavemet deeri
geilmitir.
6. Alminaya ktlece %0,5 MgO takviyesi hem ekme hem de eme mukavemetdeerlerini artrmakta, MgO takviye miktar ktlece %1 olduunda ise mukavemet deerleri maksimum olmakta, ancak MgO takviye miktar
ktlece %1,5 olduunda mukavemet deerlerinde d grlmektedir.
7. Takviyesiz alminadan retilmi ekme numunelerinde, maksimum younluk deeri 3,11 g/cm3 ve %78 teorik
younluk elde edilmitir. Ktlece %1 MgO takvi3yeli alminadan retilmi ekme numunelerinde maksimum
younluk deeri 3,44 g/cm ve %86,8 teorik younluk elde edilmitir. Takviyes3iz alminadan retilmi eme
numunelerinde, ortalama younluk deeri 3,12 g/cm ve %78,7 teorik younluk elde edilmitir. Ktlece %1
MgO takviyeli alminadan retilmi eme numunelerinde ortalama younluk deeri 3,45 g/cm3 ve %87,1 teorik
younluk elde edilmitir.
8. Alminaya ktlece %0,5 MgO takviyesi younluk deerini artrmakta, MgO takviye miktar ktlece %1 olduunda
ise younluk deerleri maksimum olmakta, ancak MgO takviye miktar ktlece %1,5 olduunda younluk
deerlerinde d grlmektedir.
9. 1775 C scaklkta 6 saatte yaplan sinterleme ilemi sonucunda: byk ekme numunelerinde %17,80, kk
ekme numunelerinde %18,52 ve eme numunelerinde %16,20 bzlme gereklemitir.
10. SEM ile yaplan mikro yap incelemelerinde ktlece %1 MgO takviyeli numuneler daha az gzenekli ve dzgn
sinterlenmi grnm sergilemektedir.
534

Teekkr
Bu alma, Gazi niversitesi Bilimsel Aratrma Projeleri tarafndan desteklenmitir.
KAYNAKLAR
1. Karata, ., Sarta, S., Toz Enjeksiyon Kalplama: Bir Yksek ve Teknoloji malat Metodu, Gazi niversitesi Mhendislik Mimarlk Fakltesi Dergisi, Ankara, 13 (2): 193-228, (1998).
2. ztrk, M., SiC laveli Almina Seramik Kompozitler, Yksek Lisans Tezi,
Sakarya niversitesi Fen Bilimleri Enstits, Sakarya, 1-83 (2007).
.ran, M., Alminann Ekstrzyonla ekillendirilmesi, Yksek Lisans Tezi, Afyon Kocatepe niversitesi Fen
Bilimleri Enstits, Afyon, 1- 4 (2006).
4.Byung-Ki, K., Seong-Hyeon, H., Sang-Ho, L., Alternative explanation for the role of magnesia in the sintering of
alumina containing small amounts of a liquid phase, Seoul National University, Korea, 634-635 (2003).
5.Hwang, K.S., Hsieh, C.C., Injection-Molded Alumina Prepared with MgContaining Binders, The American Ceramic Society, USA, 2349-2359 (2005).
6.Vielma, P.T., Cervera A., Levenfeld, B., Varez, A., Production of alumina parts by powder injection molding with a
binder system based on high density polyethylene, Universidad Carlos III de Madrid, Spain, 763-771 (2008).
7. Yang, W.W., Yang, K.Y., Hon, M.H., Effects of PEG molecular weights on rheological behavior of alumina injection molding feedstocks, National Cheng Kung University, Taiwan, 416-424 (2002).
8. Oliveira, R.V.B., Soldi, V., Fredel, M.C., Pires, A.T.N., Ceramic injection moulding: influence of specimen dimensions and temperature on solvent debinding kinetics, Universidade Federal de Santa Catarina, Brazil, 213-220
(2005).
9. Wei, W.C.J., Wu, R.Y., Ho, S.J., Effects of pressure parameters on alumina made by powder injection moulding, National Taiwan University, Taiwan, 1301-1310 (2000).
10. Loebbecke, B., Knitter, R., Hauelt, J., Rheological properties of alumina feedstocks for the low-pressure
injection moulding process, Institute for Materials Research III, Germany, 1595-1602 (2009).
11.Bakan, H.I., Gne, M., Development of Water Soluble Binder Systems for Low Pressure Injection Molding of
Alumina, TUBITAK-MRC Materials and Chemical Technologies Research Institute, Turkey, 313-316 (2004).
12. Ycel, ., Toz enjeksiyon kalplanm alminann mekanik zellikleri, Yksek Lisans Tezi, Gazi niversitesi
Fen Bilimleri Enstits, Ankara, 1-117 (2007).
13. Trunec, M., Cihlar, J., Thermal Debinding of Injection Moulded Ceramics, Technical University of Brno,
Czech Republic, 203-209 (1997).
14. Krauss, V.A., Oliveira, A.A.M., Klein, A.N., Al-Qureshi, H.A., Fredel, M.C., A model for PEG removal from alumina injection moulded parts by solvent debinding, Federal University of Santa Catarina, Brazil, 268-273 (2007).
15. Yang, W.W., Yang, K.Y., Wang, M.C., Hon, M.H., Solvent debinding mechanism for alumina injection molded
compacts with water-soluble binders, National Cheng Kung University, Taiwan, 745-756 (2003).
16. Wong, T.L., Li, R.K.Y., Wu, C.M.L., Injection Moulding of SiC / Al2O3 Composites, City University of Hong
Kong, Hong Kong, 399-404 (1997).
17. Mannschatz, A., Hhn, S., Moritz, T., Powder-binder separation in injection moulded green parts, Fraunhofer Inst. for
Ceramic Tech. and Systems, Germany, 1-6 (2010).
18. Trunec, M., Cihlar, J., Thermal removal of multicomponent binder from ceramic injection mouldings, Technical
University of Brno, Czech Rep., 2231-2241 (2002).
19. Wei, W.C., Tsai, S.J., Hsub, K.C., Effects of mixing sequence on alumina prepared by injection molding, Nationai
Taiwan University, Taiwan, 1445-1451 (1998).
20. Say, C.A., Earl, D.A., Thompson, M.J., Optimization of the sintered density of aluminum oxide compacts, New
York State College of Ceramics at Alfred University, USA, 262-267 (2002).
21. Heraiz, M., Merrouche, A., Saheb, N., Effect of MgO addition and sintering
parameters on mullite formation through reaction sintering kaolin and alumina, International Islamic University
Malaysia, Malaysia, 285-290 (2006).
22. Park, C.W., Yoon, D.Y., Abnormal grain growth in alumina with anorthite liquid
and the effect of MgO addition, Korea Advanced Institute of Science and Technology, Korea, 1585-1593
(2002).
23. Erdem, O., Toz enjeksiyon yntemiyle kalplanm MgO takviyeli alminann
mekanik zelliklerini aratrlmas, Yksek Lisans Tezi, Gazi niversitesi Fen Bilimleri Enstits, Ankara, 1-117
(2010).
535

MAGNEZYUMUN LAVESNN Al4Cu TM ALAIMININ YALANMA

DAVRANIINA ETKLER
Azim GKE*, Fehim FINDIK**, Ali Osman KURT***
Sakarya niversitesi Teknik Eitim Fakltesi Metal Eitimi Blm,54187, Sakarya, azimg@sakarya.edu.tr
Uluslararas Sarajevo niversitesi, Mhendislik ve Fen Bilimleri Fakltesi, Mmakine Mhendislii Blm,
71000, Saraybosna, Bosna-Hersek, ffindik@ius.edu.ba
***
Sakarya niversitesi, Mhendislik Fakltesi, Metalurji ve Malzeme Mhendislii Blm, 54187, Sakarya,
aokurt@sakarya.edu.tr
**
zet
Bu almada elementel olarak hazrlanm % 4 bakr ieren alminyum alamna farkl oranlarda magnezyum
katks yaplm, alamn yapay yalanma davran mikroyap ve sertlik sonularyla incelenmitir. Magnezyum
ilavesi Al4Cu toz metal ana malzemesinin yalandrma ile sertlik kazanma kabiliyetini artrmaktadr. Magnezyum
ilavesiz numunede sertlikte 6 saatlik yalandrma ile yaklak % 40lk bir art salanrken, ayn numuneye % 0,5
magnezyum ilavesi ile 6 saatlik bir yalandrma sonras sertlik art yaklak % 95 olmaktadr. almada en yksek
sertlie (117 HB) % 2 magnezyum ieren alamn 24 saat yapay yalandrlmas sonucu ulalmtr.
Anahtar Kelimeler: Al Toz Metal, Mikro Alamlama, Sinterleme, Toz Metal Isl lemleri.
EFFECTS OF THE MAGNESIUM ADDITION ON THE AGING BEHAVIOR OF

Al4Cu PM ALLOY
ABSTRACT
In this study, various levels of magnesium added into pre-mixed Al4Cu powder metallurgy alloy and aging behavior
of the alloy was investigated. The addition of Mg resulted in an increase in age hardening ability of the onto the main
Al4Cu PM alloy. The alloy without Mg addition has only 40 % increase in hardness after 6 hours ageing whereas
with an 0,5 wt% Mg addition on to the same alloy resulted in an 95 % increase in hardness after 6 hours ageing.
In the study, the highest hardness value was obtained with an alloy (Al4Cu2Mg) of 2 % Mg addition after 12 hour
ageing.
Keywords: Al Powder Metallurgy, Micro-Alloying, Sintering, Powder Metallurgy Heat Treatments.
1. GR
Alminyum alamlarnn dk zgl arlk, yksek korozyon direnci, geri dnm gibi zellikleri toz metalurjisi
ynteminin avantajlar ile birlemesiyle tozmetal alminyum alamlar son yllarda giderek artan bir oranda endstriyel ve teknolojik rnlerde kullanm alan bulmaktadr. Alminyum tozlarndan retilen alamlar ilenmi alminyum alamlar ile byk oranda benzer bileimdedir.
Alminyum tozlarnn sktrlma zellii, genel olarak toz morfolojisine ve boyut dalmna bal olmakla beraber,
350 MPa basn altnda teorik younluunun %90na kadar ulalabilmektedir. Demir esasl tozlara nispeten alminyum tozmetal malzemelerin sinterlenmesi iin ok daha dk scaklklar yeterli olmaktadr. Bu ise zamandan
ve enerjiden byk tasarruf salamaktadr [1].
536

Alminyumun toz metalurjisinde kullanmndaki byk sorunlardan biri yzey oksididir. Alminyum zerindeki oksidin kalnl ortam scakl, alminyum tozunun retiminde kullanlan sre, sakland ortamdaki nem gibi deikenlere baldr. Oda scaklnda ktle alminyum yzeyindeki oksidin kalnl yaklak 10 20 dur. Atomize alminyum zerindeki oksit kalnl ise 50-150 arasndadr. Alminyum zerindeki oksit genellikle amorf ve emilen
su tabakas nedeniyle hidrolize olmu durumdadr. 350 oC zerindeki scaklklarda tavlama srecinde oksit tabakas
g-Al2O3 halinde kristalize olur. Oksit tabakas dk ergime dereceli metallerde kat faz sinterlemeyi engelleyici bir
faktrdr. Bu yzde alminyum alamlarnn sinterlenmesinde sv faz daha ok tercih edilir bir yntemdir. Baz
metallerin alam sistemine katlmas sinterleme srasnda oksit tabakasn elimine edici etki yapabilir. Magnezyum
katksnn yzeyde oluan oksit tabakasn krmak sratiyle alminyum alamlarnn sinterlenmesinde olumlu katk
yapt bilinmektedir[2,3,4,5]. Sisteme magnezyum katlmas durumunda; oluan reaksiyon aadaki gibidir[6].
3Mg + 4Al2O3
3MgAl2O4 + 2Al (1)
Scheaffer[6] yapt TEM almalar ve mikroyapsal analizler ile Al 2xxx serisine yaplan Mg katksyla Spinel
fazn olutuunu gstermitir. Sinter esnasnda magnezyumun alminyum matris iine nfuz etmektedir Sonrasnda yukardaki reaksiyon sonucu oksit film tabakas zerinde hacimce deiim meydana gelmekte ve bundan
dolay oluan kesme gerilmesi oksit tabakasnn krlmasna sebep olmaktadr. Bylelikle yaynm (difzyon), slatma sonucunda sinterlemenin daha iyi olmasn salamaktadr. Dolaysyla, oksit tabakas bir problem olmaktan
kmaktadr.
Alminyum bakr alamlarnn mukavemetinin artrlmas iin sl ilem uygulanmas pratikte sklkla kullanlan bir
yntemdir. Bu yntem zeltiye alma, su verme ve yalandrma olarak basamaktan olumaktadr[7].
Bu almada elementel tozlarla hazrlanm Al4Cu ana alamna eitli miktarlarda (% 0,5 2) magnezyum ilavesinin mikroyapya ve yalandrma sonucunda ana malzemenin sertliine olan etkileri incelenmitir.
2.1 Hammadde ve Kompozisyon Hazrlama
almada kullanlan tozlarn zellikleri Tablo 1de verilmitir. Tablo 2`de ise almada retilen alamlarn bileimleri grlmektedir.
Tablo1. Deneysel almalarda kullanlan tozlarn zellikleri
Toz
Alminyum
Bakr
Magnezyum
Tedariki
Grel Makine A..
Grel Makine A..
Magnezyum Metal A..
Safiyet (%)
99,60
99,60
99,95
,00
Toz Boyutu ( m)
-53
-53
-53
Tablo 2. retilen alamlarn bileimleri

Alam Kodu
Alam Kodu
Al4Cu
Al4Cu0.5Mg
Al4Cu0.5Mg1Mg
Al4Cu0.5Mg2Mg
Alam Elementi (% a.)

Cu
4,00
4,00
4,00
4,00
Al
96,00
95,50
95,00
94,00
Mg
-0,50
1,00
2,00
Alamn bileimine uygun olacak ekilde tozlar 0,0001 gr hassasiyetli Precisa hassas terazide tartlm sonrasnda
taban 35 mm apnda 80 mm yksekliinde geni azl silindirik HDPE ielere konmutur. Kartrma ileminin
daha etkili olmas asndan 5mm apnda ZrO2 bilyeler kullanl olup, ielerin hacimce 1/3 karm toz, 1/3
ZrO2 bilye ile doldurulmu 1/3lk ksm ise bo braklmtr. Kartrma ilemlerinde Turbula-T2F Mixer kullanlm
olup kartrma sresi 3 saat olarak belirlenmitir.
537

2.2. ekillendirme lemleri

Kompaktlarn retilmesinde 14 Ton kapasiteli manel hidrolik bask cihaz kullanlmtr. Numune retiminde kullanlan basn 400 MPadr. retilen silindirik ham paralarn ap 16 mm ykseklii ise 4 mm olacak ekilde ayarlanmtr. Ham paralarn sinter ncesi younluklar ktlelerinin hesaplanm olan hacimlerine blnmesi ile bulunmutur. Kalp anmasnn engellenmesi iin her bir ekillendirme ilemi ncesi kalp boluu ve kalp zmbalar inko
stearat ile yalanmtr. inko stearattn yzeye dalm yksek safiyetli alkol ile gerekletirilmitir.
2.3. Sinterleme lemleri
Sinterleme ilemlerinde Honeywell DC2500 kontrol nitesi ile programlanabilen silindirik yatay tp frn kullanmtr.
Frnn reaktr tp 316 L paslanmaz elikten zel olarak imal edilmitir. zeltiye alma ilemlerinde de ayn frn ve
tp kullanlmtr. Numuneler frna Al2O3 altlklar zerinde yerletirilmitir. Sinterleme ilemlerinde yksek safiyette
azot gaz kullanlmtr. Gaz iindeki olas ok dk oksijen safszlnn nne geilmesi amacyla tpten kan
gaz frna girmeden nce silika jel ile doldurulmu gaz ykama iesinden geirilmitir. Gaz ak hz sinter esnasnda 1 lt/dk olarak belirlenmitir.
Sinterleme scakl 615 C olup bu scakla 15 oC/dk hzla klmtr. Kontrolsz olarak frn ierisinin bu scaklklarn zerine almasn engellemek amal 600 C`nin zerinde frn stma hz 1 oC/dk olarak gerekletirilmitir
(ekil 1). oCoCzeltiye alma ve yalandrma scaklklar her 3 grup numune iin de ayndr. zeltiye alma ilemi
sonrasnda ar doymu yap elde edilmesi amacyla frndan kartlan numuneler oda scaklndaki su ierisine
drlmtr. Isl ilem sreci olarak dkm alminyum alamlarna uygulanan T6 sl ilemine benzer bir sre olan T51 sreci seilmitir (ekil 1). Bu srece gre sinter sonrasnda numuneler oda scaklna dmeden
zeltiye alma scaklna kontroll olarak soutulmaktadr. Yalandrma ilemleri Protherm-PFL-130/6 kl frnda
yaplm olup yalandrma sresi 6, 12, 24 ve 48 saat olarak seilmitir.
2.4. Sinter Sonras lemler
Sinterlenen numunelerin younluklar Arimet Prensibine gre belirlenmitir. Younluk belirleme ilemleri karm
hazrlamada kullanlan hassas teraziye balanan younluk lm kiti ile yaplmtr. Younluk lm sonrasnda
numuneler hassas kesme cihaz ile ortadan kesilip herhangi bir kontrolsz yalanmann engellenmesi iin souk
olarak reineye alnmtr. Mikroyapsal inceleme iin numuneler geleneksel metalografik ilemlerden geirilmi
nihai parlatmada 0,3 mlik almina sspansiyon kullanlmtr. Optik mikroskop olarak Clemex Image Analysis yazlm ile senkronize alan Nicon Eclipse L150A metal mikroskobu, elektron mikroskobu olarak Jeol JSM 6060LV
taramal elektron mikroskobu kullanlmtr.
Sertlik lmlerinde BMS 200 RB sertlik lm cihaz kullanlm olup seilen yk 62,5 kg ve yk uygulama sresi
10 saniyedir. Her bir numuneden 5 lm alnm ortalama deer o numunenin sertlik deeri olarak kabul edilmitir.
ekil 1. Sinterleme almalarnda kullanlan scaklk-zaman grafii.
538


Deneysel almalarda kullanlan tozlarn morfolojik zelliklerinin incelenmesi amacyla ekilmi olan elektron mikroskobu grntleri ekil 2de verilmitir.
ekil 2. Kullanlan tozlarn SEM grntleri a)Al b)Cu c)Mg (. l izgisi a, b ve c iin 100 mdir). ve d iin ise
50 m`dir. l izgisleri daha da belirginletirilecek
Literatrde alminyum-bakr alamlarnn sinterlenmesi ile ilgili almalarda sinterlemenin 580-620 oC scaklklar
arasnda yapld grlmtr[6,8,9,10]. Sinterleme scaklnn belirlenmesinde bakr oran arttka sinterleme
scakl dmektedir. Alminyum bakr denge diyagramna gre (ekil 3) % 4 bakr katks ile tektik sv faza gei
scakl yaklak olarak 590 Cdir. Bu scaklk zerinde yaplan sinterleme ilemi sv faz olarak adlandrlr. Oluan
tektik sv fazn kapiler basn etkisiyle paracklarn arasn doldurmas ile daha youn bir yap elde edilmesini
salar. Daha nce yaplan bir alma[3] magnezyum katks ile birlikte sv faz oluma scaklnn dtn
gstermitir. Bu yzden almada kullanlan sinter scakl olan 615 Cde oluan tektik fazn diyagramda belirlenenden daha fazla olduu dnlmektedir. zeltiye alma scakl olan 550 Cde bakrn tamam yapya girerken
oda scaklnda alminyum iinde bakrn ok az bir ksm znebilmektedir. Bu durumda ani soutma ile ar
doymu bir yap elde edilmektedir.
ekil 3. Al-Cu faz diyagramnn alminyumca zengin ksm.

ekil 4de sinterlenmi Al4Cu ve Al4Cu2Mg alamlarna ait mikroyaplar grlmektedir. Magnezyum ilavesi ile
birlikte yapda tane bymesi grlrken tane snrlar da magnezyum ilavesiz numuneye gre daha belirgindir.
Magnezyum ilavesi ayn zamanda mikroyapda tespit edilebilir belirgin ekilde porozitede arta sebep olmutur
(ekil 5). Magnezyumun spinel faz oluturarak alminyum yzeyindeki oksit tabakasn krmas dolaysyla sv faz
oluumunu kolaylatrmas ve tane snrlarndaki sv faz miktar artyla beraber daha kaln tane snrlar olutuu
dnlmektedir.
539

ekil 4. Sinterleme ilemi sonrasnda a)Al4Cu b) Al4Cu2Mg alam.
ekil 5. retilen alamlarn sinter sonras % teorik younluk deerleri.

Al4Cu numunesine ait zeltiye alma sonucunda oluan optik mikroyap grnts ekil 6-ada; taramal elektron
mikroskobu grnts ise ekil 6-bde verilmitir. ekil 6-a genel yapnn grlmesi amacyla en dk bytmede
(50X) ekilirken ekil 6-b keltilerin ve gzenek byklnn daha iyi incelenmesi amacyla yksek bytmede
alnmtr. ekil 6-ada verilen numunede makro porozite grlmemektedir.
ekil 6. zeltiye alma ilemi sonucu Al4Cu numunenin a) optik b) SEM grnts
ekil 6-bde belirtilen noktalara ait EDS analiz sonular Tablo 3de sunulmutur. Yapda grlen beyaz blgelerin
demir ve bakrca zengin blgeler olduu grlmekle beraber zellikle demirce zengin blgeler inemsi yapda keltiler oluturmutur. Al4Cu numunesinin zeltiye alma sonras ekilmi XRD grafiinde (ekil 7) yapda Al-Cu-Fe
intermetalik faznn olutuunu tespit edilmitir.
540

Tablo 3. ekil 6-bde belirtilen noktalarn EDS analiz sonular.

Nokta
Al
69,874
95,131
98,836
97,879
1
2
3
4
Element (% a.)
Cu
21,952
4,869
1,164
1,762
Fe
8,174
--0,359
ekil 7. Al4Cu numunenin zeltiye alma sonras XRD grafii. (-Al7Cu2Fe, -Al)
Yapda grlen demir tozlarn retim safhasnda ve safszlk olarak gelmektedir. Demir faz iinde znerek
Al7Cu2Fe fazn oluturmaktadr. Bu faz mikroyapda inemsi/ubuksu formda yer almaktadr (ekil 6-b).
Al4Cu2Mg numunenin zeltiye alma ilemi sonucu mikroyaps ekil 8de verilmitir. Magnezyum ilavesi ile birlikte
ilavesiz numuneye oranla en byk fark olarak magnezyumun btn mikroyapda dalmas ve analiz yaplan noktalarda bulunan oksijen dikkat ekmektedir (Tablo 4). Matris olarak ifade edilebilecek 1 numaral nokta da dahil olmak zere analiz yaplan her noktada oksijen bulunmasnn nedeni, yapy oluturan elementlerin oksijene ilgisinin
yksek olmasndandr. Bakr ieriinin yksek olduu 3 ve 4 numaral noktalarda demir ieriinin de yksek olmas
XRD sonularn (ekil 7) dorular niteliktedir.
ekil 8. Al4Cu2Mg numunenin zeltiye alma ilemi sonucu mikroyap grnts

Tablo 4. ekil 8de belirtilen noktalara ait EDS elementel analiz sonular.
Nokta
1
2
3
4
Al
84,133
92,121
43,621
43,617
Element (% a.)
Cu
1,342
1,366
17,346
17,539
Mg
2,714
1,725
3,440
3,091
O
11,811
4,788
32,280
28,664
Fe
--3,311
7,088
Al4Cu2Mg numunesinin 24 saat yalandrma sonucu mikroyap grnts ekil 9da verilmitir. Mikroyap grntlerine gre tane snrlar belirgin olmakla beraber kimi noktalarda ikincil fazn daha belirgin olduu dikkat ekmektedir. zeltiye alma ilemi sonrasnda zeltiye alnamayan Al-Cu-Fe intermetaliinin (ekil 7) mikroyapda
541

farkl renkte grnd tespit edilmi olup tane snrlarnda youn olarak biriken bu fazn sertlik zerinde olumlu bir
etkisi olsa da mekanik zellikler zerinde olumsuz bir etkisinin olaca dnlmektedir. Bu fazn bakrca zengin
blgelerde daha youn bulunduu EDS analizi ile tespit edilmi olup matris olarak ifade edilecek 1 ve 4 numaral
noktalarda demir tespit edilmemesi bu faz zeltiye alnamad kantlar niteliktedir.
ekil 9. Al4Cu2Mg numunenin 24 saat yalandrma sonucu grnts.

Tablo 5. ekil 9da belirtilen noktalarn EDS analiz sonular
Nokta
Al
96,667
43,917
96,242
91,216
1
2
3
4
Cu
1,865
39,113
1,481
1,293
Element (% a.)
Mg
1,468
1,976
2,277
1,566
O
-11,201
-5,925
Fe
-3,792
---
retilen alamlara ait sertlik deerleri Tablo 6a verilmitir. Sonulara gre en yksek sertlik deeri 24 saat yalandrlan Al4Cu2Mg numunesinde elde edilmitir. % 2 magnezyum ilavesi, alam sertliinde hibir sl ilem olmadan
% 50 art salamaktadr. Magnezyumun sinter kolaylatrc etkisi ve yapda ince bir ekilde dalmas bunun balca sebebidir. Ayrca magnezyum katks arttka yalanma iin gerekli sre ksalmtr. Elde edilen sertlik deerleri
literatrdeki benzer almalardan daha yksektir[11,12,13].
Tablo 6. retilen alamlarn sertlik deerleri
Sertlik (HRB)
Alam
Al4Cu
Al4Cu0.5Mg
Al4Cu1Mg
Al4Cu2Mg
Sinter
zeltiye
alma
42,2
44,0
53,6
62,2
50,5
53,8
78,8
97,7
6 saat
59,2
86,2
92,4
111,1
Yapay Yalandrma
12 saat
24 saat
62,3
73,6
81,6
92,4
89,2
105,2
110,5
118,12
48 saat
72,2
94,3
96,6
101,8
4. SONULAR
zetle bu almada aadaki sonulara ulalmtr.
Hammadde olarak kullanlan tozlardan safszlk olarak gelen demir Al-Cu ile birleerek Al7Cu2Fe intermetalii
oluturmaktadr ve bu intermetalik zeltiye alma sl ilemi ile yapda zlememektedir.
Al-Cu-Mg alamna eklenen mikro dzeyde magnezyum ile sertlikte yaklak %50 art elde edilmitir.
Magnezyum ilavesi yalandrma ile sertlik kazanma kabiliyetini artrmaktadr.
Magnezyum ilavesiz numunenin sertlii 6 saatlik yalandrma ile yaklak % 40lk bir sertlik art salanrken,
ayn numuneye % 0,5 magnezyum ilavesi ile 6 saatlik bir yalandrma ile salanan sertlik art yaklak % 95dir.
En yksek sertlik 118,2 HB ile k elde edilebilirkenen yksek sertlik deerine te ulalmtr. en % 2`lik magnezyum katks yaplan numunelerin 24 saat yalandrlmas ile elde edilmitir.
Alamlandrma ve sl ilem ile Al4Cu alamnn sertlii % 179 artrlabilmektedir.
Silisyum ilavesinin % 1`e karlmas ile en yksek sertlie 6 saatte klabilmektedir.
542

TEEKKR
Bu alma Sakarya niversitesi Bilimsel Aratrma Projeleri Komisyonunca desteklenmitir (SA-BAPK 200950-02-020). Yazarlar, tozlarn teminindeki desteinden dolay Grel Makina A.. ve Magnezyum Metale teekkr
eder.
KAYNAKLAR
1. nternet Sitesi - European Powder Metallurgy Association- http://www.epma.com/New_non_members/structural_parts.htm
2. Lumley, RN., Sercombe, TB., Schaffer, GB., Surface Oxide and the Role of Magnesium During the Sintering of
Aluminum, Metallurgical and Materials Transactions A, Vol. 30A, pp. 457-463, 1999.
3. Kondoh, K., Kimura, A.,Watanabe, R., Effect of Mg on Sintering Phenomenon of Aluminium Alloy Powder
Particle, Powder Metallurgy, Vol. 44, pp. 161-164, 2001.
4. Gke, A., Fndk, F., Kurt, AO., Microstructural Examination and Properties of Premixed Al-Cu-Mg Powder
Metallurgy Alloy, Materials Characterization, Vol. 62, pp. 730-735, 2011.
5. MacAskill, IA., Hexemer Jr, RL., Donaldson, IW., Bishop, DP, Effects of Magnesium, Tin and Nitrogen on the
Sintering Response of Aluminum Powder, Journal of Materials Processing Technology, Vol. 210, pp. 22522260, 2010.
6. Schaffer, GB., Sercombe, TB., Lumley, RN.,Liquid Phase Sintering of Aluminium Alloys, Materials Chemistry
and Physics,Vol. 67,pp. 8591, 2001.
7. Smith, WF., Mhendislik Alamlarnn Yap ve zellikleri, eviri:Dr.Mehmet Erdoan, Nobel Yaynlar, Ankara,
2001.
8. Kyung, HM., Kang, SP., Lee, BH., Lee, JK., Kim, YD., Liquid Phase Sintering of the Commercial 2xxx Series Al
Blended Powder, Journal of Alloys and Compounds, Vol. 419(1-2), pp. 290-293,2006.
9. Hall, BJ., Schaffer, GB., Statistical Experimental Design of Al-Cu-Mg-Si P/M Alloys, Journal of Light Metals,
Vol. 2(4),pp. 229-238, 2002.
10. Lefebvre, LP., Thomas, Y.,White, B., Effects of Lubricants and Compacting Pressure on the Processability and
Properties of Aluminum P/M Parts, Journal of Light Metals, Vol. 2(4), pp. 239-246, 2002.
11. Kent, D., Schaffer, GB., Drennan, J., Age Hardening of a Sintered Al-Cu-Mg-Si-(Sn) Alloy, Materials Science
and Engineering: A, Vol. 405(1-2), pp. 65-73, 2005.
12. Delgado, ML., Ruiz-Navas, EM., Gordo, E., Torralba, JM., Enhancement of Liquid Phase Sintering Through
Al-Si Additions to Al-Cu Systems, Journal of Materials Processing Technology, Vol. 162-163, pp. 280-285,
2005.
13. ...c. T Durmus HK., Meric C., Age-hardening Behavior of Powder Metallurgy AA2014 Alloy, Materials and
Design, Vol. 28(3), pp. 982-986, 2007.
543

W-Ni-Fe alamlarnda balayc faz bileiminin mekanik

zelliklere etkisi
N. Kaan ALIKAN*, Nuri DURLU**, nder M. SOYER*, akir BOR***
*TBTAK-SAGE, Metal ve Seramik Malzemeler Birimi, PK 16, Mamak, Ankara,
** TOBB, Ekonomi ve Teknoloji niversitesi, Makina Mh Bl., 06560, Ankara,
***Orta Dou Teknik niversitesi, Metalurji ve Malzeme Mh. Bl., Ankara
ZET
Tungsten ar alamlar sv fazl sinterleme teknikleri kullanlarak retilmekte ve balayc faz olarak genellikle NiFe alam kullanlmaktadr. Bu almada %97 arlk orannda W ieren ar alamda, balayc faz iindeki Ni:Fe
orannn (2, 3, ve 4) mekanik zelliklere etkisi incelenmitir. Numuneler souk izostatik presleme ile 300 MPa basn
altnda preslenmi ve 1480Cde hidrojen ve argon altnda 30 dakika sre ile sinterlenmitir. Sv fazl sinterlenmi
numunelerin mekanik zellikleri belirlenmi ve mikroyaplar optik mikroskop ve taramal elektron mikroskop ile
incelenmitir. Balayc faz iindeki Ni:Fe orannn artmasna bal olarak ekme dayanmnn ve snekliin azald gzlenmi ve bu deiimin sinterlenmi numuneler iinde bulunan tungsten ve balayc fazn dnda oluan
nc bir faz ile ilgili olduu belirlenmitir.
Anahtar Kelimeler: Tungsten ar alamlar, sv fazl sinterleme, W-Ni-Fe, mekanik zellikler
EFFECT OF BINDER PHASE COMPOSITION ON The MECHANICAL

PROPERTIES OF W-N-Fe Alloys
ABSTRACT
Tungsten based alloys are produced by liquid phase sintering technique. Ni-Fe alloys are the most commonly used
binder phase in the manufacturing of tungsten alloys. This study investigates the effect of Ni:Fe ratio (2,3 and 4) on
the mechanical properties of tungsten based alloys with 97 wt.% tungsten. Samples were cold isostatically pressed
under 300 MPa and sintered at 1480C for 30 minutes under hydrogen and argon. The mechanical properties of
the liquid phase sintered samples were determined, and the microstructures were investigated with optical and
scanning electron microcopy. The study show that increase in Ni:Fe ratio of the binder phase decreases the tensile
strength and % elongation of the samples. The decrease in the mechanical properties of the heavy alloys is related
to the formation of a third phase in these alloys.
Key Words : Tungsten heavy alloys, liquid phase sintering, W-Ni-Fe, mechanical properties
1. GR
Tungsten ar alamlar sv fazl sinterleme ile retilen, yksek younluk ve yksek mekanik zelliklere sahip iki
fazl metal matriks kompozitleridir. Bu tr alamlarda ana faz yaklak olarak %90-%98 arlk oranlarnda kullanlan ve dayanm yksek olan hacim merkez kbik kristal yapl W, ikinci faz ise (matriks veya balayc faz) sv fazl
sinterleme ilemi srasnda bir miktar Wnin znd yzey merkez kbik kristal yapl ve sneklii yksek olan
Ni-Fe-W ve Ni-Cu-W kat zeltileri oluturmaktadr. Balayc faz bileiminde Nie ek olarak Fe veya Cu kullanm,
544

Wnin Ni iindeki znrln azaltarak zellikle krlganla yol aan nc fazlarn oluumunu engellemekte
ve mekanik zelliklerde arta yol amaktadr.
Tungsten ar alamlarnn retiminde en yaygn olarak kullanlan l sistem W-Ni-Fe sistemidir. Bu l sistemde
balayc faz bileimindeki Ni:Fe orannn 7:3 olduu durumda intermetalik faz oluumlarnn engellenerek sinterlenmi durumdaki en iyi mekanik zellikleri verdii ifade edilmitir [1]. zellikle W miktarnn %90-%98 arlk orannda ve balayc faz bileimindeki Ni:Fe orannn 7:3 olduu alamlarda salanan yksek dayanm (850-1000
MPa) ve yksek sneklik (%12-%30 uzama) deerleri, bu tr alamlarn savunma sanayisinde yaygn olarak
kullanmna yol amtr.
Sv fazl sinterlenmi tungsten ar alamlarnn mekanik zellikleri zerine yaplan bir almada, balayc faz
bileimindeki Ni:Fe orannn 7:3 olduu ve W arlk oranlarnn %80 ile %92 arasnda deitii W-Ni-Fe kompozit
malzemelerinde, mekanik zelliklerin sadece tungsten paracklarna bal olduu ve balayc faz miktarndan
etkilenmedii bulunmutur [2]. Balayc faz bileimindeki Ni:Fe orannn ayn olduu ancak tungsten arlk oranlarnn %88 ile %97 arasnda deitii W-Ni-Fe kompozitlerinin mekanik zellikleri zerine yaplan bir almada,
1480Cde 30 dakika sre ile hidrojen ve argon altnda sinterlenen numunelerde, 888-986 MPa arasnda ekme
dayanm deerleri ve %12 ile %35 arasnda sneklik deerleri elde edilmitir [3]. almada en yksek dayanm
deeri 93W-4,9Ni-2,1Fe alamnda, en dk sneklik ve dayanm deeri ise balayc faz miktarndaki azalmaya
bal olarak 97W-2.1Ni-0,9Fe alamnda gzlenmitir. Tungsten miktarnn %93 arlk oranndan fazla olduu
numunelerin (%95W ve %97W) boyun vermeden krld, ve krlmalarn nemli lde tane snrlar boyunca
olduu, tungsten miktarnn daha fazla olduu numunelerde ise (%88W, %90W ve %93W) numunelerin boyun
vererek krld gzlenmitir. Dayanmn en yksek olduu 93W-4,9Ni-2,1Fe numunelerinde yaplan krk yzey
incelemelerinde krlmalarn nemli lde W tanelerinden olduu gzlenmitir [3].
Tungsten ar alamlarn mekanik zellikleri toz zelliklerinden, alam bileiminden, retim srelerinden ve sinterleme ilemi sonrasnda oluan mikroyapdan etkilenmektedir. zellikle sv fazl sinterleme ilemi srasnda oluan gzenekler, sv fazl sinterleme ilemi sonrasnda balayc faz bileimine ve soutma koullarna bal olarak
oluan intermetalik fazlar, sv fazl sinterleme ileminin yapld hidrojen ortam ve tozlarn iinde bulunan safszlk
atomlarnn yol at gevreklemeler mekanik zellikleri olumsuz etkilemekte [4-10], ve istenilen mekanik zelliklerde para imalat iin btn srecin iyi bir ekilde kontrol edilmesi gerekmektedir.
W-Ni-Fe sisteminde retilen ar alamlarn nemli bir blmnde salad iyi mekanik zellikler nedeni ile balayc faz bileiminde Ni:Fe oran 7:3 olarak kullanlmaktadr. Bunun nedeni bu faz bileiminin krlganla yol aabilecek intermetalik bileiklerin oluumunu engellemesi ve buna bal olarak yksek dayanm ve yksek sneklik
deerlerinin salanabilmesidir. Ancak, baz almalarda sinterlenmi durumda bulunan numunelerde balayc faz
bileimindeki Ni:Fe orannn 2 ile 4 arasnda olduu durumlarda en iyi mekanik zelliklerin salanabilecei ifade
edilmitir [12]. almamzn amac, %97 arlk orannda W ieren W-Ni-Fe alamlarnda, nemli bir deiken olan
balayc faz iindeki Ni:Fe orannn (2, 3, ve 4) mekanik zelliklere etkisinin incelenmesidir
2. DENEYSEL YNTEM
Deneysel almalarda kullanlan Fe, Ni ve W metal tozlarnn zellikleri izelge 1de verilmitir. Tozlarn ortalama
tane byklkleri lazer tane bykl analiz cihaz (Model: Malvern Mastersizer 2000) ile llmtr. Tozlarn
parack ekli taramal elektron mikroskop ile incelenmi ve ekil 1de verilmitir.
izelge 1. almada kullanlan metal tozlarn zellikleri.
Toz
Fe
Ni
retici
W. Rowland Ltd.
AEE
Eurotungstene
Saflk
99.5+
99.9+
99.9+
Toz ekli
Kresel
Kresel
Poligonal
D10(m)
3.6
5.2
1.7
D50(m)
7.8
9.1
4.2
D90(m)
27.3
16.1
10.3
Elementel metal tozlarndan yaklak olarak 3 kg olarak hazrlanan 97W-2Ni-1Fe, 97W-2,25Ni-0,75Fe ve 97W2,4Ni-0,6Fe toz karmlar Turbula kartrcda (Model: T2F Glenn Mills) dakikada 67 devir ile 45 dakika sre ile
545

kartrlmlardr. Toz karmlarnn ekillendirilmesinde polimerik kalplar kullanlm ve numuneler souk izostatik
presleme cihaznda (Model: Flow Autoclave Engineers CIP 42260) yaklak 15 saniye boyunca 300 MPa basn
altnda sktrlarak ekillendirilmilerdir. ekillendirilen W-Ni-Fe alamlarn ya numunelerinin yaklak %65 teorik
younlua ulatklar belirlenmitir.
Sinterleme almalar yksek saflkta hidrojen gaz altnda (ilenme noktas = - 60C), 1480Cde atmosfer
kontroll frn (Linn HT-1800) kullanlarak gerekletirilmitir. Sinterleme dngs u ekilde uygulanmtr : 9C/
dakika stma hz ile 1000Cye stma, saf H2 altnda 1000Cde 30 dakika oksit indirgeme, 3C/dakika stma hz
ile 1480Cye stma, 1480Cde 20 dakika sre ile H2 altnda ve 10 dakika sre ile argon altnda sinterlemenin
ardndan frnda soutma.
Sinterlenen numunelerin mekanik zelliklerini belirleme almalarnda kullanlmak zere ekme testi ubuu ve
sertlik, younluk lm ve iyap incelemeleri iin ise kk numune retimi yaplmtr. ekme deneyinde kullanlan numuneler uluslararas standarda uygun ekilde (ISO 6892) hazrlanmtr. ekme testi (Model: 3369 Instron)
0.5mm/dakika ekme hznda gerekletirilmitir. ekme testi sonular 3 adet numunenin ortalamas alnarak verilmitir.
ekil 1. almada kullanlan Fe, Ni ve W metal tozlarnn taramal elektron mikroskop grntleri.
Alam numunelerinin iyaps geleneksel metalografi yntemleri ile incelenmitir. yap incelemeleri iin hazrlanan numuneler literatrde nerilen Murakami zeltisi (10 g K3Fe(CN)6, 10g NaOH, ve 100 ml saf H2O) ile dalanmtr. Numunelerin iyap incelemeleri nokta sayma yntemi kullanlarak optik ve elektron mikroskop grntleri zerinden gerekletirilmitir. Fazlarn hacimce miktarnn belirleme almalar ASTM E562 standardnn
uygulanmas ile gerekletirilmitir. Tungsten bitiiklik deeri ise optik mikroskop ve elektron mikroskop grntleri
zerine 10x10cmlik ve 1cm aralkl matrislerin izilmesiyle her bir izgiye den W-W balantsnn saylmasyla
gerekletirilmitir.
Bitiiklik deerinin hesaplanmasnda kullanlan basit denklem u ekildedir [12].
NWW = izgi bana den W-W balant says

NWM = izgi bana den W-balayc faz balant says
Sinterlenmi numunelerin younluk lmleri hassas terazi kullanlarak Arimet prensibi ile gerekletirilmitir. Younluk lmlerinde sv olarak ksilen (younluk 0.86g/cm3) kullanlmtr. W-Ni-Fe alamlarndaki faz dnm
scaklklar ise DSC cihaz (Model: Setaram Setsys Evolution) kullanlarak belirlenmitir. DSC cihaznda argon
atmosferi altnda yaplan lmlerde stma ve soutma hz olarak 10C/dakika kullanlmtr.
546


Sinterlenmi numunelerin taramal elektron mikroskop grntleri ekil 2de verilmitir. Mikroyap, ortalama tane
bykl 20-25 mikron olan kresel W tanelerinden (ak faz) ve balayc fazndan (siyah faz) olumaktadr.
Younluk lmlerinde sinterlenmi numunelerin younluklarnn %99 teorik younluun zerinde olduu gzlenmitir. Optik mikroskop ile parlatlm yzeylerde yaplan mikroyap incelemelerinde sv fazl sinterlemenin tamam
ile younlam 2 fazl bir mikroyapya yol at ve mikroyapda ok az miktarda (<%1) gzenek olduu belirlenmitir.
(a)
ekil 2. Sinterlenmi numunelerin taramal elektron mikroskop grntleri.

(a) 97W-2Ni-1Fe, (b) 97W-2,25Ni-0,75Fe, (c) 97W-2.4Ni-0,6Fe
Taramal elektron mikroskop grntlerinden, grnt yazlm ile yaplan incelemelerde sinterlenmi numunelerdeki toplam balayc faz miktarnn %5,5 ile %6,75 arasnda deitii, balayc faz iindeki Ni:Fe oran arttka,
balayc faz miktarnn azald gzlenmitir. Numunelerin taramal elektron mikroskop grntlerinden bitiiklik
lmleri yaplm ve bitiiklik deerlerinin Ni:Fe oranndaki arta bal olarak 0,52 ile 0,66 arasnda deitii belirlenmitir. Bitiiklik, W-W temas alannn toplam yzey alanna oran olarak tanmlanr. Bitiiklik ar alam iindeki
W miktarna ve iki dzlemli aya kat-kat-sv l noktasndaki a baldr [12]. Bitiiklik deerinin artmas,
W-W temas alann artracandan numunelerin snekliinde azalmaya yol aar.
Sinterlenmi numunelerin mekanik zellikleri izelge 2de verilmitir. Sinterlenmi numuneler arasnda en yksek
ekme dayanm (921 MPa) ve uzama deeri (%13) 97W-2Ni-1Fe numunesinde gzlenmitir. Rabin ve German
tarafndan W-Ni-Fe alamlar zerine yaplan bir almada [3], alam bileiminin 97W-2,1Ni-0,9Fe olduu sinterlenmi ve sl ilem grm bir numunede ekme dayanm 888 MPa, uzama ise %12,4 olarak llmtr. almamzda 97W-2Ni-1Fe numunesinde elde edilen ekme dayanm ve uzama deerleri Rabin ve German tarafndan
yaplan alma ile [3] benzerlik gstermektedir. Ancak almamzda elde edilen mekanik zellik deerleri balayc
faz iindeki Ni:Fe orannn daha dk olduu durumda (Ni:Fe = 2) elde edilmitir. Bu sonu W-Ni-Fe sistemindeki
ar alamlarda kullanlan balayc faz iindeki Ni:Fe orannn 7:3 gibi bir sabit deerde en yksek mekanik zellikleri vermediini, ve daha dk Ni:Fe oranlarnnda yksek mekanik zellikler salayabileceini gstermektedir.
547
(b)

izelge 2. 1480Cde hidrojen ve argon altnda 30 dakika sre ile sinterlenmi ve

frnda soutulmu numunelerin mekanik zellikleri.
Numune
97W-2Ni-1Fe
Balayc Faz
Ni:Fe Oran
2
ekme Dayanm
(MPa)
921 18
Uzama
(% )
13 1,2
97W-2,25Ni-0,75Fe
769 27
3,3 0,6
97W-2,4Ni-0,6Fe
750 11
2,6 0,7
Balayc faz iindeki Ni:Fe orannn artmasna bal olarak, 97W-2,25Ni-0,75Fe ve 97W-2,4Ni-0,6Fe numunelerinin ekme dayanmnda ve % uzama deerlerinde nemli azalmalar gzlenmitir (izelge 2). Bu iki numunenin,
zellikle uzama deerlerindeki yksek orandaki dn, balayc faz iindeki Ni miktarnn artmasna bal olarak
sinterleme ilemi srasnda ve/veya sonrasnda oluan intermetalik faz veya karbrlerden kaynakland dnlmtr.
Edmonds ve Jones tarafndan W-Ni-Fe ve W-Ni-Cu sistemlerindeki tungsten alamlarnn gevreklii zerine yaplan bir almada sinterleme ileminden sonra yaplan frnda soutma ileminin tungsten ile balayc faz ara
yzeyinde intermetalik faz oluumuna yol at ve buna bal olarak alamlarn gevrek davran gsterdii ifade
edilmitir [5]. Sv fazl sinterlenmi 90W-7Ni-3Fe ve 90W-5Ni-5Fe alamlarnda yaplan analitik transmisyon elektron mikroskop almasnda tungsten-balayc faz arayzeyinde oluan fazn W(Ni,Fe) intermetalik bileii olduu
ifade edilmitir [5]. Muddle tarafndan 90W-4,5Ni-4,5Fe alamnda, Posthill ve Edmonds tarafndan 90W-5Ni-5Fe
alamnda yaplan transmisyon elektron mikroskop ve Auger spektroskopisi almalarnda [7,8], arayzeyde oluan 3. fazn W(Ni,Fe) intermetalik bileii yerine sinterleme ortamndaki Ca bal olarak oluan (Ni,Fe)6W6C veya
(Ni,Fe)3W3C l karbr olabilecei ifade edilmitir.
Balayc faz iindeki Ni:Fe orannn yksek olduu numunelerde yaplan X-n krnm almalarnda ana faz
tungsten ve balayc faz Ni-Fe-W kat zeltisinin dnda nc bir faz gzlenmemitir. Bunun olas nedeni mekanik zelliklerde azalmaya neden olan intermetalik faz ve/veya karbr faznn miktarnn dk olmasdr. Taramal
elektron mikroskop ile dalanm numune yzeylerinden yaplan mikroyap incelemelerinde nc bir faz tespit
edilememitir. Ancak Ni:Fe oranndaki arta bal olarak zellikle uzama deerlerinde meydana gelen nemli ldeki azalmann bu alamlardaki nc bir faz oluumu ile ilgili olabileceini gstermektedir.
Sinterlenmi numunelerde yaplan DSC almalarnda faz dnm scaklklar belirlenmitir. Numunelerin stma
erilerinden yaplan incelemelerde 97W-2Ni-1Fe numunesinde balayc faz olarak bulunun Ni-Fe-W kat zeltisinin katgen scaklnn 1443C ve svgen scaklnn da 1467C olduu belirlenmitir. Balayc faz iindeki Ni
miktarnn artna bal olarak 97W-2.25Ni-0,75Fe ve 97W-2.4Ni-0,6Fe numunelerinin katgen scaklklar 1441C
ve 1409C, svgen scaklklar ise 1471C ve 1483C olarak llmtr. Balayc faz bileiminin deiimine bal
olarak katgen ve svgen scaklklarndaki deiimin, balayc faz iindeki W znrllnn farkl olmas ve de
zellikle Ni:Fe orannn 3 ve 4 olduu numunelerdeki olas 3. faz ile ilgili olduu dnlmtr.
Balayc faz bileimindeki Ni:Fe orannn 3 ve 4 olduu numunelerin DSC stma erilerinde, katgen scaklnn
zerinde 2. bir faz dnmne karlk gelen deiimler gzlenmitir. kinci faz dnmne karlk gelen scaklklar 97W-2.25Ni-0,75Fe numunesi iin yaklak olarak 1465C, 97W-2.4Ni-0,6Fe numunesi iin ise yaklak
olarak 1472C olarak belirlenmitir. 97W-2.25Ni-0,75Fe ve 97W-2.4Ni-0,6Fe alamlarnn DSC stma erilerinde
gzlenen 2. faz dnmnn, bu alamlar iinde W faz ve Ni-Fe-W kat zeltisinden ayr olarak bulunan 3. bir
faz ile ilgili olduu dnlmtr. W-Ni-Fe sistemindeki ar alamlar zerinde yaplan almalar [7,8], 3. fazn
sinterleme ileminden sonra soutma srasnda oluan (Ni,Fe)6W6C veya (Ni,Fe)3W3C faz olabileceini gstermektedir. Balayc faz iindeki Ni:Fe orannn yksek olduu durumda, olumas olas olan dier bir fazda Ni-W ikili
sisteminde bulunan Ni4W intermetalik fazdr. Bu numunelerdeki mikroyap almalar devam etmektedir. Yaplacak
olan detayl tramsmiyon elektron mikroskop almalar ile 3. faz bileimi ve kristal yaps belirlenecektir.
4.SONULAR
Bu almada 1480Cde hidrojen ve argon altnda yarm saat sre ile sv fazl sinterlenen ve yksek younlua
ulalan 97W-2Ni-1Fe, 97W-2,25Ni-0,75Fe, 97W-2,4Ni-0,6Fe alamlarnda, balayc faz iindeki Ni:Fe orannn
(2, 3, ve 4) mekanik zelliklere etkisi incelenmitir. allan tungsten ar alamlarnda, balayc faz iindeki
548

Ni:Fe orannn artmasna bal olarak ekme dayanmnn ve sneklik deerlerinin azald ve bunun tungsten ve
balayc fazn dndaki nc bir faz ile balantl olduu belirlenmitir.
TEEKKR
Taramal elektron mikroskop almasndaki katklarndan tr Orta Dou Teknik niversitesi, Metalurji ve Malzeme Mhendislii Blmnden Cengiz Tan ve Serkan Ylmaza teekkr ederiz.
5.KAYNAKLAR
[1] German R.M., Bourguignon L.L., Rabin B.H., Microstructure Limitations of High Tungsten Content Heavy Alloys, Journal of Metals, Vol. 37, No : 8, pp. 36-39, 1985.
[2] Krock R.H., Sheppard L.A., Mechanical Behavior of the Two-Phase Composite, Tungsten-Nickel-Iron, Transactions AIME, Vol. 227, No:11, 1127-1134, 1963.
[3] Rabin B.H., German R.M., Microstructure Effects on Tensile Properties of Tungsten-Nickel-Iron Composites,
Metall. Trans. A, Vol.19A, No:6, 1988
[4] Churn K.S., Yoon D.N., Pore formation and its effect on mechanical properties in W-Ni-Fe heavy alloy, Powder
Metallurgy, Vol. 2, No:4, pp. 175-179, 1979.
[5] Edmonds D.V., Jones P.N., Interfacial Embrittlement in Liquid-Phase Sintered Tungsten Heavy Alloys, Metall.
Trans. A, Vol. 10A, No:3, pp. 289-295, 1979.
[6] German R.M., Churn K.S., Sintering Atmosphere Effects on the Ductility of W-Ni-Fe Heavy Metals, Metall.
Trans. A, Vol. 15A, No:4, pp. 747-754, 1984. .
[7] Muddle B.C., Interphase Boundary Precipitation in Liquid Phase Sintered W-Ni-Fe and W-Ni-Cu Alloys, Metall.
Trans. A, Vol. 15A, No:6, pp. 1089-1098, 1984.
[8] Posthill J.B., Edmonds D.V., Matrix and Interfacial Precipitation in the W-Ni-Fe System, Metall. Trans. A, Vol.
17A, No:11, pp. 1921-1934, 1986.
[9] Yoon H.K., Lee S.H., Kang S.J.L.,Yoon D.N., Effect of vacuum-treatment on mechanical properties of W-Ni-Fe
alloy, J. Mater. Sci., Vol. 18, pp. 1374-1380, 1983.
[10] Edmonds D.V., Structure/Property Relationships in Sintered Heavy Alloys, Refractory Metals and Hard Materials, Vol. 10, pp. 15-26, 1991.
[11] Caldwell S.G., Heat Treatment of Tungsten Heavy Alloys, International Journal of Powder Metallurgy, Vol.
39, No:7, pp. 43-51, 2003.
[12] German R.M., Sintering Theory and Practice, John Wiley, Kanada, 1996.
549

Bakr ve Grafit Katkl N Alamlanm Astaloy mO Toz

Karmnda SNTERLEME ile sertletirme
Ahmet Murat GE*, Nuri DURLU*, Ayta ATA**, Hsn ZDURAL**
*TOBB Ekonomi ve Teknoloji niversitesi, Makine Mhendislii Blm, Stz Caddesi No:43, Ankara,
**Tozmetal Ticaret ve Sanayi A.. stanbul Caddesi No:75 Grpnar, Bykekmece, stanbul
ZET
Sinterleme ile sertletirme ilemi, ikincil bir sl ileme gerek kalmakszn toz metal paralarn retiminde kullanlan
tek aamal ve dk maliyetli bir imalat ilemidir. Bu almada, %2Cu ve %0.7C ieren n alamlanm Astaloy
Mo (Fe-1,5Mo) toz karmnda sinterleme ile sertletirme ilemi incelenmitir. Deneylerde presleme basnc olarak
600 MPa kullanlm, sinterleme ilemleri ve sinterleme ile sertletirme ilemleri sanayi lekli frnda 1120Cde
metan gaz ortamnda yaplmtr. Sinterleme ile sertletirme ileminin mekanik zelliklere etkisinin belirlenmesi iin
sinterlenmi numunelerin bir blmne ikincil bir sl ilem uygulanmtr. Sinterlenmi, sinterleme ile sertletirilmi,
sinterlenmi ve ikincil sl ilem uygulanm numunelerin makrosertlik deerleri, apraz krlma dayanm deerleri
belirlenmi ve mikroyaplar incelenmitir. alma uygun soutma koullar salanabildiinde, tek aamal sinterleme ile sertletirme ileminin ikincil bir sl ileme gerek kalmakszn istenilen mekanik zellikleri salayabileceini
gstermitir.
Anahtar Kelimeler: Toz metalurjisi, sl ilem, sinterleme ile sertletirme, n alaml tozlar, alamlama, sertleebilirlik.
SINTER HARDENING IN PREALLOYED ASTALOY MO ADMIXED WITH

COPPER AND GRAPHITE
ABSTRACT
Sinter hardening is a low cost one step process which eliminates secondary heat treatment in the manufacturing
of powder metallurgy components. In this study sinter hardening behavior of prealloyed Astaloy Mo (Fe-1,5Mo)
powder with %2Cu and %0,7C additions was examined. Samples were pressed at 600 MPa, sintered at 1120C
under methane atmosphere in an industrial furnace. After sintering the samples were sinter hardened at two different cooling rates. In order to understand the sinter hardening behavior, a secondary heat treatment was done with
the sintered samples. The macrohardness and transverse rupture strength of the sintered, sinter hardened, and
sintered and heat treated samples were measured. Microstructure of the samples were examined with optical and
scanning electron microscopy. The study show that, under favorable cooling conditions, sinter hardening can give
comparable properties in comparison to sintered and heat treated samples.
Key Words : Powder metallurgy, heat treatment, sinter hardening, prealloyed powders, alloying, hardenability
1.GR
Demir esasl toz metal alamlarn mekanik zellikleri temel olarak sinterleme sonras younluk ve buna bal
olarak para gzenekliliine baldr.[1]. Demir esasl toz metal alamlar genellikle sinterleme ilemi sonrasnda,
martensitli bir yap elde edilebilmesi, ve daha yksek sertlik ve dayanm deerleri iin, ikincil sl ilemlere tabi
tutulmaktadr. retilen paralarda mekanik zelliklerin arttrlmas iin gerekletirilen ikincil sl ilemler retim sra-
550

snda maliyet artna neden olmaktadr [2]. Bu nedenle, sinterleme ile sertletirme ilemi ikincil sl ilemi ortadan
kaldrabilmek iin, gn getike nemini arttran bir ilem haline gelmitir [3].
Sinterleme ile sertletirme ilemi temel olarak sinterlenme tamamlandktan sonra, retilen paralarn sinterleme scaklndan hzl soutmaya tabi tutularak sertlik artnn salanmasdr. Bu nedenle sinterlemenin gerekletirildii
frnda, soutma hz ayarlanabilir bir soutma nitesi olmas gerekir. [4] Soutma ilemi frnda, sinterleme evrimi
tamamlandktan sonra, soutma nitesinde yksek hzl hava akm oluturularak gereklemektedir. Bu sayede
sinterleme ilemi sonras yaplacak olan ikincil sertletirme ilemlerine gereksinim duyulmakszn martensitli bir
yap elde edilebilir. Bunun yannda geleneksel su verme ilemleri olduu gibi, malzeme ya veya su ile temasa
sokulmadan hzl soutma ilemi gerekletirilmektedir [3]. Sonu olarak, su verme ilemi srasnda oluabilecek
korosif etkiler de engellenmi olacaktr. Sinterleme ile sertletirme ilemi srasnda, ok yksek olmayan soutma
hzlar sayesinde, geleneksel ikincil su verme ilemlerine oranla daha iyi boyut kontrol salanabilmektedir [3].
Sinterleme ile sertletirme ileminin baar ile gerekletirilebilmesi iin, sinterleme ileminden sonra yaplan soutma ileminin i parasnda beynitli ya da martensitli mikroyap oluumuna yol amas gerekir [5]. Hava akm
ile soutma ilemi yeterli soutma hzlarna ulaamyor ise, malzeme sistemine eklenecek alam elementleri ile
malzemenin sertleebilirlikleri arttrlarak, parann mekanik zelliklerinde azalmaya neden olmakszn, martensitli
veya beynitli mikroyap oluumu salanabilmektedir. Molibden, nikel, krom ve bakr gibi alam elementleri demir
esasl paralarn sertleebilirliini artrarak sinterleme ile sertletirme ileminin istenilen mekanik zelliklere ulamasn salar [6-8]. Sertleebilirliin artmasnda rol oynayan bir dier faktr ise stenit tane boyutudur. ri stenit
taneleri, mikroyapda bulunacak tane snr miktarn azaltaca iin, tane snrlarndan balayan prlit dnm
azalacaktr ve sonu olarak malzemenin sertleebilirlii artacaktr [9]. Bu nedenle sinterleme sresi ve sinterleme
scakl sinterleme ile sertletirme ileminde nemli deikenlerdir [2].
Bunlarn yan sra, sinterleme ilemi gerekletirilecek parann bykl, sinterleme ile sertletirme ileminin sonucunu etkiler. Daha byk paralarda, gerekletirilecek olan s transferi daha yksek olaca iin, soutma hz
ya da malzemenin sertleebilirlii daha yksek olmaldr [4]. Para boyutunun yannda, sinterleme ile sertletirme
ileminde, toz metal paralarla alld iin, younluk nemli bir deikendir. zellikle para gzeneklilii, para
boyunca oluacak s transferini etkilemektedir, bu nedenle Engstrm ve dierlerinin yapt bir almada, gzenekliliin sinterleme ile sertletirme ilemine etkisi allmtr [9].
Molibdenum, nikel, krom ieren n alamlanm Astaloy tozu sinterleme ile sertletirme ileminde yaygn olarak
kullanlmaktadr. Warga ve Lindberg tarafndan Cu, Ni ve deiik oranlarda C eklenmi n alamlanm Astaloy Mo
tozunda yaplan bir almada 1120Cde 30 dakika sre ile yaplan sinterleme ileminden sonra 1-8C/s arasndaki
hzl soutma hzlarnda sinterleme ile sertletirilmi numunelerin mekanik zellikleri belirlenmitir [10]. almalar
sonucunda Astaloy Mo tozuna eklenen %2 Cu veya %2Ni ve %0,4-%0,6Cnun sertleebilirlii ve mekanik zellikleri
nemli lde artrd gzlenmitir.
Maroli ve dierleri tarafndan yaplan bir dier almada Mo, Ni, Cr ve Mn ieren n alamlanm Astaloy tozlarnda soutma hznn mekanik zelliklere ve mikroyapya etkisi incelenmitir [11]. Bileimi Fe-2Ni-1,5Mo-0,5C
olan alamdan hazrlanan numuneler 1120 Cde 30 dakika sre ile sinterlendikten sonra 0,1-8 C/saniye soutma
hzlarnda sinterleme ile sertletirilmi, ve mikroyapda beynit ve martensit gzlenmitir Soutma hznn 8 C/
saniyeden hzl olduu durumlarda mikroyapda byk oranda martensit olduu ve az miktarda da kalnt stenit
olutuu belirlenmitir. n alamlanm Astaloy Mo (Fe-1,5Mo) tozuna %2Cu ve %0,65C (veya %0,8C) eklenmesi
ile oluturulan iki alam sisteminde ayn artlarda yaplan sinterleme ileminden sonra soutma hzndaki deiime
bal olarak yava soutma hzlarnda (1-1,5 C/saniye) beynit ve martensit, hzl soutma hzlarnda ise (5-6 C/
saniye) martensit oluumu gzlenmitir [11]. . Bu almann amac %2Cu ve %0,7C eklenen n alamlanm
Astaloy Mo (Fe-%1,5Mo) toz karmnda sinterleme ile sertletirme ileminin incelenmesi, sinterleme ileminden
sonra ikincil sl ilemin sinterleme ile sertletirme ilemiyle karlatrlmasdr.
2.DENEYSEL YNTEM
Bu almada, Hganas firmasnn su atomizasyon yntemiyle rettii n alamlanm Astaloy Mo tozu kullanlmtr. Tozun tane boyutu 50-150 mikron arasnda deimektedir. almalarda kullanlan tozun bileimi ve zellikleri
izelge 1 de verilmitir. n alamlanm Astaloy Mo tozunun iine %2Cu ve %0,7C eklenmitir. Toz metalurjisi ile
retilen paralarda Mo sertleebilirlii ve sktrlabilirlii artrmak iin, Cu sinterlenen paradaki boyutsal deiimi
551

en aza indirmek iin, C (Grafit UF4) ise hem sertlii arttrmak hem de yalayc etkisi yaratmak iin kullanlan bir
alam elementidir. Tozlarda yalayc olarak inko stearat kullanlmtr.
izelge 1. almada kullanlan toz bileimi ve toz zellikleri.
Miktar
Grafit
Cu
Mo
Fe
Grnr younluk
Akkanlk
% arlk
0,7
1,5
Kalan
3,32 g/cm3
33 s/50 g
Numunelerin preslenmesi 600 MPa basn altnda 60 tonluk Instron marka ekme-basma cihaznda tek ynl
basma yaplarak gerekletirilmitir. Presleme ileminden sonra numunelerde 7,04 g/cm3lk ham younluk elde
edilmitir. Bu ilemde iki farkl geometride numune preslenmitir. Bu numuneler; nokta eme deneylerinde kullanlmak zere preslenen ubuk numuneler ve makro sertlik, mikro sertlik ve mikroyap almalar iin kontrol
numunesi olarak preslenen pelet numunelerdir. 16 mm apl pelet numunelerde 8,5 g toz kullanlrken ubuk numunelerde 17 g toz kullanlmtr. ubuk numuneler TS 4222 EN ISO 3325 standartlarna uygun, apraz krlma
testlerinde kullanlmak zere hazrlanmtr.
Sinterleme ilemi ve sinterleme ile sertletirme ilemleri, Tozmetal firmasndaki endstriyel lekli frnda gerekletirilmitir. Sinterleme ilemleri sresince koruyucu atmosfer olarak metan kullanlmtr. Frnda yaplan ilemler
sras ile; 700Cde yalayc ve balayc giderme ilemi, 1120Cye kadar kademeli olarak stma ve 20 dakika sre
ile sinterleme. Normal soutma koullar 5 Hz olarak ayarlanmtr. Sinterleme ile sertletirme ilemi iki ayr soutma hzyla gerekletirilmitir. Bu soutma hzlar kullanlan frnn kapasitesine gre dk hzl soutma (15 Hz) ve
yksek hzl soutma (30 Hz) olarak gerekletirilmitir. Frnn bant hz 200 mm/dk olup ve bir sinterleme evrimi
80 dakikada tamamlanmaktadr. Sinterleme ileminden sonra numunelere ikincil bir sl ilem uygulanmtr. kincil
sl ilem, 0,5 NH3 ortamnda, 150 dakika boyunca 890C scaklkta 0,4 C ortamnda karbonitrrleme ilemini, ortam
scaklnn 850Cye indirilmesinden sonra 1 dakika sre ile 1,0 C ve 0,5 NH3 ortamnda bekletmeden sonra, ayn
scaklkta 30 dakika sreyle 0,75 C ve 0,5 NH3 ortamnda bekletme ve 70Cye ya banyosu iinde hzl su verme,
ve 85Cde ykama ilemlerini iermektedir.
Mikroyap almalar, makro ve mikro sertlik lmleri pelet numunelerin kesitinden yaplmtr. Yaplan metalografik yzey hazrlama almalar sonrasnda numunelerin gzenek yaps incelenmi, daha sonra %3 nital zeltisi kullanlarak dalanm yzeylerde mikroyap incelemesi yaplmtr. Makro sertlik lmleri HRC leinde a
Wilson-Wolpert marka sertlik cihaznda, mikro sertlik lmleri HV0,1 leinde Buehler marka sertlik cihaznda
gerekletirilmitir. Sertlik lmleri radyal ve dikey eksende alnmtr. Her bir numuneden 10 adet sertlik lm
alnmtr. Mikro sertlik deneylerinde lmler radyal eksende 2 mm ve dikey eksende ise 1,25 mm aralklarla
gerekletirilmitir. apraz krlma deneyleri standartlara uygun olarak (TS4222 EN ISO 3325) hazrlanm ubuk
numunelerle gerekletirilmitir. Deneyler 5 tonluk Instron marka cihaznda standartlara uygun ekilde hazrlanm
nokta basma deney dzenei ile 1mm/dakika basma hznda gerekletirilmitir.
3.DENEYSEL SONULAR ve TARTIMA
3.1.Mekanik zellikler
Sinterlenmi, sinterleme ile sertletirilmi, ve ikincil sl ilem uygulanm numunelerin llen mekanik zellikleri
izelge 2 de verilmitir.
izelge 2. Sinterlenmi, sinterleme ile sertletirilmi, sinterlendikten sonra ikinci sl ilem uygulanm numunelerin makrosertlik ve apraz krlma dayanm deerleri.
Numune
(Fe-%2Cu-%1,5Mo-%0,7C)
orta hzda soutma
yksek hzda soutma
ikincil sl ilem
Makrosertlik
(HRC)
apraz Krlma Dayanm

(MPa)
391
88926
441
70260
451
73331
482
91868
552

Sinterlenmi ve yava soutulmu numunelerin sertlik deeri 39 HRC olarak llmtr. Sinterleme ileminden
sonra iki farkl soutma hznda yaplan sinterleme ile sertletirme ilemi sertlik deerlerinde yaklak olarak %12%15 civarnda bir art salam, ve sertlik deerleri 44 HRC ve 45 HRC olarak llmtr.
Maroli ve dierlerinin yapt bir almada %2Cu ve %0,6C (veya % 0,8C) eklenen n alamlanm Astaloy Mo
tozunda, azot ve hidrojen gaz karm ortamnda 1120Cde laboratuar lekli frnda yaplan sinterleme ileminden
sonra sinterleme ile sertletirme ileminde soutma hznn 1-1,5 C/s olduu durumda sertlik deeri %0,6C iin 315
HV10, %0,8C iin ise 340 HV10 olduu gzlenmitir [11]. Sinterleme ile sertletirme ilemindeki soutma hznn
artrlmas ile (2-3C/s ve 5-6C/s) sertlik deerlerinin %0.6C ieren numuneler iin 360 HV10 ve 430 HV10, %0,8
C ieren numuneler iin ise 375 HV10 ve 455 HV10 deerlerine ulat gzlenmitir [11]. almamzda sinterleme sonrasnda yava soutma koullarnda elde edilen sertlik deeri (39HRC) ve orta ve yksek hzda yaplan
sinterleme ile sertletirme ilemi sonrasnda elde edilen sertlik deerleri (44 HRC ve 45 HRC) Maroli ve dierleri
i[11] tarafndan yaplan almada orta ve yksek soutma hzlarnda elde edilen sertlik deerlerine benzerlik gstermektedir.
Sinterleme ileminden sonra yaplan ikincil sl ilem sonrasnda numunelerin sertlik deerlerinde %25e yakn bir
art gzlenmi ve sertlik deeri 48 HRC olarak llmtr. Sertlik deerindeki artn nedeni 800 C zerinde yaplan karbonitrrleme ilemine bal olarak azot ve karbonun numune yzeyine yaynarak yzey bileimini deimesi
ve daha sonra yaplan yada suverme ilemi ile martensit faznn oluturulmasdr. Sinterlendikten sonra ikincil sl
ilem yaplm numunelerde kesit boyunca mikrosertlik lmleri yaplm ve sonular ekil 1de verilmitir. Kenar
blgelerde karbonitrrleme ilemine ve soutma hznn yksek olmas ile martensit faznn oluumuna bal olarak
yksek sertlik deerleri (835 HV0,1) elde edilirken, orta blgede soutma hznn dk olmasna bal olarak
dk sertlik deerleri (580 HV0,1) elde edilmitir.
Sinterlenmi, sinterleme ile sertletirilmi, ve sinterleme sonras ikincil sl ilem uygulanm numunelerin apraz
krlma dayanm deerlerinin 702 ile 918 MPa ararsnda deitii belirlenmitir. Sinterleme ilemi sonrasnda yava
soutulmu numunenin apraz krlma dayanm deeri 889 MPa olarak llm, sinterleme sonras orta ve yksek
hzda yaplan sinterleme ile sertletirme ilemi sonrasnda apraz krlma dayanm deerleri 702 MPa ve 733 MPa
olarak belirlenmitir. En yksek apraz krlma dayanm deeri (918 MPa) sinterlendikten sonra ikincil sl ilem grm numunede gzlenmitir. Sinterleme ile sertletirme ilemi sinterleme ilemine kyasla sertlik deerlerinde art
salarken apraz krlma dayanm deerlerinde azalmaya yol amtr. Bunun nedeni, sinterleme ile sertletirme
ilemi sonrasnda, soutma hzndaki arta bal olarak numunelerin sertlik deerlerinin 44 HRC ve 45 HRCye
ykselmesi ve buna bal olarak numune iinde bulunan gzeneklerin atlak etkisi gstererek gevrek krlmaya yol
amasdr [12].
ekil 1. Sinterleme sonras sl ilem grm numunenin kesiti boyunca sertlik deiimi.
3.2. Mikroyap ncelemeleri
ekil 2de sinterlenmi numunenin parlatlm yzeyden ve dalanm yzeyden elde edilen optik mikroskop grntleri verilmitir. Sinterlenmi mikroyap kk ve byk gzeneklerden olumaktadr (ekil 2.a). Sinterleme
553

sonras yaplan younluk lmlerinde numune younluu yaklak olarak 7.1 g/cm3 olarak bulunmutur. Dalama
ilemi sonrasnda mikroyapda beynit (koyu faz) ve martensitten (ince inemsi faz) oluan iki fazl bir mikroyap
gzlenmitir. Sinterlenmi ve yava soutulmu numunede yaplan detayl mikrosertlik incelemeleri ile beynit faznn mikrosertlik deeri 422 HV0,1, martensit faznn mikrosertlik deeri ise 729 HV0,1 olarak belirlenmitir
ekil 2. 1120C de metan gaz ortamnda 20 dakika sinterlenen ve yava soutulan numunenin mikroyaplar. (a)
Parlatlm yzey, 100X, (b) Dalanm yzey, 1000X
Sinterleme ileminden sonra orta hzda ve yksek hzda yaplan sinterleme ile sertletirme ileminden sonra optik
mikroskopta elde edilen dalanm mikroyap grntleri ekil 3te verilmitir. Orta ve yksek hzda yaplan sinterleme ile sertletirme ilemi, soutma hznn artmasna bal olarak numunelerdeki martensit miktarn artrm ve
beynit miktarn azaltmtr. Sinterleme ile sertletirme ilemi sonrasnda yaplan makrosertlik lmleri sinterlenmi
numuneye kyasla sertlik artnn %15 civarnda olduunu gstermitir (izelge 2). Numuneler zerinde yaplan
detayl mikroyap incelemeleri, sinterleme ile sertletirme ilemi srasnda, martensit ve beynitin yansra ok az
miktarda kalnt stenit oluumu olduunu da gstermitir (ekil 2.b, ak beyaz yuvarlak faz).
ekil 3. 1120C de metan gaz ortamnda 20 dakika sinterlenen ve orta ve yksek hzda sinterleme ile sertletirilen numunelerin dalanm mikroyaplar. (a) Orta hz, 100OX, (b) Yksek hz, 1000X.
Sinterleme ileminden sonra yaplan ikincil sl ilem numunenin sertlik deerinde yaklak olarak %25 civarnda bir
arta yol amtr (Tablo 1). Bunun nedeni karbonitrrleme ilemi srasnda numunenin yzeyinde azot ve karbon
yaynmna bal olarak yzey bileiminin deiimi ve karbonitrrleme ileminden sonra yaplan hzl soutma ilemine bal olarak martensit faznn oluumudur. Karbonitrrleme ilemi sonrasnda numunenin yzey blgesinde
oluan martensit mikroyaps optik mikroskop grnts ekil 4.ada, taramal elektron mikroskop grnts ekil
4.bde verilmitir.
ekil 3. 1120C de metan gaz ortamnda 20 dakika sinterlenen ve ikincil sl ilem uygulanan numunelerin mikroyap grntleri (a) Kenar blge, optik mikroskop 100OX, (b) Kenar blge, taramal elektron mikroskop, 3000X.
554

4. SONULAR
Fe-%2Cu-%1,5Mo-%0,7C toz alamnda 1120Cde 20 dakika sre ile yaplan sinterleme ilemi 39 HRC sertlik
deerine, sinterleme sonrasnda iki farkl soutma hznda yaplan sinterleme ile sertletirme ilemi 45 HRC sertlik
deerine, sinterleme ileminden sonra yaplan ikinci sl ilem ise yaklak olarak 48 HRC sertlik deerine yol amtr.
Sinterlenmi ve sinterleme ile sertletirilmi numunelerde yaplan mikroyap incelemelerinde, mikroyaplarn
martensit ve beynitten olutuu ve numunelerde ok az miktarda kalnt stenit bulunduu belirlenmitir.
TEEKKR
Bu alma TOBB Ekonomi ve Teknoloji niversitesi ve Tozmetal A. firmasnn katklar ile gerekletirilmitir. Taramal elektron mikroskop almasndaki katklarndan tr Cengiz Tan ve Serkan Ylmaza teekkr ederiz.
5.KAYNAKLAR
[1] Bocchini G.F., Rivolta B., Silva G., Poggio E., Pinasco M.R., Ienco M.G., Microstructural and Mechanical Characterisation of some Sinter Hardening Alloys and Comparisons with Heat Treated PM Steels, Powder Metallurgy,
Vol. 47 No. 4, 343-351, 2004
[2] James W. B., What is Sinter Hardening, International Conference on Powder Metallurgy & Particulate Materials, May 31-June 4, 1998, Las Vegas, Nevada, USA.
[3] Hatami S., Malakizadi A., Nyborg L., Wallin D., Critical aspect of sinter-hardening of prealloyed Cr-Mo steel,
Journal of Materials Processing Technology 2010 1180-1189.
[4] Maroli B., Berg S., Larsson M., Hauer I., Performance of Sinter-Hardened P/M Steels, EUROMAT ITALY, 2001
[5] Blais C., Serafini R.E.Jr., LEsprance G., Effect of Hydrogen Concentration in Cooling Zone on Sinter Hardening, International Journal of Powder Metallurgy Volume 41, Issue 4, 33-41, 2005
[6] Rutz H. G., Graham A. H., Davala A. B., Sinter-Hardening P/M Steels, nternational Conference on Powder
Metallurgy & Particulate Materials, June 29-July 2, 1997, Chicago, IL USA.
[7] Causron R.J., Fulmer J.J., Sinter Hardening Low-Alloy Steels, Powder Metallurgy World Congress San
Francisco, CA, June 21-26, 1992.
[8] Engstrm U., Frykholm R., Milligan D., Warzel R., Cost Effective Materials for Sinter Hardening Applications,
PM2008 Washington, USA, June 11, 2008.
[9] Krauss G., Steels: Processing, Structure, and Performance, ASM International, 316-317, 2005
[10] Warga D., Lindberg C., Efficient Sintering and Hardening in the Conveyor Belt Sintering Furnace, 1993,
Powder Metallurgy World Congress, Kyoto, Japan, pp.983.
[11] Maroli B., Berg S., Larsson M., Hauer I., Performance of Sinter-Hardened P/M Steels, Euromat, Italy, 2001.
[12] Straffelini G., Fontanari V., Hafez A., Benedetti M., Tensile and Fatigue Behavior of Sinter Hardened Fe-15Mo0.6C Steels, Powder Metallurgy, Volume 41, Issue 4, 298-303, 2009.
555

556

557

CHARACTERIZATION
OF POWDER AND
PARTS
www.turkishpm.org
558

Abrasive wear behaviour of PMD 23 and M2 cold

work tool steels
Ferhat GL1, Melik ETN2
Gazi University, Technology Faculty, Metallurgical and Materials Engineering, Teknikokullar, Ankara, Turkey
2
Karabuk University, Technical Education Faculty, Division of Metal Casting,
Karabuk, Turkey 1fgul@gazi.edu.tr, 2mcetin@karabuk.edu.tr
ABSTRACT
In this study, abrasive wear behaviour of PMD 23 and M2 cold work tool steel produced through two different methods (powder metallurgy and conventional ) was investigated. The wear tests were carried out at sliding velocities
of 0.1 m s-1 and under 10 N, 20 N, and 30 N variable loads. The sliding distance was 10 m for all the tests and by
rubbing the specimens to abrasive Al2O3 grains with 38, 65 and 150 m. Abrasive wear tests revealed that, abrasive
wear loss increased with increasing abrasive particle size. The wear loses of PMD 23 steel was found to be lower
than that of the M2 cold work tool steel under the same test conditions.
Keywords: Wear, tool steel, abrasive grain size.
1. Introduction
The utilize of powder metallurgy (PM) processes to manufacture near-net-shape steel components has increased
quickly in current years, mainly because PM processes are capable of producing material compositions that are impractical to obtain by conventional casting processes[1,2]. Materials produced by PM processes acquire outstanding structural homogeneity and fine microstructure. Also these days, many high alloyed cold-working tool steels are
developed by advanced powder metallurgy (PM) methods, such as hot isostatic pressing (HIP), powder injection
moulding and spray forming and so on. On the consideration of their fine and homogeneous microstructure, high
alloyed PM cold-working tool steels with excellent strength and good wear resistance are presently employed for
stamping forming dies, industrial knives, slitters, plastic mold inserts and wear parts[3-6]. PM high alloyed coldworking tool steels are commonly strengthened by tempered martensite and high volume fraction of carbides [2].
PMD 23 is a new cold work-tool steel developed by Drrenberg Edelstahl, Germany. It is an development over the
familiar cold work-tool steel. PMD23 is a new tool steel, little information is available in literature related to its wear
behaviour. Therefore, in this study, the effect of microstructure on the hardness and abrasive wear behaviour of
PMD 23 and M2 cold work tool steel produced through two different methods (powder metallurgy and conventional)
conditions were determined.
2.Experimental procedure
Experimental study was performed on a PMD 23 and M2 cold work tool steel. The chemical composition of PMD
23 is 1.30C4.20Cr5.00Mo3.10V6.40W-Fe(wt.%), which was produced by Drrenberg Edelstahl, Germany.
M2 cold work tool steel chemical composition is 0.90C4.10Cr5.00Mo1.90V6.40W-Fe(wt.%), and it was made
by conventional method. The samples subjected to wear tests were wire cutted from the forged-and-soft annealed
master blocks. Then they were austenitized at 1180oC for 30 min in vacuum with uniform N2 gas quenching and
than they were tempered at 550oC for 3 h, the details of each step being illustrated in Fig. 1. Specimens for metallographic observations were prepared by grinding down to 1200 grit abrasive papers followed by polishing with 0.3
m diamond paste. The microstructure of the specimens was investigated by means of the optical microscopy. The
559

Vickers hardness of the PMD 23 and M2 cold work tool steel were determined using Instron Wolpert Testor DIA
Testor 7551 using a load of 1 kg and each hardness value is an average of 10 measurements. The hardness of the
tempered PMD 23 and M2 cold work tool steel are about 860HV1, 840 HV1, respectively.
Abrasive tests of the PMD 23 and M2 cold work tool steels were carried out on the two-body pin on disc apparatus
shown in Fig. 2 under the loads of 10 N, 20 N, and 30 N at the speed of 0.1 m s-1, by rubbing the specimens having 6,25 mm diameter and 50 mm length, on bonded abrasive Al2O3 abrasive. During the wear tests, specimens
that were rubbing on the abrasives were moving perpendicular to the sliding direction so that they always passed
over fresh abrasives. Six different particle sizes (38, 65 and 150 m) of abrasive Al2O3 abrasives were used to test
each specimen. Total sliding distance of the specimens on the abrasives were 10 m. Specimens were weighed,
before and after the test, using an electronic scale with a resolution of 104 g in order to determine wear losses as
weight loss. The abrasion tests were performed three times for each sample and the results were calculated using
the mean values.
Fig. 1. Schematically representation of heat treatments
Fig. 2.A schematic pin-on-disc wear test configuration

3. Result and discussion
Fig. 1(a) and (b) show the typical microstructure of the PMD 23 and M2 cold work tool steel after austenitized and
tempered, respectively. For typical austenitization temperature at 1180oC, the equilibrium phase situate consists
of the austenitic matrix and carbides. Microscopic examinations revealed that light coloured needle like vanadium
carbides and they are regularly distributed in the tempered martensitic matrix. Previously, vanadium carbides in
microstructure of cold work tool steel after austenitized and tempered have also been reported [4, 7]. The carbides
in the martensitic matrix produce an natural wear resistance [7].
560

Fig. 3: Microstructure of the specimens (a) PMD 23 cold work tool steel (b) M2 cold work tool steel
centrifugally casting
Results of abrasive wear tests on the PMD 23 cold work tool steel and M2 cold work tool steel after austenitized
and tempered, are shown in Fig. 4 and Fig. 5, respectively. The weight loss of the PMD 23 and M2 cold work tool
steels increased with increasing the applied load, and abrasive particle size. PMD 23 cold work tool steels (high
vanadium steels) exhibit low weight loss than M2 cold work tool steel under the loads of 10-30N for all the abrasive
particle sizes (Fig. 4 and Fig. 5). They are excellent candidates for replacing sintered carbides and other materials
that are highly resistance to wear in machinery. The most important result of the abrasive wear test is that abrasive
Al2O3 grain size and applied load have an important effect on the wear lose of the investigated PMD 23 and M2 cold
work tool steels Fig. 4 and Fig 5 obviously shows that, abrasive wear lose of PMD 23 and M2 cold work tool steels
increased with increasing abrasive grain size in accord with the work of Cetin and Gul [8] and Shue and Lin [9].
Fig. 4: The effect of the size of abrasive

Al2O3 grain and loads on the wear loss of
the PMD23 cold work tool steel
Fig. 5: The effect of the size of abrasive

Al2O3 grain and loads on the wear loss of
the M2cold work tool steel
561

Conclusion
An experimental study of wear behaviour of PMD23 and M2 cold work tool steel used in this investigation at different
load and the size of abrasive Al2O3 grains value reveals the following conclusion:
1. The microstructure of the PMD23 cold work tool steel had finer grains than M2cold work tool steel. Decreasing
grain size led to increase in hardness
2. Wear lose values increased with the increment of load and abrasive Al2O3 grain size
3. The wear lose of PMD23 steel was found to be lower than that of the M2 cold work tool steel under the same
test conditions.
Acknowledgement
The authors are thankful to Saglam Metal (Istanbul-TR) and and Mr. Fatih YALAVA for providing PMD23 cold work
tool steel.
References
1.
2.
3.
4.
5.
6.
7.
8.
9.
R.M. German, Powder Metalurgy of Iron and Steel, John Willey and Sons, U.S.A.
K. S. Narasimhan, Materials Chemistry and Physics, Volume 67, Issues 1-3,2001, Pages 56-65
H.K. Moon, K.B. Lee, H.Kwon, Materials Science and Engineering A 474 (2008) 328334
S. Weber, W. Theisen, F. Castro, A. Pyzalla, Materials Science and Engineering: A, Volume 515, Issues 1-2,
25 July 2009, Pages 175-182
J. Richter, Materials Characterization, Volume 50, Issues 4-5, June 2003, Pages 339-347
J. Yao, X.H. Qu*, X.B. He, L. Zhang, Materials Science and Engineering A 528 (2011) 41804186
R.M. Muoz Riofano, L.C. Casteletti, L.C.F. Canale, G.E. Totten, Wear, Volume 265, Issues 1-2, 25 (2008)
57-64.
M.etin and F.Gul, TEKNOLOJ, Cilt 11(2), 137-144, (2008).
C-Y. Sheu, S.-J. Lin, Scripta Materialia, Volume 35, Issue 11, 1 December 1996, Pages 1271-1276
562

SOME PROPERTIES OF CLINOPTILOLITE AFTER

LONG-TERM HOT ACID LEACHING
Osman AN*, Remzi GREN*, Cem ZGR*, Muhterem KO**, Tuba ERGLER*, Ali MARETL*
*
Dumlupnar University, Department of Ceramic Engineering, Ktahya, 43100, Turkey,
osmansan@dumlupinar.edu.tr, rgoren@dumlupinar.edu.tr, cozgur@dumlupinar.edu.tr,
tubaerguler@gmail.com, imaretli@gmail.com
**
Celal Bayar University, Turgutlu Vocational School, Department of Industrial Glass and Ceramic, Manisa,
45400, Turkey, muhterem.koc@bayar.edu.tr
ABSTRACT
This study presents an investigation on the purification of a natural zeolite (clinoptilolite) by acid leaching conducted
in hot solution (75C and 5 M HCl) for the period up to 72 h and examines some properties of the powder samples
such as change in chemical compositions, specific surface areas, X-ray detected phases and size of the particles.
The treatment increased the specific surface area from 47.87 m2/g to 154.3 m2/g, with the SiO2 content being 97.5
wt.%. The reduction of aluminum, potassium, iron and calcium oxides was significant. The longer time leaching
removed the clinoptilolite phase but did not remove the impurity phases such as cristoballite, quartz and tridimite.
The leaching process significantly decreased the size of particles. The material may potential be used as high silica
ceramic powder.
Keywords: Zeolite powders, chemical preparation, silicate
1. Introduction
Abundant deposits of zeolitic tuffs have been discovered in many countries. Among them, clinoptilolite is the most
common and industrially important natural zeolite. It is a natural zeolite mineral from the tectosilicates group. Its typical unit cell formula is Na6[(AlO2)6(SiO2)30] 24H2O [1]. The most important property of clinoptilolite is its high cation
exchange capability which makes it a potential candidate in the removal of inorganic contaminants from water and
wastewater [2-5]. In addition, it is also possible to remove nonionic organic contaminants in liquids by a modified
clinoptilolite through adsorption of cationic surfactants [6]. In addition, clinoptilolite is abundant and inexpensive,
making this zeolite an attractive alternative to use of a ceramic powder. Fusibility of the clinoptilolite at relatively low
temperatures has great importance since they are used in the ceramic industry as sintering aids [7-8]. Recently, a
natural zeolite was used as a phase-transforming agent for quartz to cristobalite [9]; the zeolite was melted at a low
temperature (around 800C), and further heating provided good dispersion of the liquid phase through the quartz
particles.
The chemical modification of zeolites by acid can increase both porosity and the capacity of adsorption. However,
not only adsorption capacity of the material is altered, but acid treatment could also alter the secondary porosity and
the crystalline network of the zeolite [10]. It is necessary to investigate the chemical changes produced by the acidic
treatment of zeolites in order to verify that the desired improvements occur without altering properties of interest for
the final application. In this study, the clinoptilolite was investigated as high silica- containing ceramic powder. For
this purpose, the clinoptilolite powder was leached for long-term treatment.
2. Materials and Methods
Natural zeolite (clinoptilolite) was obtained from a mine located at Manisa-Grdes in Turkey (Enni Mining). The
sample was wet ground in attrition mill for 1 h using alumina balls. The slurry was dried at 105oC for 24 h, and then
563

leached in 5 M HCl solution at 75oC. The treatment duration was selected as 72 h [11]. During leaching, 10 g of
clinoptilolite sample was weighed and poured into 200 ml of solution, the solution was then stirred continuously at
500 rpm using a magnetic stirrer and a thermostat was used to keep the reaction medium at constant temperature.
After a predetermined period of time, the solid product was filtered and washed with distilled water.
The study of the samples included: (i) chemical composition measurement by X-ray fluorescence (Spectro X-LAB
200), (ii) crystalline phase identification by X-ray analysis (Rigaku Miniflex powder diffractometer employing CuK
radiation in 2 = 10-65o at a ganiometer rate of 2 = 2o/min.), (iii) particle-size determination by zeta sizer (MalvernNano S) and (iv) determination of specific surface areas by BET (Quantachrome-Nova 2200e).
3. Results
3.1. Dissolution during leaching
The raw clinoptilolite powder was treated in hot-acid solutions of 5M HCl at 75 C to remove impurities such as,
alkaline earth and alkali metal compounds as well as the alumina. The amount of total dissolving components from
the powder sample was determined as 25 wt.% for the long-term processing (72 h).
3.2. Analysis of the crystal structure
3.2.1. The as-received clinoptilolite
The X-ray diffraction analysis of the raw clinoptilolite powder is given in Fig. 1. It shows an essentially clinoptilolite
phase with crystalline phases which are cristobalite, quartz and tridymite.
Figure 1. XRD pattern of as-received clinoptilolite powder.

3.2.2. The leached clinoptilolite
After leaching, the clinoptilolite phases of the sample undergo and the other crystalline phases such as cristobalite,
quartz and tridimite could not be removed. The long-term leaching showed that during stirring the presence of hard
constituents in the solvent medium tended to facilitate the break-down of coarse clinoptilolite particles. This phenomenon induced a more amorphous structure and the shapes of amorphous peaks became broader.
3.3. Influence of leaching time on chemical composition
Changes in the chemical compositions of the as-received clinoptilolite after leaching for 72 h are given in Table 1.
The de-alumination of the powder material was succeeded and the iron contamination was significantly reduced.
The leached powder samples exhibit less crystalline structure (see Fig. 2) and being a high-grade silica material,
having more than 97 wt.%SiO2.
564

Figure 2. XRD pattern of leached clinoptilolite powder.

Table 1. Chemical composition of the as-received and leached clinoptilolite (wt.%).
Oxides
SiO2
Al2O3
K2O
Fe2O3
CaO
Na2O
MgO
TiO2
MnO
P2O5
SO3
As-received
83.88
8.27
3.67
1.77
1.81
0.26
0.64
0.10
0.04
0.02
0.02
Leached
97.50
1.00
1.10
0.48
0.084
0.02
0.31
0.07
0.01
0.02
0,02
3.4. Influence of leaching times on particle size and distribution

The size distributions of the untreated and leached clinoptilolite powders were investigated by zeta sizer (MalvernNano S). Fig. 3 presents the plot of cumulative mass percent finer versus particle size. After leaching the particle
size of the sample became finer due to fracture of the large particles and the sample acquired a monomial and
narrow size distribution.
Figure 3. Size distributions of raw and leached clinoptilolite powders.

3.5. Influence of leaching on the specific surface area
The BET surface area values of the raw and leached powders are given in Table 2. As evident from the table, the
surface area of clinoptilolite greatly increased after the leaching. The reason for the increase in the specific surface
area could mainly be due to the breakdown and/or very intensive erosion of the larger particles through the longterm processing.
Table 2. Specific surface area of the clinoptilolite with and without leaching.
Samples
Raw clinoptilolite
Leached clinoptilolite
Specific surface area, m2/g

47.87
154.30
565

4. Discussion
Motivation of the present study was the previous finding that a high silica-containing ceramic powder has been investigated from diatomite where a low-grade diatomite having 68.08 wt. % SiO2 was leached through long-term
(240 h) and a high silica-containing material containing 98 wt. % SiO2 was obtained. Phase analysis of the sample indicated a highly amorphous structure and the remaining phase was only a small quantity of quartz [11]. The
powder was used for the fabrication of beta-cristobalite ceramic material for filtration application in harsh thermal
environments. The small amount of impurities had no significant influence on the thermal behavior of the ceramic
material and the thermal expansion coefficient was found as 11.42 x 10-6C-1 [12].
The present study indicated that the leached clinoptilolite for 72 h has great potential for the production of betacristobalite ceramic material with high silica-content which could be obtained after a shorter time treatment (72 h)
and the resulting impurities would be quite low.
5. Conclusion
These following salient conclusions related to the leaching treatment can be made:
1. High SiO2 ceramic powders having 97 wt.% SiO2 can be successfully prepared from impure raw zeolite (clinoptilolite) after a prolonged time (72 h) of hot-acid (75C and 5 M HCl) leaching.
2. When the raw zeolite powder is treated with hot acid solution (5 M HCl) for the longer time (72 h), the surface
area of powder increases from 47 to 154 m2/g.
3. The leaching process provides a decrease in average particle size significantly from 825 nm to 100 nm.
4. Also, the leaching process makes possible the production of ceramic powders containing high-silica with several ratios by adjusting the leaching conditions.
REFERENCES
[1] T. Armbruster, Studies in surface science and catalysis, in: A. Galarnau, F. Di Renzo, F. Faujula, J. Vedrine
(Eds.), yqq1, vol. 135, Elsevier, Amsterdam, 2001.
[2] D.W. Breck, in: Zeolite Molecular Sieves, John Wiley, New York, 1974, pp. 529588.
[3] N.A. Hernndez-Beltrn, M.T. Olgun, Elemental composition variability of clinoptilolite-rich tuff after the treatment with acid phosphate solutions, Hydrometallurgy 89 (2007) 374378.
[4] J. Hlavay, G. Vigh, V. Olaszi, J. Inczedy, Ammonia and iron removal from drinking water with clinoptilolite tuff,
Zeolites 3 (1983) 188-190.
[5] G. Blanchard, M. Maunaye, G. Martin, Removal of heavy metals from waters by means of natural zeolites,Water
Res. 18 (1984) 1501-1507.
[6] B. Ersoy, Adsorption mechanisms of cationic surfactants onto clinoptilolite and removal of non-ionic organic contaminants by modified clinoptilolite , Ph.D. Thesis, Istanbul Technical University, Istanbul, 2000, p. 212.
[7] F. Andreola, T. Manfredini, E. Passaglia, G.C. Pellacani, P. Pozzi and M. Romagnoli, Utilization of an Italian
Zeolite in ceramic bodies, Materials Engineering, 5 (1994) 299-312.
[8] R. de Gennaro, P. Cappelletti, G. Cerri, M. de Gennaro, M. Dondi, G. Guarini, A. Langella and D. Naimo, Influence of zeolites on the sintering and technological properties of porcelain stoneware tiles, Journal of the
European Ceramic Society 23 (2003) 2237-2245.
[9] O. an, S. Abal and . Hoten, Fabrication of microporous ceramics from ceramic powders of quartz-natural
zeolite mixtures, Ceramic International, 29 (2003) 927-931.
[10] N.A. Hernndez-Beltrn, M.T. Olgun, Elemental composition variability of clinoptilolite-rich tuff after the treatment with acid phosphate solutions, Hydrometallurgy, 89 (2007) 374378.
[11] O. an, R. Gren, C. zgr, Purification of diatomite powder by acid leaching for use in fabrication of porous
ceramics, Internal Journal of Mineral Processing, 93 (2009) 6-10.
[12] O. an, C. zgr, Preparation of a stabilized cristobalite ceramic from diatomite, Journal of Alloys and
Compounds, 484 (2009) 920-923
566

Investigation on the Use of Natural Zeolite

for Ceramic Pigment
Eda Tasci1, Mustafa Tuncer1 and Ismail Ozden Alp2
1
Dumlupnar University, Ceramic Engineering Department, Kutahya, TURKEY

2
Altn Ceramic Company, Kutahya, TURKEY
Abstract
Pigments for ceramic glaze were obtained by treating clinoptilolite type-natural zeolite with aqueous solution of
FeCl3. The powders calcined at different temperature were characterized using X-ray diffraction, chemical analysis.
Coloring properties of pigment powders tested in transparent floor tile glaze was analysized using LAB instrument.
The results showed that the whiteness value (+L) of pigments decreased while redness value (+a) increase with
increasing calcination temperature from 1000 to 1200 oC. It can be started that natural zeolite with ion exchange are
expected to be useful for ceramic pigment.
Keywords: Pigment, clinoptilolite, ion exchange.
1. Introduction
The term pigments is applied to black, white and colored organic or inorganic powders that are insoluble in the substrate in which they are incorporated not chemically and physically altered by it [1]. Ceramic pigments were synthesized by solid-state reactions and the color developed in a suitable ceramic glaze was investigated in comparison
with the color developed by the pigments prepared from pure SiO2. Raw materials which are mostly metallic oxides
or salts of the desired metals with industrial chemical purity are used for pigment production [2].
Some minerals are employed as host materials for colorant ions because of specific crystal structure. One of these
is naturally occurring zeolites. They are microporous aluminosilicate materials with wide use in catalysis, molecular
sieving, animal nourishment and slow release fertilizers [3]. These applications are related to their structure with
cages and channels of molecular size ranging from about 2- 15 in size. The replacement of Si+4 by Al+3 creates
negative charge in zeolite framework. This charge is compensated by cations positioned in the structure. These
cations can easily be inserted into framework, leading to new ceramic phase. So the new materials can be development [4]. The aim of present study was to produce ceramic pigments based on zeolite previously exchanged with
colorant ions. FeCl3 was chosen as colorant agent.
Industrial quality clinoptilonite-type zeolites have been used as starting raw materials for the pigment preparation.
Firstly, zeolite was leached to eliminate cations such as sodium, potassium and calcium that are in the pores of zeolite and then ion exchange procedure was conducted as follow. In a 300 cc glass bottle, FeCl3.6H2O (5.5 g) was dissolved in 200 cc of deionized water and mixed until to get clear solution. The leached zeolite (5.2 g) was dispersed
in Fe-solution. The bottle was sealed and kept at 70 oC for 2 days. This procedure was repeated three times. The
powders were filtered, subsequently washed for twice with 50 ml distilled water. It was centrifuged at 9000 rpm for
5 min, dried at 90 oC overnight and finally gentle crushed in agate mortar. The obtained mixture has been calcined
in a closed porcelain crucibles at different temperatures (1100, 1175 and 1200 oC) for 60 min of soaking time and
then dry milled. The phase content of powders were identified by X-ray diffractometer (Rigaku, Miniflex) using Cu
K radiation over the range of 2080o at a rate of 2o/min. the oxide content were determined by X-ray fluorescence
567

(Spectra). The morphology and microstructure of the powders have been examined by Scanning Electron Microscopy (SEM, Zeiss Supra 50 VP )
The obtained powders have been tested as pigments for glaze coloring. A ceramic glaze, having a typical composition for porcelainized stoneware, has been used for pigment application. The pigments, added to the composition at
3 wt%, have been wet mixed with the ceramic frit for 30 min in a blender-mixer and then dried. The dried powders
have been pressed at 40 MPa to produce wires (40mm diameter) that have been fired in an industrial high-speed
roller kiln using a typical industrial cycle of 40 min. Color measurements have been performed on both pigments
and glazes by UVvis spectroscopy (model Lambda 19, Perkin Elmer) using the CIElab method in order to obtain
L*, a* and b* values.
3. Results and Discussion
Table 1 reports the chemical analysis of clinoptilolite type zeolite. Regarding the loss of ignitions the elemental
analysis defines that the hydrogen content is 0.15 wt %, the nitrogen content is 0.16 wt % while the carbon content
is 11 wt % in accordance with light green color of the zeolite. The chemical analysis, thus, confirms that the as received clinoptilolite type zeolite, though with 11 wt% of loss of ignition, is a waste that contains a 67 wt% of very pure
silica. Other oxides are all lower than 3 wt%; the chromofore oxides, in particular Fe2O3 and TiO2, that can influence
the color developed by the pigment in a ceramic matrix, are present only as traces. After the exchange process, the
amount of iron oxide in zeolite was increased from 1.79 to 3.55.
Table 1. Oxide composition of raw and exchanged zeolite
Oxides (%)
SiO2
Al2O3
Fe2O3
CaO
MgO
K 2O
Na2O
TiO2
LOI**.
Total
Raw Zeolite
67,1
11,8
1,79
3,87
1,21
2,29
0,3
0,11
11,49
100
Exchanged
Zeolite
84,71
6,11
3,55
0,63
1,04
1,09
2,86
99,99
Fig. 1 shows XRD pattern of raw zeolite. Clearly, it had clinoptilolite phase with minor silica.
Fig. 1. XRD patterns of raw zeolite (Q: Kuvars, C: Klinoptilolit, P: Olajioklas).

Fig.2. shows XRD patterns of ion exchanged-clinoptilolite calcined at different temperature. The XRD results
showed cristobalite was main phase. Fe-exchanged clinoptilolite was transformed to new ceramic phase, which is
cristobalite. This new phase acted as host crystal for Fe ion.
Fig.2. XRD analysis of Fe-exchanged zeolite calcined at different temperature (C: cristobalite).
568

The successful formation of the cristobalite based pigments has been also confirmed by colorimetric analysis. In
fact, the b* parameter, indicating the predominance of the yellow color (+b*) on the blue color (b*), increases with
the calcination temperature, irrespective of the silica precursor used. The color developed by the two precursor is
quite the same and reach the higher yellowness at 1200 oC. For this reason only the pigments calcined at 1100 oC
have been used to verify their chemical stability in a ceramic glaze. The color developed by these pigments added
both at 3 wt% in an industrial glaze for high temperature is reported in Table 2. The table shows that Table 1. L*a*b*
values for the sintered pigments and the applications (glazes 3 wt% of pigment).
The obtained pigments developed a good yellow color, irrespective of the raw materials used, indicating the chemical and thermal stability of the synthesized powders.
Table 2. CIElab values of the obtained glazes.
Colour parameters
Thermal Treatment
Hue
(C)
1100
89,32
0,49
4,72
Light pink
1175
81,75
6,38
16,89
Middle pink
1200
77,43
9,99
23,6
Pink
4. Conclusion
Fe-exchanged zeolite was successfully produced using ion exchange procedure. The Cristobalite type structure
formed after heat treatment. The obtained pigments were stable and develop an intense pink color that is very
similar to the colored by the pigments obtained starting from pure quartz. The result showed that the clinoptilolite
type zeolite can be used as host material for coloring.
Acknowledgements
The authors would like to thanks Ceramic Engineer Mehmet Akkas for XRF Analysis.
References
1. P. A. Lewis, Pigment Handbook, (1988), Vol. I, 2nd Ed., John Wiley & Sons, New York, USA 945 pp.
2. Federica Bondioli, Fernanda Andreola, Luisa Barbieri, Tiziano Manfredini and Anna Maria Ferrari, Effect of rice
husk ash (RHA) in the synthesis of (Pr,Zr)SiO4 ceramic pigment, Journal of the European Ceramic Society 27
(2007), p.34833488.
3. V. M. PogrebenkovandM. B. Sedelnikova, Ceramic Pigments Based on Natural Minerals, Glass and Ceramics,
Volume 59, Numbers 11-12,396-399.
4. V. M. Pogrebenkov,M. B. SedelnikovaandV. I. Vereshchagin, Zeolites: Raw material for ceramic pigments,
Glass and Ceramics, Volume 55, Numbers 1-2,55-56.
569

FUNCTIONAL GRADED HARD METALS PREPARED

BY POWDER METALLURGY
Irina CARCEANU*, Emilia Maria COMAN (CIOVICA)**
Metallurgical Research Institute of Bucharest, 39 Mehadia Street, code 060543,
6 County, Bucharest Romania, irina_carceanu@yahoo.co.uk,
**
VALAHIA University of Targoviste, 2nd Carol I Street, code 130024, Targoviste, Dambovita Romania,
emilia_ciovica@yahoo.com
*
Abstract
WC-Co cemented carbides are widely used as machining tools, mining tools and wear resistant parts. Multilayer
graded structures with Co/Ni content from 10 to 30 wt% from one side of the structure to the other, have been
prepared by using either solid-state or liquid - phase sintering. This paper presents briefly the experimental works
performed for manufacturing parts from functional graded hard metals with designed structure aiming at the wear
resistance increase.
Keywords: Functional graded hard metals; Multilayer graded structures; Mining inserts;
INTRODUCTION
The necessity to improve continuously the working performances of the parts equipping mining tools requires new
materials with mechanical properties superior to those of the existent ones, these new materials being obtained
as well by changing the chemical composition as the method of material making. The obtaining of materials with
designed structure based on sintered hard metals, by using powder metallurgy technologies, which determine
changes just during the processing, were considered from the beginning as an attractive alternative to the current
manufacturing methods. The advantages of this technology concern both economic aspects and practically unlimited possibilities of using specific methods for pulverous materials processing in order to obtain various functional
combinations.
EXPERIMENTAL TECHNIQUE
In the case of obtaining WC-Co materials with designed structure, a world-wide accepted method presented in the
paper consists in creating the property gradient in one stage of the technological stream, i.e. during the stage of
powder compaction by an adequate pressing method, followed by liquid phase sintering.[1]
Experiments, which are furtheron briefly emphasized, had in view to realize those tungsten and cobalt carbide compositions in optimal alloys, which confer as well resistance to abrasion as to shocks and determine an optimal behaviour of the parts used for percussive rotary drilling under extreme conditions imposed by their efficient using[2].
Taking into account the above mentioned considerations, the selected hard metals systems are the following: WCCo hard metals system (G 20 grade);WC-(Ta, Nb) C - Co hard metals system (K 45 grade).
The pressing, binder removal-presintering and sintering operations were the targets of the experimental works, in
order to analyse the repeatability of the main technological parameters specific to powder metallurgy, having in view
the obtaining of inserts with performant physico-mechanical and structural properties.
The standardized profiles of the grades for core bits, G 115 code, are presented in figure 1. The tips of G 115 type
equipping the removable heads of the tools for percussive rotary drilling are used for rocks excavation in the underground exploitations.
570

Figure 1 The shape of G115 mining inserts

RESULTS AND DISCUSSIONS
Having in view the above presented, the aim was the creation of this tip type from sintered hard metals with Co
structural gradient, the working part of which has to be realised from an alloy, which is harder than the sublayer, but
of comparable toughness.
After the die manufacturing, the compacts were obtained by cold pressing on an self-acting press with mechanical
driving and volume filling. Table 1 presents the pressing characteristics of the double-layer compacts obtained by
successive batching of the powder into the die, the batching being calculated so that the upper part should contain
the whole working part of the piece and lie minimum 3 mm under the cap boundary line.
Table 1. Pressing characteristics of the G 115 tip obtained from a double-layer material
Double-layer
Mass
Upper layer
[g]
21,5
G 115 grade
K 45 / G 20
Bottom layer
[g]
63
Specific
Pressure
[ daN/cm2 ]
1455
The parts formed by cold pressing at the above mentioned specific pressure were submitted to binder removal-presintering in a periodic electrically heated furnace with Kanthal resistances in reducing flow (hydrogen at 220 l/h) at
a temperature of 800 C with two holding levels at 380 C and 450 C of approx. 30 minutes each. The intermediary
holding levels of 380 C and 450 C are necessary, because they provide the temperature equalization in the charge
mass and paraffin is completely removed before it is decomposed on pieces or furnace walls.
After pressing and binder removal-presintering the parts were submitted to sintering in order to obtain the set of properties, required by the working conditions: TRS = min. 2400 N/mm2 and HV 30 = min. 1300. The sintering operation
was performed in a BALZERS type vacuum induction furnace showing following operation parameters: sintering
temperature: 1370 C; sintering atmosphere: vacuum; the holding time at sintering temperature: 40 min.; total cycle
time: 8 h. The obtained density values are presented in table 2.
Table 2. Apparent density values determined on the lot parts.
Mean values
[g/cm3]
14.25
Average density
[ g/cm3 ]
14.21
14.18
14.21
Table 3 presents the values of the bending breaking strength determined on sintered specimens with parallelepipedic shape from the heat containing also parts from the testing lot.
Table 3. Values of the bending breaking strength determined on sintered specimens.
Transverse rupture strength
[ N/mm2 ]
Average values [ N/mm2 ]

2420
2480
2460
2454
571

In order to emphasise the structural gradient created during the processing, the the cobalt content variation was
studied at the interfaces of the double-layer parts, on a cross section, by electron microscopy with an ELECTROSCAN Philips microscope equipped with EDAX system for the quantitative analysis of elements, by passing over the
piece from the point 1 to the point 7 and maintaining a x 1250 magnification - figure 2.
Figure 2. EDAX quantitative analysis on K 45 - G 20 system.

One used a window of 25 x 20 m size , i.e. with a surface of 500 m2, representative for each analysed zone.
Figures 3 and 4 shows the microstructure of the interface zone.
Figure 3-4. Microstructures of the G20/K45 separation interface Murakami etching 2000X
On the basis of performed experimental works it was established and finalized the technology for manufacturing
mining inserts of G115 type from materials with structural gradient and thus, the testing lot was obtained. The physico-mechanical and dimensional characteristics of the parts of the testing lot are presented in table 4.
Table 4. Physico-mechanical and dimensional characteristics of the G115 parts corresponding to the
manufactured testing lot.
Average density
[ g/cm ]
14.18
3
Transverse rupture
strength
[ N/mm2 ]
2460
572
Hardness
HV 30
[ N/mm2 ]
12811314
Shrinkage
[%]
18,2

ConclusIons
The results of the performed experiments and tests, which are presented shortly in this paper, allowed the following
conclusions:
The sintered hard metals with structural gradient are obtained on powder metallurgy base, by successive batching in the stage of bilateral pressing, followed by liquid phase sintering, at the end of which the material structure is finalized. The mass transfer phenomena taking place during the liquid phase sintering, which characterizes
the WC-Co systems, allowed the obtaining of a Co structural gradient depending on the Co concentrations of
the contact layers.[3]
One obtained in the pressing stage, by powder successive batching, multi-layer compacts with a stationary Co
gradient, the Co content for each layer being the following:
- in the upper layer, corresponding to the working cutting part of the insert, the Co content amounts to 15% and in
the bottom part 12%. [2]
The Co structural gradient finalized in the heat treatment stage, emphasised and quantized by electron microscopy, varies at the end of the sintering stage from the upper part to the bottom from 13,76 to 12,18% Co. [2]
The structural gradient determined on one hand a hardness variation, so that in the working zone the hardness
was the expected one and the assemble toughness - of minimum 2400 N/mm2. [2]
All analysed specimens of the testing lot showed the presence of an admissible remanent porosity, A 01,
without free carbon, thus highlighting the fact that heat treatment regimes are adequate and characteristics
repeatability is guaranteed.
References
1. K. Dreyer, D. Kassel, Functionally Graded Hardmetals and Cermets Preparation, Performance and Production Scale Up, 15-th International Plansee Seminar, Vol 2, Reutte, 2001.
2 C.Coman & others Multilayer hard alloy designed for hard rock dislocation, Matnantech Project C 81, (20012002).
3 C. Colin Processing of composition gradient WC-Co Cermet, 13-th International Plansee Seminar, Vol 1,
Reutte, 1993, pag. 522-537.
573

Yalandrma ISIL leminin tOZ ENJEKSYON KALIPLAMA METODU

LE RETLM Speralamlarn Anma Davranna Etkisi
zgr ZGN*, H. zkan GLSOY**, Ramazan YILMAZ***, Fehim FINDIK****
*Bingl niversitesi, Teknik Bilimler Meslek Yksekokulu, Bingl, Trkiye, oozgun@bingol.edu.tr
**
Marmara niversitesi, Teknolojoji Fakltesi, Gztepe, stanbul, 34722, Trkiye
**
TBTAK MAM, Malzeme Enstits, Gebze - Kocaeli, 41470, Trkiye, ozkan.gulsoy@mam.gov.tr
***
Sakarya niversitesi, Teknik Eitim Fakltesi, Metal Eitimi Blm, Esentepe Kamps, 54187, Sakarya,
Trkiye, ryilmaz@sakarya.edu.tr
****
International University of Sarajevo, Faculty of Engineering and Natural Sciences
Department of Mechanical Engineering, 71000 Sarajevo, Bosnia-Herzegovina, ffindik@ius.edu.ba
ZET
NI 718 speralam, oda scaklnda sahip olduu yksek mukavemet deerlerini yksek scaklklarda da muhafaza edebilmesinin yannda stn korozyon direncine de sahip olmasndan dolay zellikle havaclk ve otomotiv
sektrlerinde yaygn uygulama alan bulmaktadr. Bu almada, NI 718 numuneleri karmak geometrilere sahip
paralarn hassas llerde, ince taneli, homojen iyapl ve stn mekanik zelliklere sahip olmasn salayabilen
Toz Enjeksiyon Kalplama (TEK) metodu kullanlarak retilmilerdir. Optimum younluk salayan scaklk ve srede
retilen paralara yalandrma sl ilemi uygulanmtr. Isl ilemlerin malzemenin anma davranlarna etkisi
aratrlmtr. Uygulanan yalandrma ileminin malzemenin anma direncine olumlu etki yapt ve ama deneylerinde uygulanan yk ve kayma hznn artna paralel olarak anma kaybnda iddetli art meydana geldii
tespit edilmitir.
Anahtar Kelimeler: Toz Enjeksiyon Kalplama (TEK), speralam, NI 718, anma,
The Effect of Aging Treatment On Wear Behavior of pOWDER

INJECTION MOLDED Superalloys
ABSTRACT
NI 718 superalloys are widely used especially in aerospace and automotive sectors due to having higher strength
at both room temperature and elevated temperatures, and also superior corrosion resistance. In this study the
samples of NI 718 superalloys were produced by Powder Injection Moulding (PIM) process, which provides fine
grained homogeneous microstructure of the materials with the net shape size of complex shaped of the pieces with
the superiors mechanical properties. Age treatments were applied on those superalloys produced by using suitable
sintering temperature and duration at which optimum density was provided. The effects of age treatments on the
wear behaviours were investigated. The aging has positive effectives on the hardness and wear resistance of the
materials. On the other hand, the load and sliding speeds has great influences on the wear behaviour of the materials. Wear loses increases by parallel increasing of the loads and sliding speeds applied during wear tests.
Key words: Powder Injection Moulding (PIM), superalloy, NI 718, wear
1. GR
Bir toz metalurjisi ilemi olmasna ramen geleneksel kalpla presleme ile retilen paralardan daha yksek younluk ve dolaysyla daha stn mekanik zellikler elde edilmesini salayan Toz Enjeksiyon Kalplama (TEK)
574

teknolojisi, gerek talal imalat gerekse de dkm yntemlerine nazaran daha karmak ekilli paralarn yksek
yzey kalitesine sahip olacak ekilde yksek l hassasiyetiyle retilebilmesine olanak tanmakla kalmaz; bunun
yannda ince tane yapsna sahip ve kimyasal bileimi her yerinde homojen olan paralarn ekonomik olarak retilmesini de salar [1].
Yksek scakla dayankl bir alam snf olan speralamlar nikel, nikel-demir veya kobalt esasl olabilmektedirler. Speralamlar hem kriyojenik scaklklarda hem de yksek scaklklarda mukavemet ve yzey kararllnn
mkemmel bir kombinasyonunu sergilemektedirler [2]. NI 718 bugn dnyada en ok kullanlan speralamdr [3].
NI 718 kelme ile sertletirilebilen nikeldemir esasl bir speralam olup, iyi korozyon direnci ve yksek mukavemet ile stn kaynak edilebilirlik ve yksek scaklklarda (~650oC) mikroyapsal kararllk gibi zelliklerin belirgin
bir kombinasyonuna sahip olmasndan dolay gaz trbinlerinde, roket motorlarnda, uzay aralarnda, nkleer reaktrlerde, pompalarda ve takmlarda yaygn olarak kullanlmaktadr. NI 718de mukavemet artrma mekanizmasn
temel olarak kbik veya kresel ekilli nano llerdeki Ni3Al ve lens gibi disk ekilli Ni3Nb keltileri oluturmaktadr [48]. 718 alam ounlukla geleneksel dkm yntemi ile retilmektedir. Fakat elementel segregasyon
ve arzu edilmeyen fazlarn olumas byk boyutlu ingotlarn retiminde karlalan ciddi problemlerdir [9]. NI
718 alamndan bu dkm hatalarnn elimine edilmesi zaman alc ve pahal olan bir sre gerektirmektedir [10].
Uygulanan sl ilemlerle malzemelerin daha mukavemetli ve daha yksek anma direncine sahip olmalar umut
edilmektedir. Paralara uygulanan sl ilemlerin anma davranlarna etkisi ile sertlik davranlarnn karakterize
edilmesi bu tr malzemelerin zelliklerinin gelitirilmesi bakmndan ilgin olacaktr. Bu nedenlerden dolay bu almada gaz atomizasyonu ile retilmi n alaml NI 718 tozlar TEK teknii ile ekillendirilmi ve daha sonra optimum scaklk ve srede sinterlenerek retilmitir. retilen paralara yalandrma sl ilemi uygulanmtr. Bylece
uygulanan sl ilemin bu tr malzemelerin sertliine ve anma davranlarna etkisi aratrlmtr.
Deneylerde Osprey firmas tarafndan gaz atomizasyonu yntemi ile retilmi n alaml NI 718 tozu kullanlm
olup bu tozun kimyasal bileimi Tablo 1de verilmitir. Tozun tane boyut dalmnn belirlenmesi amacyla Malvern
Mastersizer marka cihazla gerekletirilen analize ait eri ekil 1de, toz eklinin belirlenmesi amacyla ekilmi
olan SEM grnts ekil 2de verilmitir. Tablo 2de toza ait baz zellikler gsterilmitir.
Tablo 1. Kullanlan NI 718 speralam tozunun kimyasal kompozisyonu
% arlk
NI 718
Ni
Cr
Fe
Nb
Mo
Al
Ti
Si
Mn
52,300
18,7
19,306
5,0
3,1
0,33
0,71
0,011
0,29
0,24
ekil 1. Deneylerde kullanlan NI 718 tozuna ait tane boyut dalm erisi
Hacimce % 60 ana toz ve %40 balayc ierecek ekilde tasarlanan besleme stou, NI 718 tozu ile parafin mum,
brezilya mumu, polipropilen ve stearik asitten oluan ok bileenli balayc sisteminin zel olarak tasarmlanm bir
kartrcda 170oCde ve vakum altnda 30 dk kartrlmasyla oluturulmutur. Oluturulan besleme stou granle
edilerek 12,5 MPa basn ve 20 saniye tutma sresi ile standartlara uygun olacak ekilde kalplandktan sonra
575

balayc giderme ilemine tabi tutulmulardr. Balayc giderme ilemi 70oCye karlm heptan ierisinde 6 saat
bekletilen numunelerin almina altlk stnde ve vakum ortamnda 2oC/dk stma hz ile stlrken 200, 400, 500
ve 600oC scaklklarda 2er saat bekletildikten sonra yine 2oC/dk hzla 900oCye stlp burada bir n sinterlenme
meydana gelecek ekilde 1 saat bekletilmesi eklinde tasarlanan sl evrime maruz braklmasyla iki aamada
gerekletirilmitir. Ayn zamanda toz paracklarn balayan balaycnn uzaklatrlmas nedeniyle parada ekil
kayb meydana gelmemesini salamak amacyla balayc gidermenin termal aamasnda 900oCye klp 1 saat
beklemeyle bir n sinterleme salanmtr.
Tablo 2. Kullanlan NI 718 speralam tozuna ait baz zellikler
zellik
retici
retim yntemi
Toz ekli
NI 718
Osprey
Gaz atomizasyonu
Kresel
Vurgu younluu (g/cm3)
4,9
Teorik younluk (g/cm )
8,323
Partikl boyutu (m)

D10
4,5
D50
11,9
D90
26,2
ekil 2. NI 718 tozuna ait SEM grnts

Sinterlenen numunelerin Arimet prensibine gre younluklar llm, NIKON LP 1200 ELIPSE marka optik mikroskop ile grntleri alnm ve Shimadzu (Japan) marka cihaz ile 100 g ykn 10 saniye uygulanmas suretiyle
mikrosertlik lmleri gerekletirilmitir. Yaplan bu incelemeler sonucunda en iyi sonucun alnd numuneler,
standatlarda bu malzeme iin belirlenmi 980oCde 1 saat bekletme [11] eklinde zeltiye alma ilemi sonrasnda
farkl srelerde yalandrlmlardr. Yalandrma ilemi sonrasnda tekrar sertlik lm yaplarak optimum sonucu
veren numuneler anma testine tabi tutulmulardr. Anma testleri Pin-on disk yntemiyle yaplmtr. Andrc
olarak 62 HRc sertlie sahip 100Cr6 rulman eliinden hazrlanm disk kullanlmtr. Deneyler sinterlenmi durumdaki ve yalandrlm durumdaki numunelerin andrc disk zerinde 10N ve 20Nluk ykler altnda 1 ms1 ve
2ms2 hzlar ile 5000 m kaymas eklinde gerekletirilmitir.
Farkl scaklklarda ve farkl srelerde gerekletirilen sinterleme ilemleri sonucunda en yksek bal younluk deerine (%95,84) 1300oCde 3 saat sren sinterleme ilemiyle ulald grlmtr. Fakat bu sinterleme parametrelerinde numunelerde ksmi ergimeler sonucu ekil kayb olduu gzlenmitir. 1290oCde 3 saat sreyle yaplm
olan sinterleme ilemi sonucunda da yaklak olarak ayn bal younluk deeri elde edilmi ve numunelerde ekil
kayb olmad grlmtr. 1290oCnin altnda yaplan sinterleme ilemlerinde yeterli younlua ulalamamtr.
Bu nedenle yalandrma ilemlerinde ve anma testlerinde kullanlacak olan numuneler 1290oCde 3 saat sre ile
sinterlenmilerdir. ekil 3de 1290oCde 3 saat sre ile sinterlenen ve bal younluu %95,81 olan numuneye ait
optik grnt verilmitir.
576

ekil 3. 1290oCde 3 saat sinterlenen numunenin optik mikroyap grnts.

ekil 4te sinterleme sonras farkl tutma sreleriyle gerekletirilen yalandrma sl ilemleri sonras numunelerden
llen sertlik deerleri verilmitir. Standartlara uygun olarak 980oCde 1 saat zeltiye alnarak [11] suda soutulan
numuneden llen sertlik deeri 227 HV0,1 olmutur. Yalandrma sonucu en iyi sertlik artnn 720oCde 9 saat
bekletildikten sonra frndan karlmadan frn scakl 620oCye drlp 8 saat bekleme sonucu suda soutulan
numunede 454 HV0,1 olarak elde edildii gzlenmitir. Yalandrma ilemiyle meydana gelen bu sertlik art istenilen kelti fazlarnn olutuunu dndrmektedir. Bu srenin zerinde gerekletirilen yalandrmalar sonucu
sertlikte d olmas ar yalanma olduunu dndrmektedir. Elde edilen bu sertlik deeri literatrde [12] bu
malzeme iin belirtilen ve takriben 360 Hv sertliine denk gelen 36 HRc sertlik deerinden olduka yksektir. Sertlik
deerinin literatrde belirtilen sertlik deerinden olduka yksek olmas toz enjeksiyon kalplama yntemiyle retilmi olan bu malzemelerin ince taneli oluuna balanmaktadr.
ekil 4. 720oCde farkl srelerde bekletildikten sonra 620oCde 8 saat bekletilen numunelerde
ulalan sertlik deerleri
Yalandrma ileminden nce ve sonra numuneler anma testlerine tabi tutulmutur. 10N ve 20N ykler altnda
5000 m yolu 1ms1 ve 2ms2 hzlarla kayan numunelerde meydana gelen arlk kayplar ekil 5.a ve ekil 5.bde
verilmitir. Farkl yk ve hzlarla gerekletirilen anma testleri sonucunda hem sinterlenmi numunelerde hem de
yalandrlm numunelerde arlk kaybnn ykten ok hzn artmasyla artt grlmtr. Dier bir ifadeyle bu
tr malzemelerin anmasnda hzn uygulanan ykten daha etkili olduu grlmtr. Yalandrlm numunelerde
sinterlenmi durumdaki numunelerden daha az anma kayb grlmekte olup, bu durumun yalandrma ilemiyle
malzeme iinde meydana gelen kelti fazlarnn salad sertlik artndan kaynakland dnlmektedir.
(a)
(b)
ekil 5. Anma testine tabi tutulan numunelerden, a) 1ms1 hzla, b) 2ms1 hzla kayan numunelerde meydana
gelen arlk kayplar (SS-Sinter Sonras, YS-Yalanma Sonras).
577

ekil 6da 10N ve 20N ykler altnda 5000 m yolu 1ms1 ve 2ms2 hzlarla kayan numuneler iin, anan malzeme
hacminin yola blnmesi eklinde hesaplanan anma oranlar verilmitir. Anmayla meydana gelen arlk kaybna paralel bir ekilde yalandrlm malzemelerin anma orannn sinterlenmi durumdaki malzemelerden daha
dk olduu, bu tr malzemelerde uygulanan yk ve anma hz arttka anma orannn da artt, fakat hzn
anma oranndaki etkisinin ykten daha ok olduu grlmtr.
(a)
(b)
ekil 6. Anma testine tabi tutulan numunelerden, a) 1ms1 hzla, b) 2ms1 hzla kayan numunelerde meydana
gelen anma oranlar (SS-Sinter Sonras, YS-Yalanma Sonras).
Nikel esasl speralamlarn dk termal iletkenliklerinden dolay talal ilem esnasnda takm malzemesi ile
temas eden blgede scaklk artnn meydana geldii belirtilmektedir [13]. Anma testleri esnasnda yukardaki
aklamaya uygun olarak hem sinterlenmi hem de yalandrlm numunelerde ve andrc diskte scakln ok
ykseldii gzlenmitir. ekil 7.ada sinterlenmi durumdaki numunenin 20N yk altnda 2ms1 hzla andrldktan
sonra yzeyinden alnan SEM grnts verilmitir. Bu tr malzemelerin pin-on disk yntemiyle andrlmasnda,
anma olaynn daha ok adhesiv anma eklinde gerekletii grlmektedir. Ezugwu ve arkadalar tarafndan
yaplan bir almada [14], nikel esasl speralamlarn ilenmesinde kesme hznn artna paralel olarak ara yzeyde oluan scakln da artt, takm tala ara yzeyinde ok yksek kesme hz aralklarnda speralamlarn
ergime scaklna ulaan scaklklarn meydana geldii bildirilmitir. Ayn almada nikel esasl speralamlarn
uzun sre yksek hzl kesme artlarnda ilenmesinin yeni oluturulmu yzeylerin yumuamas ile sonuland
ve i paras malzemesinin takma adhezyonu ile birlikte takmda anma olumaya balad belirtilmitir [14].
Benzer durum bu almada elde edilen anma yzeyinin SEM grntsnde de grlmektedir (ekil 7a). Scaklk
ykselmesine bal olarak malzemede baz ksmlarn atlad, yumuayan ve zayflayan ksmlarn kopmu olduu gzlenmekte, kopan malzemelerin andrma diskine yapm olduu dnlmektedir. Benzer durum, yaplm
baka bir almada yine yksek kesme hzyla ilemede seramik kesici takm zerine Inconel 718 i parasnn
yapmas eklinde gzlenmitir [15]. Elde edilen sonu bu almada elde edilen sonularla uyumaktadr. Inconel
718 speralamnn seramik takm ile ilenmesi zerine yaplan bir almada abrasif anma, adhezyon anmas,
mikro krlmalar ve talalanma etkin anma mekanizmas ve tipleri olarak grlmtr [16]. ekil 7. bde yalanm
numunenin anma sonras grnts verilmi olup, sinterleme sonras andrlan numuneye gre anmaya kar
direncin daha fazla olduu grlmektedir.
(a)
(b)
ekil 7. a) Sinter sonras 20N yk altnda 2m/s hzla anan, b) yalanma sonras 10N yk altnda anan
numunenin SEM grnts (KY, kayma yn)
TEK rn malzemelerin anma davranlarn etkileyen en nemli parametre yap ierisindeki gzenek miktar
ve dalmdr. Gzenek miktarnn %7nin altnda olmas durumunda anma kayplar gz nne alnmayacak
deerlerdedir ve dikkate alnmaz [17,18]. Gerekletirilen deneysel almalarda ise gzenek miktar %4 seviyesinde olup, sl ilemli ve sl ilemsiz numuneler iin ayn seviyededir. Bu durumda anma kayplarndaki nemli
farklarn sadece sl ilem artlarna bal olarak gerekleen sertlik artlar ile dorudan ilikisi vardr. zellikle
ekil 7.ada grld zere anma yzeylerinde kayma yn dorultusunda nemli bir delaminasyon grlmektedir. ekil 7.bde ise, sertlik artna bal olarak kayma ynne bal olarak anma yzeylerindeki delaminasyon
azalmaktadr [1719].
578

4. Sonular
Bu almada n alaml NI 718 tozundan TEK metodu ile para retimi yaplm, retilen paralar sl ilem ve
anma testlerine maruz braklmlardr. Yaplan deneysel almalardan aadaki sonular karlmtr.
1. Balang tozuna yaplan boyut dalm analizi, tozlarn %50sinin 11,9 m boyutunda olduunu ve TEK iin
kullanlmaya uygun aralkta olduunu gstermitir.
2. ok bileenli bir balayc sisteminin kullanlmasyla ekillendirilen paralarn eklini muhafaza edebilmesi bakmndan kullanlabilecek en yksek sinterleme scaklnn 1290oC olduu tespit edilmi, bu scaklkta 3 saat
sreyle gerekletirilen sinterleme ilemi sonucunda %95,81 bal younlua ulalmtr.
3. 980oCde 1 saat zeltiye alma sonrasnda gerekletirilen farkl srelerdeki yalandrma ilemelerinde, en
yksek sertlik art 720oCde 9 saat+620oCde 8 saat bekleme sreleriyle elde edilmi olup, bu deer 454
HV0,1dir.
4. Hem sinterlenmi durumda hem de yalandrlm durumda 5000 m yolu 10N ve 20N ykler altnda, 1ms1 ve
2ms1 hzlarla kayan numunelerde yk ve hzn artmasyla arlk kayplar ve anma oranlar da artmtr. Bu
tr malzemelerde anma kayplar zerinde hzn uygulanan ykten daha etkili olduu grlmtr.
5. Anma deneylerine tabi tutulan numunelerden sinterleme sonras sl ileme tabi tutulan numunelerin olutuu
dnlen intermetalik keltilerin salad sertlik artna bal olarak sinterlenmi durumdaki numunelere
nazaran anmaya kar daha direnli olduklar tespit edilmitir.
TEEKKR
NI 718 tozlarnn temini konusundaki desteklerinden dolay Osprey Co. (UK) firmasna teekkr ederiz.
KAYNAKLAR
1. R. M. German, Powder Injection Molding, ASM Handbook, Volume 7, Powder Metal Technologies and Applications, sayfa: 843848, 1998.
2. ASM Specialty Handbook: Nickel, Cobalt, and Their Alloys, compiled by J.R. Davis, ASM International, Materials Park, OH., 2000.
3. R. E. Schafrik, D.D.Ward, J.R. Groh, in: E.A. Loria (Ed.), Application of Alloy 718 in GE Aircraft Engines: Past,
Present and Next Five Years, Superalloys 718, 625, 706 and Various Derivatives, TMS, sayfa: 111, 2001.
4. D. F. Paulonis, J. M. Oblak, and D. S. Duvall, Precipitation in nickel-base alloy 718, Trans. ASM, cilt: 62, no:
3, sayfa: 611622, 1969.
5. R. Cozar and A. Pineau, Morphology of and precipitates and thermal stability of inconel 718 type alloys,
Metallurgical Transactions, cilt: 4, no: 1, sayfa: 4759, 1973.
6. I. Kirman and D. H. Warrington, Precipitation in Nickel-Based Alloys Containing both Niobium and Titanium,
Institute of Metals, cilt: 99, sayfa:197- 199, 1971.
7. W. E. Quist, R. Taggart and D. H. Polonis, The Influence of Iron and Aluminium on the precipitation of metastable Ni3Nb Phases in the Ni-Nb System, Metallurgical and Materials Transactions, no:3, cilt: 2, sayfa:
825832, 1971.
8. M. C. Chaturvedi and Ya-fang Han, Strengthening Mechanisms in Inconel 718 Superalloy, Metal Science, cilt:
17, sayfa:145149, 1983.
9. S. T. Wlodek and R. D. Field, Freckles in Cast and Wrought Products, Superalloys 718, 625, 706 and Various
Derivatives, ed. E. A. Loria, (TMS, Warrendale, PA), sayfa:167176, 1994.
10. A. R. Braun and J. F. Radavich, Microstructnral and Mechanical Properties Comparison of P/M 718 and P/M
TA 718, Superalloy 718 - Metallurgy and Applications (Warrendale PA, E.A.Loria, Metals and Materials
Society), sayfa: 623629, 1989.
11. Donald J. Tillack, James M. Manning, and J. R. Hensley, Heat Treating of Nickel and Nickel Alloys, ASM Handbook, Volume 4, Heat Treating, sayfa: 2042, 1991.
12. W.L. Mankins and S. Lamb, Nickel and Nickel Alloys, ASM Handbook, Volume 2, Properties and Selection:
Non Ferrous Alloys and Special-Purpose Materials, sayfa: 1387, 1990.
13. D. A. Axinte, P. Andrews, W. Li, N. Gindy and P. J. Withers, Turning of advanced Ni based alloys obtained via
powder metallurgy route, Annals of the CIRP, 55/1 2006.
14. E. O. Ezugwu, J. Bonney, Y. Yamane, An overview of the machinability of aeroengine alloys, Journal of Materials Processing Technology, cilt: 134, sayfa: 233253, 2003.
15. A. R. MOTORCU, Nikel Esasl Speralasmlarn ve Titanyum Alamlarnn lenebilirlii, II. Blm: Seramik
Kesici Takmlarn Performanslarnn Deerlendirilmesi, Makine Teknolojileri Elektronik Dergisi, cilt: 7, No: 2,
sayfa: 117, 2010.
16. L. Li, N. He, M. Wang, Z. G. Wang, High speed cutting of Inconel 718 with coated carbide and ceramic inserts,
Journal of Processing Technology, cilt:129, sayfa: 127130, 2002.
17. N. P. Suh, An overview of The Delamination Theory of Wear, Wear, cilt: 44, sayfa: 116, 1997.
18. K.V. Sudhakar, P. Sampathkumaran, E.S. Dwarakadasa, Dry Sliding Wear High Density Fe2%Ni Based P/M
Alloy, Wear, cilt: 242, sayfa: 207, 2000.
19. H.O. Gulsoy, Dry Sliding Wear in Injection Molded 174 PH Stainless Steel Powder With Nickel Boride Additions, Wear, cilt: 262, sayfa: 491497, 2007.
579

MAGNEZYUMUN LAVESNN Al4Cu TM ALAIMININ YALANMA

DAVRANIINA ETKLER
Azim GKE*, Fehim FINDIK**, Ali Osman KURT***
Sakarya niversitesi Teknik Eitim Fakltesi Metal Eitimi Blm,54187, Sakarya, azimg@sakarya.edu.tr
Uluslararas Sarajevo niversitesi, Mhendislik ve Fen Bilimleri Fakltesi, Mmakine Mhendislii Blm,
71000, Saraybosna, Bosna-Hersek, ffindik@ius.edu.ba
***
Sakarya niversitesi, Mhendislik Fakltesi, Metalurji ve Malzeme Mhendislii Blm, 54187, Sakarya,
aokurt@sakarya.edu.tr
**
zet
Bu almada elementel olarak hazrlanm % 4 bakr ieren alminyum alamna farkl oranlarda magnezyum
katks yaplm, alamn yapay yalanma davran mikroyap ve sertlik sonularyla incelenmitir. Magnezyum
ilavesi Al4Cu toz metal ana malzemesinin yalandrma ile sertlik kazanma kabiliyetini artrmaktadr. Magnezyum
ilavesiz numunede sertlikte 6 saatlik yalandrma ile yaklak % 40lk bir art salanrken, ayn numuneye % 0,5
magnezyum ilavesi ile 6 saatlik bir yalandrma sonras sertlik art yaklak % 95 olmaktadr. almada en yksek
sertlie (117 HB) % 2 magnezyum ieren alamn 24 saat yapay yalandrlmas sonucu ulalmtr.
Anahtar Kelimeler: Al Toz Metal, Mikro Alamlama, Sinterleme, Toz Metal Isl lemleri.
EFFECTS OF THE MAGNESIUM ADDITION ON THE AGING BEHAVIOR OF

Al4Cu PM ALLOY
ABSTRACT
In this study, various levels of magnesium added into pre-mixed Al4Cu powder metallurgy alloy and aging behavior
of the alloy was investigated. The addition of Mg resulted in an increase in age hardening ability of the onto the main
Al4Cu PM alloy. The alloy without Mg addition has only 40 % increase in hardness after 6 hours ageing whereas
with an 0,5 wt% Mg addition on to the same alloy resulted in an 95 % increase in hardness after 6 hours ageing.
In the study, the highest hardness value was obtained with an alloy (Al4Cu2Mg) of 2 % Mg addition after 12 hour
ageing.
Keywords: Al Powder Metallurgy, Micro-Alloying, Sintering, Powder Metallurgy Heat Treatments.
1. GR
Alminyum alamlarnn dk zgl arlk, yksek korozyon direnci, geri dnm gibi zellikleri toz metalurjisi
ynteminin avantajlar ile birlemesiyle tozmetal alminyum alamlar son yllarda giderek artan bir oranda endstriyel ve teknolojik rnlerde kullanm alan bulmaktadr. Alminyum tozlarndan retilen alamlar ilenmi alminyum alamlar ile byk oranda benzer bileimdedir.
Alminyum tozlarnn sktrlma zellii, genel olarak toz morfolojisine ve boyut dalmna bal olmakla beraber,
350 MPa basn altnda teorik younluunun %90na kadar ulalabilmektedir. Demir esasl tozlara nispeten alminyum tozmetal malzemelerin sinterlenmesi iin ok daha dk scaklklar yeterli olmaktadr. Bu ise zamandan
ve enerjiden byk tasarruf salamaktadr [1].
580

Alminyumun toz metalurjisinde kullanmndaki byk sorunlardan biri yzey oksididir. Alminyum zerindeki oksidin kalnl ortam scakl, alminyum tozunun retiminde kullanlan sre, sakland ortamdaki nem gibi deikenlere baldr. Oda scaklnda ktle alminyum yzeyindeki oksidin kalnl yaklak 10 20 dur. Atomize alminyum zerindeki oksit kalnl ise 50-150 arasndadr. Alminyum zerindeki oksit genellikle amorf ve emilen
su tabakas nedeniyle hidrolize olmu durumdadr. 350 oC zerindeki scaklklarda tavlama srecinde oksit tabakas
g-Al2O3 halinde kristalize olur. Oksit tabakas dk ergime dereceli metallerde kat faz sinterlemeyi engelleyici bir
faktrdr. Bu yzde alminyum alamlarnn sinterlenmesinde sv faz daha ok tercih edilir bir yntemdir. Baz
metallerin alam sistemine katlmas sinterleme srasnda oksit tabakasn elimine edici etki yapabilir. Magnezyum
katksnn yzeyde oluan oksit tabakasn krmak sratiyle alminyum alamlarnn sinterlenmesinde olumlu katk
yapt bilinmektedir[2,3,4,5]. Sisteme magnezyum katlmas durumunda; oluan reaksiyon aadaki gibidir[6].
3Mg + 4Al2O3
3MgAl2O4 + 2Al (1)
Scheaffer[6] yapt TEM almalar ve mikroyapsal analizler ile Al 2xxx serisine yaplan Mg katksyla Spinel
fazn olutuunu gstermitir. Sinter esnasnda magnezyumun alminyum matris iine nfuz etmektedir Sonrasnda yukardaki reaksiyon sonucu oksit film tabakas zerinde hacimce deiim meydana gelmekte ve bundan
dolay oluan kesme gerilmesi oksit tabakasnn krlmasna sebep olmaktadr. Bylelikle yaynm (difzyon), slatma sonucunda sinterlemenin daha iyi olmasn salamaktadr. Dolaysyla, oksit tabakas bir problem olmaktan
kmaktadr.
Alminyum bakr alamlarnn mukavemetinin artrlmas iin sl ilem uygulanmas pratikte sklkla kullanlan bir
yntemdir. Bu yntem zeltiye alma, su verme ve yalandrma olarak basamaktan olumaktadr[7].
Bu almada elementel tozlarla hazrlanm Al4Cu ana alamna eitli miktarlarda (% 0,5 2) magnezyum ilavesinin mikroyapya ve yalandrma sonucunda ana malzemenin sertliine olan etkileri incelenmitir.
2.1 Hammadde ve Kompozisyon Hazrlama
almada kullanlan tozlarn zellikleri Tablo 1de verilmitir. Tablo 2`de ise almada retilen alamlarn bileimleri grlmektedir.
Tablo1. Deneysel almalarda kullanlan tozlarn zellikleri
Toz
Alminyum
Bakr
Magnezyum
Tedariki
Grel Makine A..
Grel Makine A..
Magnezyum Metal A..
Safiyet (%)
99,60
99,60
99,95
,00
Toz Boyutu ( m)
-53
-53
-53
Tablo 2. retilen alamlarn bileimleri

Alam Kodu
Alam Kodu
Al4Cu
Al4Cu0.5Mg
Al4Cu0.5Mg1Mg
Al4Cu0.5Mg2Mg
Alam Elementi (% a.)

Cu
4,00
4,00
4,00
4,00
Al
96,00
95,50
95,00
94,00
Mg
-0,50
1,00
2,00
Alamn bileimine uygun olacak ekilde tozlar 0,0001 gr hassasiyetli Precisa hassas terazide tartlm sonrasnda
taban 35 mm apnda 80 mm yksekliinde geni azl silindirik HDPE ielere konmutur. Kartrma ileminin
daha etkili olmas asndan 5mm apnda ZrO2 bilyeler kullanl olup, ielerin hacimce 1/3 karm toz, 1/3
ZrO2 bilye ile doldurulmu 1/3lk ksm ise bo braklmtr. Kartrma ilemlerinde Turbula-T2F Mixer kullanlm
olup kartrma sresi 3 saat olarak belirlenmitir.
581

2.2. ekillendirme lemleri

Kompaktlarn retilmesinde 14 Ton kapasiteli manel hidrolik bask cihaz kullanlmtr. Numune retiminde kullanlan basn 400 MPadr. retilen silindirik ham paralarn ap 16 mm ykseklii ise 4 mm olacak ekilde ayarlanmtr. Ham paralarn sinter ncesi younluklar ktlelerinin hesaplanm olan hacimlerine blnmesi ile bulunmutur. Kalp anmasnn engellenmesi iin her bir ekillendirme ilemi ncesi kalp boluu ve kalp zmbalar inko
stearat ile yalanmtr. inko stearattn yzeye dalm yksek safiyetli alkol ile gerekletirilmitir.
2.3. Sinterleme lemleri
Sinterleme ilemlerinde Honeywell DC2500 kontrol nitesi ile programlanabilen silindirik yatay tp frn kullanmtr.
Frnn reaktr tp 316 L paslanmaz elikten zel olarak imal edilmitir. zeltiye alma ilemlerinde de ayn frn ve
tp kullanlmtr. Numuneler frna Al2O3 altlklar zerinde yerletirilmitir. Sinterleme ilemlerinde yksek safiyette
azot gaz kullanlmtr. Gaz iindeki olas ok dk oksijen safszlnn nne geilmesi amacyla tpten kan
gaz frna girmeden nce silika jel ile doldurulmu gaz ykama iesinden geirilmitir. Gaz ak hz sinter esnasnda 1 lt/dk olarak belirlenmitir.
Sinterleme scakl 615 C olup bu scakla 15 oC/dk hzla klmtr. Kontrolsz olarak frn ierisinin bu scaklklarn zerine almasn engellemek amal 600 C`nin zerinde frn stma hz 1 oC/dk olarak gerekletirilmitir
(ekil 1). oCoCzeltiye alma ve yalandrma scaklklar her 3 grup numune iin de ayndr. zeltiye alma ilemi
sonrasnda ar doymu yap elde edilmesi amacyla frndan kartlan numuneler oda scaklndaki su ierisine
drlmtr. Isl ilem sreci olarak dkm alminyum alamlarna uygulanan T6 sl ilemine benzer bir sre olan T51 sreci seilmitir (ekil 1). Bu srece gre sinter sonrasnda numuneler oda scaklna dmeden
zeltiye alma scaklna kontroll olarak soutulmaktadr. Yalandrma ilemleri Protherm-PFL-130/6 kl frnda
yaplm olup yalandrma sresi 6, 12, 24 ve 48 saat olarak seilmitir.
2.4. Sinter Sonras lemler
Sinterlenen numunelerin younluklar Arimet Prensibine gre belirlenmitir. Younluk belirleme ilemleri karm
hazrlamada kullanlan hassas teraziye balanan younluk lm kiti ile yaplmtr. Younluk lm sonrasnda
numuneler hassas kesme cihaz ile ortadan kesilip herhangi bir kontrolsz yalanmann engellenmesi iin souk
olarak reineye alnmtr. Mikroyapsal inceleme iin numuneler geleneksel metalografik ilemlerden geirilmi
nihai parlatmada 0,3 mlik almina sspansiyon kullanlmtr. Optik mikroskop olarak Clemex Image Analysis yazlm ile senkronize alan Nicon Eclipse L150A metal mikroskobu, elektron mikroskobu olarak Jeol JSM 6060LV
taramal elektron mikroskobu kullanlmtr.
Sertlik lmlerinde BMS 200 RB sertlik lm cihaz kullanlm olup seilen yk 62,5 kg ve yk uygulama sresi
10 saniyedir. Her bir numuneden 5 lm alnm ortalama deer o numunenin sertlik deeri olarak kabul edilmitir.
ekil 1. Sinterleme almalarnda kullanlan scaklk-zaman grafii.
582


Deneysel almalarda kullanlan tozlarn morfolojik zelliklerinin incelenmesi amacyla ekilmi olan elektron mikroskobu grntleri ekil 2de verilmitir.
ekil 2. Kullanlan tozlarn SEM grntleri a)Al b)Cu c)Mg (. l izgisi a, b ve c iin 100 mdir). ve d iin ise
50 m`dir. l izgisleri daha da belirginletirilecek
Literatrde alminyum-bakr alamlarnn sinterlenmesi ile ilgili almalarda sinterlemenin 580-620 oC scaklklar
arasnda yapld grlmtr[6,8,9,10]. Sinterleme scaklnn belirlenmesinde bakr oran arttka sinterleme
scakl dmektedir. Alminyum bakr denge diyagramna gre (ekil 3) % 4 bakr katks ile tektik sv faza gei
scakl yaklak olarak 590 Cdir. Bu scaklk zerinde yaplan sinterleme ilemi sv faz olarak adlandrlr. Oluan
tektik sv fazn kapiler basn etkisiyle paracklarn arasn doldurmas ile daha youn bir yap elde edilmesini
salar. Daha nce yaplan bir alma[3] magnezyum katks ile birlikte sv faz oluma scaklnn dtn
gstermitir. Bu yzden almada kullanlan sinter scakl olan 615 Cde oluan tektik fazn diyagramda belirlenenden daha fazla olduu dnlmektedir. zeltiye alma scakl olan 550 Cde bakrn tamam yapya girerken
oda scaklnda alminyum iinde bakrn ok az bir ksm znebilmektedir. Bu durumda ani soutma ile ar
doymu bir yap elde edilmektedir.
ekil 3. Al-Cu faz diyagramnn alminyumca zengin ksm.

ekil 4de sinterlenmi Al4Cu ve Al4Cu2Mg alamlarna ait mikroyaplar grlmektedir. Magnezyum ilavesi ile
birlikte yapda tane bymesi grlrken tane snrlar da magnezyum ilavesiz numuneye gre daha belirgindir.
Magnezyum ilavesi ayn zamanda mikroyapda tespit edilebilir belirgin ekilde porozitede arta sebep olmutur
(ekil 5). Magnezyumun spinel faz oluturarak alminyum yzeyindeki oksit tabakasn krmas dolaysyla sv faz
oluumunu kolaylatrmas ve tane snrlarndaki sv faz miktar artyla beraber daha kaln tane snrlar olutuu
dnlmektedir.
583

ekil 4. Sinterleme ilemi sonrasnda a)Al4Cu b) Al4Cu2Mg alam.
ekil 5. retilen alamlarn sinter sonras % teorik younluk deerleri.

Al4Cu numunesine ait zeltiye alma sonucunda oluan optik mikroyap grnts ekil 6-ada; taramal elektron
mikroskobu grnts ise ekil 6-bde verilmitir. ekil 6-a genel yapnn grlmesi amacyla en dk bytmede
(50X) ekilirken ekil 6-b keltilerin ve gzenek byklnn daha iyi incelenmesi amacyla yksek bytmede
alnmtr. ekil 6-ada verilen numunede makro porozite grlmemektedir.
ekil 6. zeltiye alma ilemi sonucu Al4Cu numunenin a) optik b) SEM grnts
ekil 6-bde belirtilen noktalara ait EDS analiz sonular Tablo 3de sunulmutur. Yapda grlen beyaz blgelerin
demir ve bakrca zengin blgeler olduu grlmekle beraber zellikle demirce zengin blgeler inemsi yapda keltiler oluturmutur. Al4Cu numunesinin zeltiye alma sonras ekilmi XRD grafiinde (ekil 7) yapda Al-Cu-Fe
intermetalik faznn olutuunu tespit edilmitir.
584

Tablo 3. ekil 6-bde belirtilen noktalarn EDS analiz sonular.

Nokta
Al
69,874
95,131
98,836
97,879
1
2
3
4
Element (% a.)
Cu
21,952
4,869
1,164
1,762
Fe
8,174
--0,359
ekil 7. Al4Cu numunenin zeltiye alma sonras XRD grafii. (-Al7Cu2Fe, -Al)
Yapda grlen demir tozlarn retim safhasnda ve safszlk olarak gelmektedir. Demir faz iinde znerek
Al7Cu2Fe fazn oluturmaktadr. Bu faz mikroyapda inemsi/ubuksu formda yer almaktadr (ekil 6-b).
Al4Cu2Mg numunenin zeltiye alma ilemi sonucu mikroyaps ekil 8de verilmitir. Magnezyum ilavesi ile birlikte
ilavesiz numuneye oranla en byk fark olarak magnezyumun btn mikroyapda dalmas ve analiz yaplan noktalarda bulunan oksijen dikkat ekmektedir (Tablo 4). Matris olarak ifade edilebilecek 1 numaral nokta da dahil olmak zere analiz yaplan her noktada oksijen bulunmasnn nedeni, yapy oluturan elementlerin oksijene ilgisinin
yksek olmasndandr. Bakr ieriinin yksek olduu 3 ve 4 numaral noktalarda demir ieriinin de yksek olmas
XRD sonularn (ekil 7) dorular niteliktedir.
ekil 8. Al4Cu2Mg numunenin zeltiye alma ilemi sonucu mikroyap grnts

Tablo 4. ekil 8de belirtilen noktalara ait EDS elementel analiz sonular.
Nokta
1
2
3
4
Al
84,133
92,121
43,621
43,617
Element (% a.)
Cu
1,342
1,366
17,346
17,539
Mg
2,714
1,725
3,440
3,091
O
11,811
4,788
32,280
28,664
Fe
--3,311
7,088
Al4Cu2Mg numunesinin 24 saat yalandrma sonucu mikroyap grnts ekil 9da verilmitir. Mikroyap grntlerine gre tane snrlar belirgin olmakla beraber kimi noktalarda ikincil fazn daha belirgin olduu dikkat ekmektedir. zeltiye alma ilemi sonrasnda zeltiye alnamayan Al-Cu-Fe intermetaliinin (ekil 7) mikroyapda
585

farkl renkte grnd tespit edilmi olup tane snrlarnda youn olarak biriken bu fazn sertlik zerinde olumlu bir
etkisi olsa da mekanik zellikler zerinde olumsuz bir etkisinin olaca dnlmektedir. Bu fazn bakrca zengin
blgelerde daha youn bulunduu EDS analizi ile tespit edilmi olup matris olarak ifade edilecek 1 ve 4 numaral
noktalarda demir tespit edilmemesi bu faz zeltiye alnamad kantlar niteliktedir.
ekil 9. Al4Cu2Mg numunenin 24 saat yalandrma sonucu grnts.

Tablo 5. ekil 9da belirtilen noktalarn EDS analiz sonular
Nokta
Al
96,667
43,917
96,242
91,216
1
2
3
4
Cu
1,865
39,113
1,481
1,293
Element (% a.)
Mg
1,468
1,976
2,277
1,566
O
-11,201
-5,925
Fe
-3,792
---
retilen alamlara ait sertlik deerleri Tablo 6a verilmitir. Sonulara gre en yksek sertlik deeri 24 saat yalandrlan Al4Cu2Mg numunesinde elde edilmitir. % 2 magnezyum ilavesi, alam sertliinde hibir sl ilem olmadan
% 50 art salamaktadr. Magnezyumun sinter kolaylatrc etkisi ve yapda ince bir ekilde dalmas bunun balca sebebidir. Ayrca magnezyum katks arttka yalanma iin gerekli sre ksalmtr. Elde edilen sertlik deerleri
literatrdeki benzer almalardan daha yksektir[11,12,13].
Tablo 6. retilen alamlarn sertlik deerleri
Sertlik (HRB)
Alam
Al4Cu
Al4Cu0.5Mg
Al4Cu1Mg
Al4Cu2Mg
Sinter
zeltiye
alma
42,2
44,0
53,6
62,2
50,5
53,8
78,8
97,7
6 saat
59,2
86,2
92,4
111,1
Yapay Yalandrma
12 saat
24 saat
62,3
73,6
81,6
92,4
89,2
105,2
110,5
118,12
48 saat
72,2
94,3
96,6
101,8
4. SONULAR
zetle bu almada aadaki sonulara ulalmtr.
Hammadde olarak kullanlan tozlardan safszlk olarak gelen demir Al-Cu ile birleerek Al7Cu2Fe intermetalii
oluturmaktadr ve bu intermetalik zeltiye alma sl ilemi ile yapda zlememektedir.
Al-Cu-Mg alamna eklenen mikro dzeyde magnezyum ile sertlikte yaklak %50 art elde edilmitir.
Magnezyum ilavesi yalandrma ile sertlik kazanma kabiliyetini artrmaktadr.
Magnezyum ilavesiz numunenin sertlii 6 saatlik yalandrma ile yaklak % 40lk bir sertlik art salanrken,
ayn numuneye % 0,5 magnezyum ilavesi ile 6 saatlik bir yalandrma ile salanan sertlik art yaklak % 95dir.
En yksek sertlik 118,2 HB ile k elde edilebilirkenen yksek sertlik deerine te ulalmtr. en % 2`lik magnezyum katks yaplan numunelerin 24 saat yalandrlmas ile elde edilmitir.
Alamlandrma ve sl ilem ile Al4Cu alamnn sertlii % 179 artrlabilmektedir.
Silisyum ilavesinin % 1`e karlmas ile en yksek sertlie 6 saatte klabilmektedir.
586

TEEKKR
Bu alma Sakarya niversitesi Bilimsel Aratrma Projeleri Komisyonunca desteklenmitir (SA-BAPK 200950-02-020). Yazarlar, tozlarn teminindeki desteinden dolay Grel Makina A.. ve Magnezyum Metale teekkr
eder.
KAYNAKLAR
1. nternet Sitesi - European Powder Metallurgy Association- http://www.epma.com/New_non_members/structural_parts.htm
2. Lumley, RN., Sercombe, TB., Schaffer, GB., Surface Oxide and the Role of Magnesium During the Sintering of
Aluminum, Metallurgical and Materials Transactions A, Vol. 30A, pp. 457-463, 1999.
3. Kondoh, K., Kimura, A.,Watanabe, R., Effect of Mg on Sintering Phenomenon of Aluminium Alloy Powder
Particle, Powder Metallurgy, Vol. 44, pp. 161-164, 2001.
4. Gke, A., Fndk, F., Kurt, AO., Microstructural Examination and Properties of Premixed Al-Cu-Mg Powder
Metallurgy Alloy, Materials Characterization, Vol. 62, pp. 730-735, 2011.
5. MacAskill, IA., Hexemer Jr, RL., Donaldson, IW., Bishop, DP, Effects of Magnesium, Tin and Nitrogen on the
Sintering Response of Aluminum Powder, Journal of Materials Processing Technology, Vol. 210, pp. 22522260, 2010.
6. Schaffer, GB., Sercombe, TB., Lumley, RN.,Liquid Phase Sintering of Aluminium Alloys, Materials Chemistry
and Physics,Vol. 67,pp. 8591, 2001.
7. Smith, WF., Mhendislik Alamlarnn Yap ve zellikleri, eviri:Dr.Mehmet Erdoan, Nobel Yaynlar, Ankara,
2001.
8. Kyung, HM., Kang, SP., Lee, BH., Lee, JK., Kim, YD., Liquid Phase Sintering of the Commercial 2xxx Series Al
Blended Powder, Journal of Alloys and Compounds, Vol. 419(1-2), pp. 290-293,2006.
9. Hall, BJ., Schaffer, GB., Statistical Experimental Design of Al-Cu-Mg-Si P/M Alloys, Journal of Light Metals,
Vol. 2(4),pp. 229-238, 2002.
10. Lefebvre, LP., Thomas, Y.,White, B., Effects of Lubricants and Compacting Pressure on the Processability and
Properties of Aluminum P/M Parts, Journal of Light Metals, Vol. 2(4), pp. 239-246, 2002.
11. Kent, D., Schaffer, GB., Drennan, J., Age Hardening of a Sintered Al-Cu-Mg-Si-(Sn) Alloy, Materials Science
and Engineering: A, Vol. 405(1-2), pp. 65-73, 2005.
12. Delgado, ML., Ruiz-Navas, EM., Gordo, E., Torralba, JM., Enhancement of Liquid Phase Sintering Through
Al-Si Additions to Al-Cu Systems, Journal of Materials Processing Technology, Vol. 162-163, pp. 280-285,
2005.
13. ...c. T Durmus HK., Meric C., Age-hardening Behavior of Powder Metallurgy AA2014 Alloy, Materials and
Design, Vol. 28(3), pp. 982-986, 2007.
587

TOZ METALURJS YNTEMYLE RETLEN ve MERMER (DOAL TA)

KESMEDE KULLANILAN KESC ULARA B4C LAVESNN ETKLERNN
NCELENMES
Kerim Emre KSZ *, Mehmet MR *, Yusuf AHN **
Cumhuriyet niversitesi, Metalurji ve Malzeme Mhendislii Blm, 58140, Sivas, Trkiye.
Cumhuriyet niversitesi, Metalurji ve Malzeme Mhendislii Blm, 58140, Sivas, Trkiye.
**
Gazi niversitesi, Makine Eitimi Blm, Teknik Eitim Fakltesi,
Teknikokullar, 06500 Ankara/Trkiye
*
ZET
Kesici takm malzemelerinde beklenen ortak zellikler; anma dayanm, tokluk (en nemli takm malzemesi zelliidir ve anma direnci-tokluk ilikisi takm kalitesini belirler) ve ekonomikliktir. Bu deneysel almada elmas emdirilmi Fe-Co matrisli kompozitler toz metalurjisi yntemiyle scak presleme teknii kullanlarak retilmitir. B4C
takviyeli ve takviyesiz 2 farkl kompozisyona (farkl Fe/Co oran) sahip numuneler hazrlanm, 25 MPa basn
altnda ve 900 C derece scaklkta sinterlenerek, B4C ve Fe takviyesinin etkisi aratrlmtr. Kompozitlerin mekanik
zelliklerinin tespiti iin sertlik lm yaplm ve anma deneyleri de farkl yk artlarnda pim-disk tr anma
deneyi cihaz aracl ile yaplmtr. Deneysel sonular; Fe ilavesi ile matrisin sertliinin biraz azaldn gstermitir. Fakat B4C takviye elemannn katlmasyla matrisin sertliinde art grlmtr. Kompozitlerin, (TEM) ve (EDS)
teknikleri ile karakterizasyon almalar gerekletirilmitir.
Anahtar kelimeler: Toz Metalrjisi, Bor Karbr, Kompozit, Anma.
1. GR
Kesici takmlarnn mikro yapsn belirleyen iki ana evre olan matris ile elmas ara yzeyinde sinterleme koullarnda
kimyasal bir reaksiyon olumas istenir ve bu reaksiyon, elmasl kesici takmn mrn byk lde belirler [1].
Bu ba reaksiyonun oluumu metal tozlarnn bileimine, parack boyutuna ve dalmna, gaz ortamnn koruyucu
etkisine, sinterleme scaklna, suresine ve basncna baldr. Bu ekilde mekanik bir ban yan sra kimyasal bir
ba da oluturulmaya allr [2].
Elmasl kesici takmn baarl bir ekilde retilmesindeki en nemli parametrelerinden biri metalurjik slatmayla
matrise kuvvetlice balanan elmaslarn, oturma yzeyinden koparak uzaklamaya kar direnli olmasdr. Elmas
takmlarda kullanlan matris toz karmlarnn elmaslar salam bir ekilde tutmas gerekir [3].
Kesici takmn mr asndan elmaslar tamamen kaybolmadan veya elmaslarda hasar oluturmadan metalik matris optimum bir hz ile anmaldr. ok kolay bir ekilde anan matris, elmaslarn ar bir ekilde zayflayarak
kaybolmasna yol aabilmekte, ok sert bir matris ise yzeydeki elmaslarn bir sure sonra kesme yzeylerini yitirmeleri ve alttan da yeni kesici yzeylerin kmamas neticesinde kesme ileminin kesintiye uramasna neden
olabilmektedir. Kesilmesi amalanan doal tan ncelikle sertlii dorultusunda matris bileiminin ayarlanmas
gerekmektedir [4].
lkemizin mermer rezervleri asndan zengin bir lke olmas dnldnde mermer lkemiz sanayisi iin nemli
bir sektr haline gelmitir. Bu nedenle mermerin ve doal talarn daha kaliteli ve daha ucuz bir ekilde ilenmesi
bu sektr asndan olduka nemlidir [56]. Dnyada mermer ve doal talarn kesimi su jeti ve lazer kullanmak
suretiyle ve daha birok yntemle yaplrken, lkemizde en yaygn kullanlan yntem dairesel elmas testereler ile
kesimdir. Testerenin imalat, testerenin gvdesini tekil eden dairesel elik levhayla beraber kesme ilemini yapan
elmas soketlerin imalatndan oluur [7].Yaplan bu deneysel almada toz metalurjisi yntemi ile kesici u retilmesi, retilen kesici ularn mekanik zelliklerinin belirlenmesi, mikro yap kontrol ve endstride uygulanabilirliinin
aratrlmas hedeflenmitir.
588

2. DENEYSEL ALIMA
2.1 Numune Hazrlama
Elmas ve B4C katkl MMCler toz metalurjisi yntemi kullanlarak metal tozlarnn belirli oranlarda kartrlmas ile
retilmitir. Matris dizaynnda elmaslar bir arada tutan bir balant evresinden ve sinterleme koullarnda gzenekleri kapatmaya yarayan ve kesme koullarnda hzla anarak tala akma kanallarn oluturan bir dolgu evresinden
yararlanlr. Balant evresi iin iyi slatan kobalt ve nikel veya ucuz olmas nedeniyle demir gibi elementler ve
bu elementlerin kombinasyonlarndan faydalanlr [8-9]. Dolgu evresi iin genelde sinterleme koullarnda ergiyen
bronz veya pirin kullanlr. Doal ta iin standart matris dizayn Co, Ni ve Cu-Sn tozlar zerinden yaplmaktadr.
Co ve Ni tozlar -iyi slatma zellikleri dorultusunda- elmas balayc evre olarak kullanlmaktadr. Cu-Sn katks
hem Cu ve Sn tozlarnn karm halinde veya saf bronz tozu halinde olabilmektedir [8]. Yaplan bu almada,
40/+50 mesh elmas tozlar, 75 mden kk karbonil demir tozu, 85/15 mesh bronz tozu ve 10 mden kk
B4C tozu kullanlmtr. retilen kompozitlerin matris kompozisyonu, elmas konsantrasyon deeri ve B4C miktarlar
Tablo 1de verilmitir.
Tablo 1. retilen Kompozitlerin zellikleri.
Kompozit
Matris Kompozisyonu, a. %
Elmas
B4C (g)
Kodlamalar
C2
Fe
Co
Bronz
65
25
10
Konsantrasyonu
20 konsantrasyon
C4
45
45
10
20 konsantrasyon
B4C ilaveli kompozitler

C2-B4C
65
25
10
20 konsantrasyon
0,15
C4-B4C
45
45
10
20 konsantrasyon
0,15
B4C ilaveli ve ilavesiz kompozitler 2 farkl kompozisyonlarda 24 x 10 x 10 mm boyutlarnda (farkl Fe/Co oran)
retilmitir. LS4750 kodlu endstriyel elmas tozu her bir sokette 20 konsantrasyon olacak ekilde kullanlmtr.
(4,4 konsantrasyon/cm3 younluundaki elmas tozlar 100 konsantrasyon olarak ifade edilir). Fe - (2545) a. %
Co, elmas ve B4C tozlar (bor karbrsz) 2 farkl grup olarak kartrma ilemine tabi tutulmutur. Kartrma ilemi
45 derece eimli Turbula Mixer kartrc ile 45 dakika yaplmtr. Tozlarn karmasn kolaylatrmak amacyla,
karmn homojen olmas ve akkanln ideal biimde olmas iin % 2 glialkol (C2H5OH) (% 25 gliserin + % 75
alkol) eklenmitir. Homojen bir ekilde kartrlan metal tozlar nceden hazrlanm grafit kalplara tartlarak yerletirilmitir. Grafit kalplara koyulan tozlar yksek akm sayesinde, grafitte oluan snn etkisiyle scak presleme
yntemiyle 900 Cde azot kontroll atmosfer altnda sinterlenmitir. (Dr. Fritsch DSP 510 scak sinterleme presi).
Kompozit numuneler 25 MPa basn altnda sinterleme scakl olan 900 Cye stllarak sinterlenmitir. ekil 1
uygulanan sinterleme rejim grafiini gstermektedir.
ekil 1. Kompozit numunelere uygulanan sinterleme rejim grafii.

2.2 Mekanik Testler
retilen her bir kompozit malzeme iin 5 ayr noktadan 100 kgf kuvvet altnda Brinell sertlik deerleri llm ve ortalama sertlik deerleri belirlenmitir. Elmas katkl soketlerin anma deneyleri pim-disk tr cihaz ile kuru ortamda
gerekletirilmitir. Numuneler, disk yzeyine dik bir biimde cihaza monte edilmitir. Abrasiv anma deneylerinde
numuneler ilk nce talama makinesinde apaklarndan arndrlm ve temizlenmitir. Daha sonra abrasiv anma
deneyleri tane boyut aral 8874 mikron olan 180 numara silisyum karbr zmpara kullanlarak yaplmtr. Anma
589

deneyleri; 8, 16 ve 24 N yk altnda 48 m kayma mesafesinde, 1 m/s sabit hzda, oda scaklnda gerekletirilmitir. retilen kompozit numuneler anma miktarlar; 0,0001 gr lme hassasiyetine sahip hassas bir teraziyle, deney
ncesi llen arlklarndan deney sonras tespit edilen arlklarnn karlmas ile bulunmutur.
3.1 Sertlik
Doal ta kesimleri iin sertlik elmas emdirilmi kompozit malzemelerin kalitesini belirlemek iin en sk kullanlan
parametrelerdendir. Bu sebeple sertlik testleri sinterlenmi kompozit malzemelere uygulanmtr. Tablo 2de kompozit numuneler iin llen Brinell sertlik deerleri gsterilmitir. Deneysel sonular; Fe ilavesi ile matris sertliinin
azaldn gstermitir. Fakat B4C takviye elemannn katlmas matrisin sertliini artrmtr. Maksimum sertlik deeri B4C ilaveli ve ilavesi C4 kompozisyonuna sahip numunelerde llmtr. Bu sonular Co-Fe metalleri arasnda
kat ergimenin gerekletiini ve bununda sertlik artna neden olduunu gstermektedir [810].
Tablo 2. retilen Kompozitlerin Sertlik (HBN) Deerleri
Kompozitler
HBN (ort.)
C2 65wt%Fe+25wt%Co+10wt%bronze, 20 konsantrasyon
90
C4 - 45wt%Fe+45wt%Co+10wt%bronze, 20 konsantrasyon
93
C2-B4C -65wt%Fe+25wt%Co+10wt%bronze, 20 konsant, 0.15 g B4C
97
C4-B4C - 45wt%Fe+45wt%Co+10wt%bronze, 20 konsant, 0.15 g B4C
99
3.2 Anma Testi

Scak presleme teknii ile retilen B4C katkl ve katksz kompozit malzemelerin anma testi sonunda anma kayplar ekil 2de gsterilmitir. B4C katksz kompozit numuneler iin ilk tespit edilen, her bir numune iin uygulanan
yk arttka anma kaybnn arttdr. kinci olarak tespit edilen kompozitlerdeki Fe miktar artka anma kaybnn
arttdr. 24 N yk uygulandnda C4 kompozisyonuna sahip numunedeki anma miktar 0,01535 gramdr. Bu deer 1,27 kat C2 kompozisyonuna sahip numunedekinden daha azdr. Benzer tespitler B4C katkl kompozit numuneler iinde tespit edilmitir. Sonuta B4C katksz kompozit numunelerde dier B4C katkl tm kompozit numunelere
gre daha fazla anma kayb olduu gzlemlenmitir. B4C malzemesi yksek sertliinden tr retilen kompozit
malzemelerin anma direncine arttrma ynnde katk salamtr.
ekil 2. Anma testi sonundaki anma kayplar.

3.3 Mikro yap
Optik mikroskop kullanlarak retilen kompozitlerin mikro yaplar belirlenmitir. Zmparalama ve parlatma ilemlerine tabi tutulan kompozit numuneler daha sonra amonyum perslfat ( 10 g (NH4)2S2O3 + 90 ml damtk su ) zeltisi
ile dalanmtr. ekil 3a matrisin mikro yapsn gstermektedir. B4Cnin mikro yaps B4C konsantrasyonu ok az
miktarda ve parack boyutu ok kk (<10 m) olduundan tr mikroskop altnda net bir ekilde seilememektedir. Fakat yaplan EDS analizlerinde boronun pik yapt tespit edilmitir. ekil 3b C4-B4C kompozit numunesinin
EDS analizini gstermektedir.
590


(a)
(b)
ekil 3. (a) Kompozit numunelerin mikro yaps C4-B4C (400X). (b) Kompozit numunelerin EDX analizi C4-B4C.
4. SONULAR
Yaplan bu deneysel almada Co matriksli kompozitlere Fe ve B4C ilavesinin etkileri aratrlmtr. Elmas
emdirilmi Fe-Co matriks kompozitler (soket ) scak presleme teknii kullanlarak toz metalurjisi ile retilmitir.
C4 ve C4-B4C tip kompozitler kesilecek olan doal tanda zelliine de bal olarak ta kesiminde kullanlabilir..
retilen kompozitlere, Fe ilavesinin matriksteki sertlii drd fakat B4C ile glendirilmi kompozitlerin
sertliinin dierlerine gre artt grlmtr. B4C ilaveli Fe-Co matriks kompozitlerin anma kayplarnn ilavesizlere daha az olduu gzlemlenmitir.
KAYNAKLAR
1. Karagoz, S., Zeren, M., Characterisation of Hot Pressing Behaviour of Diamond Cutting Tools, Int. PM Conf.,
Granada-spanya, 4, 208-212, 1998.
2. Karagoz S, Zeren M.,The Property Optimization of Diamond Cutting Tools with the Help of Microstructural
Characterisation, 3rd European Conference on Advances in Hard Materials Production, EUROPM, Turintalya, 399-405,1999.
3. Bailey M.W. and Bullen G.J., The de Beers sda Series of Diamond Abrasives and its Stability for the Stone
Industry, Eskenazi Semineri, 1-33, stanbul, 1987.
4. Karagoz S, Zeren M.,Srekli Disk Tipi Elmasl Kesici Takmlarda HataKarakterizasyonu, 9. Uluslararas Metalurji ve Malzeme Konf. Bildiriler Kitab, T.M.M.O.B. stanbul, 517-525, 1997.
5. Gray, A.E., Elmas Soketlerin Toz Metalurjisi ile retiminde Kobalt-Bronz Orannn Soket zelliklerine Etkisinin ncelenmesi, Yksek Lisans Tezi, Dumlupnar niversitesi F.B.E., 2005.
6. Karagz, ., Zeren., M., Doal Ta Kesiminde Kullanlan Elmas Kesici Takmlarn Anma Karakteristii, Uluslararas Katlml 4. Ulusal Toz Metalurjisi Konferans, Dzenleyen: Trk Toz Metalurjisi Dernei, Ankara,
2002.
7. Zeren, M., Elmas Kesici Takmlarda Mikroyapsal Karakterizasyon zerinden zelliklerin Optimizasyonu,
Doktora Tezi, Kocaeli niversitesi F.B.E., 2005.
8. Ucun , Aslantas K, Byksag S, Tagetiren S, An Investigation on the Effect of Diamond Concentration and
Matrix Material Composition in the Circular Sawing Process of Granites, Proceedings of the Institution of
Mechanical Engineers, Part C : Journal of Mechanical Engineering Science,1,1-11, 2010.
9. Barbosa, A., Bobrovnitchii, G., Skury, A., Guimaraes, R., Filgueira, M., Structure, Microstructure and Mechanical Properties of PM Fe-Cu-Co Alloys, Materials and Design, 31,522-526,2010.
10. imir, M., ksz, K.E., ahin, Y., Investigation of the Wear behavior of B4C Reinforced Fe/Co Matrix Composites Produced by Hot Pres, International Conference on the Mechanical Behavior of Materials, Como
Lake, Italy, 5-9 June, 2011.
591

Mo, Ni ve Cu KATKILI Fe ESASLI T/M ALAIMINDA AINMA DRENCN

ETKLEYEN PARAMETRELERN DENEYSEL VE STATSTKSEL
YNTEMLERLE NCELENMES
Serkan ZEL*, Nusret BOZKURT** ve lyas SOMUNKIRAN***
*Bitlis Eren niversitesi, Mhendislik ve Mimarlk Fakltesi, Makina Mhendislii Blm, 13000, Bitlis,
sozel@beu.edu.tr
**Bitlis Eren niversitesi, Mhendislik ve Mimarlk Fakltesi, naat Mhendislii Blm, 13000, Bitlis,
nbozkurt@beu.edu.tr
***Frat niversitesi, Teknik Eitim Fakltesi, Metal Eitimi Blm, 23119, Elaz, ilyass@firat.edu.tr
ZET
Bu almada, Toz Metalurjisi (T/M) yntemiyle retilen Mo, Ni ve Cu katkl Fe esasl toz alam zerinde anma
deneyi uygulanm ve anma direncine etkili olan deneysel parametreler Taguchi yntemi kullanarak incelenmitir.
Argon gaz atmosferinde Fe esasl toz alam preslemeden sonra 30 dk sre ile 1000, 1050, 1100, 1150 ve 1200
o
C gibi farkl scaklklarda sinterlenmitir. Farkl sinterleme scaklklarna sahip numuneler 20 N yk altnda adhasif
anma deneyine tabi tutulmutur. almada L25 (52) Taguchi ortogonal dizi ile deney tasarm gerekletirilmitir.
Deneysel parametrelerin (sinterleme scakl, kayma mesafesi) anma direnci zerindeki nem seviyesini belirleyebilmek iin istatistiksel metotlardan ANOVA ve F-test uygulanmtr. statistiksel analiz sonular deneysel
alma sonularn destekleyerek, Fe esasl toz alamnda artan sinterleme scaklnn anma direncini arttrd
belirlenmitir.
Anahtar kelimeler: T/M, Sinterleme, Anma, Taguchi, ANOVA.
THE INVESTIGATION WITH EXPERIMENTAL AND STATISTICAL

METHODS OF PARAMETERS AFFECTING WEAR RESISTANCE OF
Fe BASED P/M ALLOY ADDED Mo, Ni ve Cu
ABSTRACT
In this study, wear test was carried out on dust alloy based Fe containing Mo, Ni and Cu additives produced with
Powder Metallurgy (P/M) method, and experimental parameters affecting on wear resistance were investigated
using Taguchi method. In the argon gas atmosphere, Fe based dust alloy was sintered in different temperatures of
1000, 1050, 1100, 1150 and 1200C with duration of 30 mins after pressed. The samples having different sintering
temperatures were subjected to adhesive wear tests under 20 N load. In the study, experimental design is made up
with L25 (52) of Taguchi orthogonal series. ANOVA and F-test of the statistical analysis methods were used in order
to determine the importance level of the experimental study parameters (sintering temperature and wear distance)
on wear. Statistical analysis results supported the experimental study data and showed that the abrasion resistance
increased with the increasing of the sintering temperature in the powder alloy including Fe.
Keywords: P/M, Sintering, Wear, Taguchi, ANOVA.
592

1. GR
Toz Metalurjisi (T/M) yntemi, hassas metal paralarnn retiminde kullanlan ok gelimi bir yntemdir. Bu yntemin temel admlar, elementel tozlarn kartrlmas, sktrlmas ve sktrma sonras toz partikllerinin birlemesi
iin sinterleme ileminin uygulanmasdr. Gnmzde T/M yntemiyle para retimi ok yaygn olarak kullanlmakta
ve giderek bilinen retim yntemlerine alternatif olmaktadr. leri bir imalat yntemi olan T/M, teknolojik malzemelerin retilmesine ok uygun, kk paralarn ok sayda ve ekonomik retimini salayan bir yntemdir. Toz metalurjisinin amac, metal ve metal alamlarn tozlarn ergitmeden, basn ve scaklk yardmyla, dayankl cisimler
haline getirmektir. Sinterleme ise ergitmenin yerini tutmakta ve kullanlan metal tozunun ergitme scaklnn altndaki bir scaklkta yaplan bir sl ilemdir [1, 2, 3]. T/M yntemi, otomotiv endstrisinde kullanlan zellikle yapsal
paralar, dili, piston, balant ubuklar gibi ar para uygulamalarnda nemli rol oynamaktadr. Son yllarda, T/M
elik paralara retim maliyetinin azalmas nedeniyle talep artmtr. Buna bal olarak, otomotiv endstrilerinde
kullanlan byk paralar, toz metalurjisi ile retilmektedir [4]
Toz metalurjisi yntemi kullanlarak retilen demir esasl molibden, nikel, bakr ve karbon ilaveli toz alamlar
yksek mukavemet ve tokluk salanmas amacyla gelitirilmitir. Demir esasl toz metal malzemeler yksek anma dayanml motor ve anzman sisteminde, otomotiv endstrisinde geni uygulama alan bulmutur [5, 6]. Fe
esasl toz alamlarnda, Mo ilavesi kat zelti yaparak mukavemeti, dolaysyla bu alamlarda sertleebilirlii
arttrmaktadr. Dier yandan Mo elementi, karbon elementi ierisinde zndnde, malzemenin sertleebilirliini
arttrmaktadr. Ayn zamanda Ni elementi ile birlikte bulunduunda anma dayanmn da arttrmaktadr [7]. T/M ile
retilen elik malzemelerin sinterlenmesinde sv faz ve sertlik arttrc olarak Cu tozu ilave edilmektedir. % 1-2 bakr
ilaveli alamlar byk boyuttaki paralarn retiminde kullanlr. Ni ilavesi ile bakrn oluturduu boyutsal deimeleri azaltlabilmektedir. % 2,5 Ni tozu ilavesi ise ekme dayanm artrmaktadr [8].
Mhendislik bilimlerinde deneysel alma sonularnn istatistiksel metotlarla analizinin yaplarak doruluunun
teyit edilmesi ya da sonularn optimize edilmesi almalar yaygn olarak yaplmaktadr. Sakarya ve Glolu [9]
almalarnda, Taguchi yntemini kullanarak cep ilemede kullanlan takm yolu hareketlerinin ve kesme parametrelerinin yzey przll zerindeki etkilerini aratrmlardr. Tosun ve Cogun [10], kablo kaplama zerine yaptklar almada istatistiksel metodlardan ANOVAy kullanmlardr. Bozkurt ve Yazcolu [11], hafif beton tasarm
zerine yaptklar almada kullanlan katk tipinin ve uygulanan farkl kr srelerinin beton zellikleri zerindeki
etkilerini deneysel ve istatistiksel yntemler ile aratrmlardr.
Bu almada, T/M yntemiyle retilen Mo, Ni ve Cu katkl Fe esasl toz alamna farkl sinterleme scaklklar
uygulanm ve elde edilen numunelere anma deneyi yaplarak anma direncine etkili olan deneysel parametreler
Taguchi yntemi ile incelenmitir.
Bu almada kullanlan Fe esasl Mo, Ni, Cu toz alam, toz atomizasyon yntemiyle retilmitir. Tablo 1de bu toz
alamna ait kimyasal analiz sonular grlmektedir.
Tablo 1. Fe esasl Mo, Ni, Cu toz alamnn kimyasal analizi
Mo
Ni
Cu
C
Fe
% 0.50
% 4.04
% 1.50
% 0.01
Kalan
Fe esasl Mo, Ni, Cu toz alam, 600 MPa basn altnda tek eksenli preste basma kuvveti ile preslenmitir. Preslenen numuneler argon gaz ortamnda 1000 oC, 1050 oC, 1100 oC, 1150 oC ve 1200 oC scaklklarda 30 dakikalk
srelerde sinterlenmitir. Mikroyap incelemeleri iin numunelerin yzeyleri metalografik numune hazrlama aamalarndan geirilmitir. Numunelere uygulanan block on ring tip adhesif anma deneyi, andc olarak 32 mm
apndaki yzeyi honlanm AISI 9840 elii kullanlarak, 20Nluk ykte, 100-500 m. kayma mesafesinde, 0,15 m/
sn kayma hznda farkl srelerde gerekletirilmitir. Anma miktarlar tespitinde, anma ncesi ve sonras 10-5 gr.
arla duyarl Scaltec marka elektronik terazi kullanlarak, ktle kayb belirlenmitir.
2.1. statistiksel Analiz
Bu almada, deney parametrelerinin sonular zerindeki nem derecelerini istatistiksel olarak grebilmek iin L25
(52) Taguchi ortogonal dizi tasarm kullanlm ve ANOVA ile F-test metotlar uygulanmtr. Hesaplanan F deeri-
593

nin byk olmas deney parametrelerindeki deikenliin performans karakteristikleri zerinde byk bir deiime
neden olduu anlamna gelmektedir [10, 12, 13].
ANOVA metodunda deneysel deerler ile arzu edilen deerler arasndaki sapmay hesaplayabilmek iin bir kayp
fonksiyon kullanlmtr. Bu kayp fonksiyon daha sonra bir sinyal-grlt (S/G) oranna dntrlmtr. Karakteristik tipine bal olarak retilen farkl sinyal-grlt oranlar vardr [13]. Toz alamnn yksek performansa sahip
olmas, mekanik ve fiziksel baz karakteristik zelliklerinin yksek olmas ile belirlenebilir. Bu almada fiziksel
anlamda daha az anma kayb daha iyi karakteristie sahip malzemeyi iaret ettii iin Daha Kk Daha yidir
(Smaller is Better:SB) kayp fonksiyonu kullanlmtr. Bu kayp fonksiyona ve sinyal-grlt oranna ilikin formller aada verilmitir:
S/Gij=-10log (Lij)
(1)
(2)
Burada Lij, j.deneydeki i. performans karakteristiinin kayp fonksiyonu ve S/G ise sinyal-grlt orandr. n denemedeki testlerin saysn, y ise k. test j. denemedeki i. performans karakteristiinin deneysel deerini ifade etmektedir. Sinyal-grlt oranlarnn hesaplanmas iin kullanlan deney kontrol parametreleri ve bunlara ilikin seviyeler
Tablo 2de verilmitir.
Tablo 2. Kontrol faktrleri ve seviyeleri
Scaklk (C)
Kayma Mesafesi (m)
Seviye 1
1000
100
Seviye 2
1050
200
Seviye 3
1100
300
Seviye 4
1150
400
Seviye 5
1200
500
Presleme sonras farkl scaklklarda sinterleme ilemine tabi tutulan numunelerin ekil 1de verilen SEM fotoraflar incelendiinde, bakrn ergime derecesine bal olarak 1000 oC scaklkta sv faz sinterlemesinin meydana gelmedii, artan scaklkla beraber (1150 oC ve 1200 oC) numune iin gerekli olan sv faz sinterlemenin gerekletii
grlmektedir. Bakr sv faza geerek tane snrlarna doru ilerlemitir.
(a)
(b)
(c)
(d)
594

(e)
ekil 1. Farkl sinterleme scaklklar sonras numunelerin SEM mikroyap resimleri a)1000 oC b) 1050 oC
c) 1100 oC d) 1150 oC e)1200 oC
3.1. Deneysel Anma Deerlerinin rdelenmesi
20 N yk altnda yaplan anma deneyi sonucunda elde edilen deerler ekil 2deki grafikte verilmitir. Grafik incelendiinde en fazla anma kaybnn, en az sinterleme scaklna sahip numunede gerekletii grlmektedir.
Anma miktar sinterleme scaklnn artmas ile dmtr. Sv faz sinterlemesinin gerekletii 1150 ve 1200 oC
sinterleme scaklna sahip numunelerde anma miktar dmtr. Sv fazn olumas ile eriyen bakrn taneler
arasnda sv faz oluturmas, Cun balayclk grevi grmesi ve tane ilerine doru difzyonu ile taneler aras
ba glendirmesiyle, yksek performansta para retimi salanabilmektedir.
ekil 2. Farkl scaklklarda sinterlenen numunelerin 20N yk altndaki arlk kayb-mesafe ilikisini
veren anma grafii.

(a)
(b)
ekil 3. a)1000 oC scaklkta sinterlenen, b) 1200 oC scaklkta 30 dk. srede sinterlenen numunelerin anma
yzey fotoraflar.
Anma yzey fotoraflarna bakldnda (ekil 3-a) 1000 oCde sinterlenen numunenin anma izlerinin derin olduu grlmektedir. ekil 3-bde grlen ve 1200 oC scaklkta sinterlenen numuneye ait anma yzey fotorafnda
ise anma izlerini 1000 oCdeki numuneye gre daha az derinlie sahip olduu grlmektedir. Buda bize anma
grafiinde verilen en az anma deerinin 1200 oCdeki numuneye ait olduunu desteklemektedir.
595

3.2. statistiksel Sonularn rdelenmesi

Blm 2de belirtilen deney kontrol parametreleri iin hesaplanan S/G oranlar Tablo 3de verilmitir. Bu tabloda
deney parametrelerinin etkisinde sonular maksimum yapan seviyeler iaretlenmitir. Ayrca sonularn daha iyi
yorumlanmas iin bu deerler kullanlarak ekil 4te toz alamnn anma kayb zelliine ilikin etki grafii verilmitir.
S/G oranlar temel alnarak oluturulan ekil 4 ve varyans analizi tablosundan (Tablo 4) toz alamnn karakteristik
zelliklerinin farkl sinterlenme scaklklarndan ve kat edilen kayma mesafelerinden etkilenmi olduu istatistiksel olarak ortaya konularak deneysel alma bulgular dorulanmtr. Kat edilen kayma mesafesinin art (100
mden 500 mye artmas) ile anma kaybnda art grlmesi beklenen bir sonutur. Bunun yannda bu istatistiksel
alma ile sinterlenme scakllnda farklln olmas, anma kaybnda deney sonularn etkileyen nemli bir
deiken parametre olduu ortaya konulmutur. ANOVA tablosu incelendiinde sinterlenme scaklnn farkllk
gstermesi ile bu etkinin toz alamnn karakteristik zellii zerinde kayma mesafesi kadar olmasa da neme
sahip olduu grlr.
Tablo 3. Faktr seviyelerinin S/G oranlar
Anma Kayb
Seviye 1
Seviye 2
Seviye 3
Seviye 4
41,57
43,00
45,58
46,24
57,92*
45,58
41,39
39,98
*Deney sonularn maksimum yapan seviyeler
Scaklk
Mesafe
Seviye 5
47,72*
39,25
Kontrol parametreleri ve seviyeleri

ekil 4. Anma kayb iin deneysel parametrelerin S/G oran grafii.
ekil 4 incelendiinde, scakln artmas ile eimin artt, mesafenin artmas ile ise eimin azald grlmektedir.
Hesaplanan S/G oran deerlerine gre oluturulan bu etki grafii, sinterlenme scaklnn artmas ile toz alamnn bir karakteristik zellii olan anma kaybnda minimizasyonun; kat edilen mesafenin artmas ile bu karakteristik
zellikte maksimizasyonun (anma kayb artnn) olduunu ortaya koymaktadr.
Tablo 4. Anma kayb iin varyans analizi (ANOVA) tablosu
Kontrol Faktr
Scaklk
Kayma Mesafesi
Hata
Toplam
Serbestlik
Derecesi
4
4
16
24
Kareler
Toplam
127
1191
125
1443
Varyans
31,2
297,8
-
3,9
37,6
-
0,021
0,000
-
Tablo 4 varyans analizi sonularn ve buna bal olarak hesaplanan F-test ve P-deeri (nem-anlamllk deeri) sonularn gstermektedir. Anma deneylerinde kayma mesafesinin arlk kaybna olan etkisi bilinmektedir. Anma
kayb zerinde deney parametrelerinden kayma mesafenin, 297.8 varyans deeri, 37.6 F-test deeri ve 0 P-deeri ile en byk etkiye sahip olduu istatistiksel analiz sonucunda da ortaya koyulmutur. Scaklk parametresinin
ise varyans analizi deeri ve F-test deerinin zerinde anlaml bir etkiye sahip olduu P-deerinin 0.5 limitinden
dk olmas sonucundan anlalmaktadr.
596

4. SONULAR
- Farkl sinterleme scaklklarna sahip numunelerin mikroyaplarnda deiiklikler gzlenmitir.
- 1150 oC ve 1200 oC scaklklarda sinterlenen numunelerde sv faz sinterlenmesi gereklemitir.
- Anma miktar en fazla 1000 oCde sinterlenen numunede, ez az anma miktar ise 1200 oCde sinterlenen numunede gereklemitir.
- Deneysel alma sonular ile istatistiksel alma sonular birbirini destekler nitelikte elde edilmitir.
- statistiksel alma sonucunda kayma mesafesinin artmas ile anma kaybnn artt, sinterlenme scaklnn
arttrlmas ile anma kaybnda azalma olduu grlmtr.
KAYNAKLAR
1. Narayanasamy R., Ramesh T., Pandey K.S., Workability studies on cold upsetting of AlAl2O3 composite material, Materials and Design, Vol. 27, 7, pp. 566-575, 2006.
2. Ouz ., ztrk Z., Uzun E., Kurt A., Boz M., Gaz Atomizasyonu Yntemi le Kalay Tozu retiminde Gaz Basncnn Toz Boyutu ve ekline Etkisi, 6th International Advanced Technologies Symposium (IATS11), s.
565-568, Elaz, 2011.
3. Somunkran ., Baln A., Scak Presleme Tekniiyle retilen Co Esasl Co-Cr-Mo Toz Alamnda Presleme
Scaklnn Mikroyap zerine Etkisi, 6th International Advanced Technologies Symposium (IATS11), s.
223-228, Elaz, 2011.
4. H.Khorsand, S.M.Habibi, H.Y oozbashizadea, K.Janghorban, S.M.S.Reihani, H.Rahmani Serajib, M.Ashtari,
The role of heat treatment on wear behavior of powder metallurgy low alloy steels, Materials and Design,
Vol. 23, pp. 667670, 2002.
5. Somunkran ., zel S., Fe Esas Toz Alamnda Sinterleme Scaklnn Anma Direncine Etkisi, 10. Uluslararas Malzeme Sempozyumu, s. 153-157, Denizli, 2006.
6. Fujiki A., Present State and Futureprospects of Powder Metallurgy Parts For Automotive Applications, Materials
Chemistry and Physics, Vol. 67, pp. 298-306, 2001.
7. zgn ., Toz Metalurjisi le retilen Alaml eliklerin Mikroyapi ve Mekanik zellikleri, Sakarya niversitesi
Fen Bilimleri Enstits, Yksek Lisans Tezi, 2007.
8. Salak A., Ferrous Powder Metallurgy, ISBN:1898326O37, Cambridge International Science Publishing,
England, 1995.
9. Sakarya N. ve Glolu C., Taguchi Yntemi ile Cep lemede Kullanlan Takm Yolu Hareketlerinin ve Kesme
Parametrelerinin Yzey Przllne Etkilerinin Belirlenmesi, Gazi niv. Mh. Mim. Fak. Der., 21, 4, s.
603-611, 2005.
10. Tosun N., Cogun, C., An investigation on wire wear in WEDM, Journal of Materials Processing Technology,
Vol. 134, pp. 273-278, 2003.
11. Bozkurt N. ve Yazcolu S., Srdrlebilir Tayc Hafif Beton Tasarm ve Mekanik zelliklerinin Aratrlmas, Uluslararas Srdrlebilir Yaplar Sempozyumu (ISBS), Ankara, 2010.
12. Tosun N. and Ozler, L.,Optimisation for Hot Turning Operations with Multiple Performance Characteristics, The
International Journal of Advanced Manufacturing Technology, No 23, pp. 777-782, 2004.
13. Ross P.J.,Taquchi Tecniques for Quality Engineering, McGraw-Hill, 2nd Edition, New York, 1996.
597

COMPACTION
www.turkishpm.org
598

ON THE SEVERE PLASTIC DEFORMATION OF SINTERED STRUCTURAL

STEELS BY CONSTRAINED GROOVE PRESSING
Viorica CHERTES, Radu L. ORBAN, Ioan VIDA-SIMITI, Liviu BRNDUAN
Technical University of Cluj-Napoca,
103-105 Muncii Blv., Romania, chertes@gmail.com
ABSTRACT
The possibilities of Severe Plastic Deformation (SPD) application to improve mechanical properties of sintered
structural steels are investigated. Among the known SPD variants, Constrained Groove Pressing (CGP), was selected as it keeps the part shape and precision. It consists in part repressing in a die of similar cavity but a little larger
cross section, producing both compression and shear stresses with pore closing and microstructure refining. The
effects of compacting and sintering parameters and of re-pressing pressure, on the final density, microstructure and
hardness of sintered parts processed from Distaloy AE powder by cold die compaction/sintering is presented.
Keywords: Powder Metallurgy, Severe Plastic Deformation, Mechanical Properties.
1. INTRODUCTION
The extending of Powder Metallurgy (PM) application, as a clean, productive and cost-effective technology to
a wider range of structural parts fabrication is still limited by its known drawback of the inherent porosity, which
diminishes mechanical properties in comparison with those of their wrought counterparts with the same chemical
composition [1]. An intensive research activity is worldwide performed to overcome this drawback. Powders with
improved compressibility, more efficient compaction lubricants, die wall lubrication, new compaction technologies
like warm and high velocity compaction, more efficient sintering and post sintering treatment technologies like high
temperature sintering and sinter-quenching have been developed [2]. Even though all these have brought a notable
progress, it is not yet at the expectations and, consequently, intensive researches are still underway [3].
A method of a high potential to notable reduce porosity of sintered parts and even to refine their microstructure,
improving on these ways mechanical properties, is Severe Plastic Deformation (SPD) [4]. In spite of its proved
potential to lead to the obtaining of sub-micron or even nanocrystalline structures in bulk metallic materials and,
implicitly, to improved mechanical properties, there is a very little information on the SPD application to sintered
structural materials, most of them referring to the green compact advanced consolidation by the most investigated
SPD variant - Equal Channel Angular Pressing (ECAP). So, K. Xia et al. [5] revealed that significantly increased
density, while N. Harrison et al. [6] that also smaller grain sizes and improved hardness values can be achieved
by this method. However, although it is expected that ECAP can be also applied to sintered materials, being, in
fact, an extrusion process, can not be applied to the near-net shape part obtaining. For this purpose, J. Asami et
al. investigated die compaction at 2000 MPa for sintered structural parts [7], proving the possibility of SPD application to the near-net shape green part obtaining, of which sintering leads to mechanical strength equivalent to that
of full dense compacts. So, they have established that higher green densities, up to 7.6 g/cm3 and a fine-grain
microstructure can be achieved on this way. Furthermore, these properties can be controlled without difficulty, by
selecting the SPD degree of deformation and applied pressure. But, it was not found any published information
concerning SPD application directly to the obtaining of near-net shape sintered parts. Consequently, this possibility
has been considered in the present research with reference to the most used materials in sintered structural part
fabrication - low alloy steels. By analyzing the known SPD variants {Equal Channel Pressing (ECAP), Constrained
Groove Pressing (CGP), Differential Speed Rolling (DSR) etc.}[4], one was established that the most appropriate
for sintered parts is CGP, as it keeps the part shape and assures the obtaining of the required precision. It consists
in part repressing in a die of a similar shape cavity but of a little higher cross section, producing both compression
599

and shear stresses with pore closing and microstructure refining. Consequently, it was adopted in this research.
The effects of cold die compacting and sintering parameters in Endo-gas and of re-pressing pressure, on the final
microstructure, density, hardness, ultimate tensile strength and elongation of structural parts obtained from Distaloy
AE powder were investigated and are presented.
Hgans Distaloy AE powder low alloyed with Cu, Ni and Mo [8] has been uniaxially compacted at different compacting pressures (200, 400, 500, 600 and 700 MPa) to cylindrical samples of a diameter of 9,24 mm (cross section
area, S0 = 67.06 mm2) and a height of 8 mm, in a pressing tool with floating die, with die wall lubrication. Beside
these cylindrical samples for density determination, three tensile test samples (ISO 2740:2009) have been realized
but only at a compacting pressure of 700 MPa. All these green samples were sintered in industrial conditions, in a
belt sintering furnace, at 1120 0C, in endogas with a dew point of -40 0C for 40 min, followed by cooling in the waterjacket cooling zone of the sintering furnace (cooling rate ~30 0C/min).
In agreement to the selected CGP variant of SPD, the die re-pressing with transverse deformation of material (Fig.
1) [1] has been adopted in the experimental researches.
Figure 1. Principle of die compaction with transverse deformation of material [1].

According to the Theory of Plastic Deformation of Metallic Materials [9], even to a compression applied stress,
shear stresses also appear in the transverse directions, leading to material deformation both by compression and
by shear. In the case of porous materials, this results in the pore flattening and can lead to their wall cold welding
under the applied pressure. Therefore, after their density and hardness determination by the Archimedes method
(ISO 2738:1999/ASTM B962) and Rockwell B method (ISO 6508-1:2005/ASTM E18 respectively, all the cylindrical
samples were re-pressed in a rigid die of the same shape as the initial sintered compacts but having a higher area
of the cross section, i.e. diameter of 11,28 mm (cross section area, S1 = 100 mm2), respectively with a degree of
transversal deformation, tr 33 % with pressures of 1400 1600 and 1800 MPa and die wall lubrication using the
same lubricant as to the initial pressing, without annealing between the initial pressing and re-pressing. To avoid the
die crack, it has been consolidated with a 205Cr115 high strength steel (ASTM A-120) clamping ring. Three cylindrical samples were realized in the above mentioned conditions for each compacting pressure, respectively adopted
re-pressing pressure (i.e. a total of 36 samples). However, as the construction of a die of a higher cross section
than of the standard one and also its consolidation was more difficult, for the test samples re-pressing was adopted
the same die as for their compaction and only one re-pressing pressure, respectively 1200 MPa. To accomplish
the condition of sample transversal deformation during re-pressing in the same die as for compaction, beside their
cross section reduction by shrinkage at sintering, a supplementary reduction has been realized by uniform grinding
along to contour with a cutting depth of 0.86 mm, to assure a transverse deformation degree as that adopted for
cylindrical samples ~33%).
The re-pressed cylindrical samples were characterized by density and hardness determination in the same way as
before re-pressing, and also by their microstructure optical examination, after etching with Nital 3%, on an Olympus
50x 1000x inverted metallurgical metallographic microscope with USB digital JPG image camera, while both assintered and re-pressed tensile samples were subjected to tensile test at room temperature, in conditions of the
above mentioned ISO 2740:2009 with a loading speed 1 mm/min, on universal testing machine Sun 5, with stress
strain diagram recording.
Metallographic investigation was performed for revealing the correlation between microstructure compacting and
re-pressing pressures. As can be seen in Figure 2, presenting, for the lack of space, only typical microstructure of
600

the re-pressed samples, a dense microstructure with fine grains, oriented toward the main direction of plastic deformation (by shearing) have been formed, while porosity has been almost totally eliminated, being much lower than
of the sintered samples without re-pressing. Certainly, it depends upon the re-pressing pressure, but also upon the
initial density and, intricately, by the compacting pressure.
Figure 2. Typical microstructure of the re-pressed at 1800 MPa sample, initially compacted at 700 MPa.
Etching: Nital 3%.
The correlation between density, D compacting pressure and re-pressing pressure, P, for the same degree of
transversal deformation is graphically presented in Figure 3. For better reflecting the effect of re-pressing pressure
on the densification process, on the right Y axis of the graph has been represented the Compactness, C, i.e.
Figure 3. Effect of re-pressing pressure on the density, D and compactness, C of sintered compacts for the used
compacting pressures.
Relative density values - established in respect to the theoretical density of Distaloy AE material, calculated taking
into consideration its composition {(Cu 1.5%, Ni 4.0%, Mo 0.5 %, Fe balance (94.0 %)}[8] and density of
components respectively. As can be seen, by the common PM route of cold compaction and sintering (0 value of
re-pressing pressure on diagram), the obtained density values are in the limits provided by the Distaloy AE powder
producer, Hgans AB co. [8], proving that these operations occurred normally. Instead, as expected, a notable
increasing of density, respectively of compactness, occurred by re-pressing. Certainly, the highest density (points
filled with the same color)/compactness (points filled in yellow) values have been obtained for the highest repressing pressure (1800 MPa) and for the highest compaction pressure used in the green compact preparation (700
MPa), but well above 90 % relative densities have been also obtained for the re-pressing pressure of 1600 MPa and
even of 1400 MPa and for the compacting pressures of 600 MPa and even of 400 MPa.
601

Figure 4. Effect of re-pressing pressure on the compactness of sintered compacts increasing for the used
compacting pressures.
All these findings prove that the method can be applied at the industrial scale as 1600 and 1400 MPa re-pressing
pressures can be easier adopted than 1800 or, certainly, than 2000 MPa above mentioned as adopted by J. Asami
et al. in their research [7], while 600 and 400 MPa compacting pressures are more often used than 700 MPa in the
sintered structural part fabrication to prevent excessive wear of tools [1].
To evaluate repressing behavior and the work hardening introduced by the re-pressing of sintered samples without
their intermediate annealing advantageous from the cost point of view the compactness increasing as a function
of the re-pressing pressure has been calculated and also the main mechanical properties were determined.
So, in Figure 4 is presented the compactness increasing as a function of re-pressing pressure for all the used compacting pressures. Certainly, the increasing of this characteristic by re-pressing is as high as re-pressing pressure
is higher. However, on the first view, it appears somewhat surprising that the maximum compactness increasing
doesnt occur for the maximum used compacting pressure (700 MPa), but, on the contrary, it has the smallest values. This is an indubitable proof that, at re-pressing, densification occurs mostly by the pore elimination as a result
of the above-mentioned shear and cold welding processes and samples compacted with 700 MPa already have the
smallest porosity (< 10 %, see Fig.3) among all the samples.
Hardness and tensile rupture strength of the re-pressed samples are sensitive properties which can portray the
amount of pore closing and of cold hardening during re-pressing without an intermediate annealing process. For
the lack of space, in Figure 5 is presented hardness variation with re-pressing pressure only for samples compacted
with 700 MPa.
Figure 5. Hardness of the re-pressed compacts variation with the re-pressing pressure for the compacting
pressure of 700 MPa.
Surprisingly, it abruptly increases, with 42.69%, by re-pressing up to the re-pressing pressure of 1400 MPa (from
71.48 HRB to 102 HRB), remaining quite the same for its higher values (medium values of 102.66 for 1600 MPa
and of 104.12 for 1800 MPa) in spite of the above presented results of density increasing. This proves that hardness of sintered samples increasing at re-pressing is determined to a higher extent by the material cold hardening
than by the sample densification and there are not significant differences between the material cold hardening at
602

re-pressing with re-pressing pressures higher than 1400 MPa. The most appropriate trend-line, fitting on the best
extent the experimental variation curve (smallest value of R2), the logarithmic one (see Fig. 5) shows a tendency of
asymptotic increase of hardness as the re-pressing pressure increases, which appears more normal.
However, tensile test at room temperature seems to lead to a similar result. So the recorded stress-strain curves
for the re-pressed samples with only 1200 MPa, a re-pressing pressure smaller even to that to which the hardness
increases 1400 MPa (see Fig. 5), and of as-sintered sample (repressing pressure equal to zero), not included
hire for the lack of space, indicates a value of ultimate tensile strength of the re-pressed sample (UTS1200 = 473.18
MPa) with 24.34 % higher than of the as-sintered sample (UTS0 = 380.56 MPa). But, an unexpected increase of
the elongation at rupture, from Er0 = 7.43 % for the as-sintered sample to Er1200 = 7.64 % for the re-pressed with
1200 MPa, i.e. with ~2.8 % has been also observed. This cannot be explained by the material cold hardening, as
on the contrary, by cold hardening plasticity and, implicitly, elongation at rupture in tension decrease. So, it can be
attributed in exclusivity to densification. Consequently, one can be resumed that hardness of sintered parts increase
at re-pressing is determined mostly by the material cold hardening, while tensile properties (ultimate tensile strength
and elongation) by the sample densification.
3. CONCLUSIONS
The above presented results prove that severe plastic deformation can be successfully applied to sintered low
alloyed steels - the most used in the sintered structural parts fabrication for their both density and mechanical
properties. In the CGP variant, i.e. by the sintered compact further die compaction with transverse deformation of
material, it can be applied to parts of a high complexity, keeping their geometrical shape and precision. For the common industrial used compacting pressures (400-600 MPa), an increase in density of about 5 -12 [%], in hardness of
over 30 %, in UTS of 20-25 % and in elongation of 2.5-3.5 % can be achieved in quite simple and safe conditions,
replacing the classical calibration operation with severe plastic deformation.
REFERENCES
1. * * * ASM Handbook, Vol. 7, Powder Metal Technologies and Applications, ASMI, 1998, ISBN 978-0-87170-3873, 1238 p.
2. T. Sawayama, M. Sato, Y. Seki, T. Tsuchida and H. Yaguchi, High Performance P/M Materials by High Density
Process, Proceedings of 2000 Powder Metallurgy World Congress, The Japan Society of Powder and Powder
Metallurgy Ed., Tokyo, 2000, Part 1, p. 540-542, ISBN 4-9900214-8-7.
3. J. M. Torralba, R. De Oro and M. Campos, From Sintered Iron to High Performance PM Steels, Materials Science Forum, Ed. Trans Tech Publications Ltd, Switzerland, Vol. 672, pp. 3 11, 2011.
4. A. Azushima et al., Severe plastic deformation (SPD) processes for metals, CIRP Annals - Manufacturing
Technology 57(2), 716 (2008).
5. K. Xia and X. Wu, Back pressure equal channel angular consolidation of pure Al particles, Scripta Materialia,
Vol. 53, Issue 11, 2005, p. 1225. (2005).
6. Harrison & I. T. H. Chang, Consolidation of Elemental Aluminium Powders Using Equal Channel Angular Pressing (ECAP), Proceedings of the PM 2010 World Congress, Vol.1, p. 565-572.
7. J. Asami, N. Hirose and T. Kohno, Die Compaction at 2000 MPa for Sintered
Structural Parts, Proceedings of 2000 Powder Metallurgy World Congress, The Japan Society of Powder and
Powder Metallurgy Ed., Tokyo, 2000, Part 1, p. 570-573, ISBN 4-9900214-8-7.
8. *** Hgans Iron and Steel Powders for Sintered Components, Copyright Hgans AB, 2002, 393 p.
9. K.M. Ralls et. al., An Introduction to Materials Science and Engineering, John Wiley& Sons Ed. 1976.
603

COMPOSITES
www.turkishpm.org
604

AN EVALUATION OF SiC PARTICLE REINFORCED CEMENTED

COPPER COMPOSITES
Gozde F. CELEBI EFE, Ibrahim ALTINSOY, Mediha IPEK, Sakin ZEYTIN, Cuma BINDAL
Sakarya University, Engineering Faculty, Department of Metallurgy and Materials Engineering, Esentepe Campus,
54187 Sakarya-Turkey, E-mail:gcelebi@sakarya.edu.tr
ABSTRACT
In this study, copper powder was produced by cementation method. For comparison, cemented and commercial
copper powders were reinforced with SiC particles of 1 m size and at ratios of 0, 1, 2, 3 and 5% by weight. Powder mixtures were pressed with an axial pressure of 280 MPa and embedded in graphite powder for obviating the
oxidation. Sintering process was performed in an open atmospheric furnace at 700C for 2h. The morphology and
phases of composites were analyzed by Scanning electron microscope (SEM) and X-ray diffraction (XRD) techniques. Optical and SEM studies showed that SiC particles were located around the copper grains. Commercial
Cu-SiC composites have more homogenous microstructure than the cemented Cu-SiC composites due to the
agglomeration of cemented copper powders. Relative densities and electrical conductivities were decreased with
increasing weight percentage of SiC particles. The highest electrical conductivity of 79% IACS (International annealed copper standard) for cemented Cu-SiC composites and 86% IACS for commercial Cu-SiC composites was
obtained for Cu-1wt.% SiC composites. The microhardness of test materials increased as amount of reinforcing
materials increased.
Keywords: Cu-SiC, Composite, Cementation, Relative density, Electrical conductivity.
1. INTRODUCTION
Copper is a mostly used industrial and functional metal for various thermal and electronic applications, i.e. electronic packaging, electrical contacts and resistance welding electrodes. This is because of good thermal and electrical
conductivity, high Plasticity, softness, formability and excellent resistance to corrosion and oxidation. Although pure
copper is mostly used in electrical applications, it has a key role to play in energy efficiency and provides durable
maintenance free structures that are naturally good looking, long lasting and fully recyclable. Nevertheless, low
mechanical strength and undesirable wear resistance limit its applications [1,2]. The room temperature mechanical
strength can be improved dramatically by addition of small amount of elements such as Cr, Zr, Ag or Fe, etc. to form
precipitation- hardened alloys.
However, these copper alloys lose their high strength at higher temperature (usually 500 oC) generally related to the
structural instability caused by the coarsening of precipitation particles. Furthermore, low wear resistance and conductivity are the other two limitations of these alloys. In this respect, dispersion-strengthened copper has the ability
to retain most of its properties on exposure to high temperatures. Through adding inert, second phase particulate
materials (such as oxides, carbides, borides) in copper matrix, it can not only keep coppers excellent electrical and
thermal conductivity, but also make copper achieve appreciable strength.
The dispersion-strengthened copper alloys generally can be classified as the copper-based matrix composites.
In addition, copper-based composites physical and mechanical properties can be varied from the second phase
content. In recent years, Cu/SiC composites have received considerable attention to meet the challenges of thermal
management in the rapidly increased power of advanced electronics.
They offered a great potential for uses in electrical sliding contacts such as those in homopolar machine and railway
overhead current collection system, where high thermal electrical/thermal conductivity and good wear resistant
properties are needed, high-temperature structural applications and electronic packing due to the superior heatconductive, electric conductive and heat-releasing natures [3-6]. Methods for the production of dispersion-strengthened copper matrix composites involve ingot casting and powder metallurgy PM. processes. The PM route consists
605

of several processes like blending, compacting, and sintering. Blending is one of the crucial processes in PM where
the metallic powders are mixed with the ceramic reinforced particles. Good blending produces no agglomeration of
both the metallic and ceramic particle powders. Conventional melting and casting has distinct limitations due to the
poor wettability between ceramic particles and molten copper, leading to agglomeration of dispersoids. Moreover,
the difference in the densities and the reinforcements can also cause segregation in the melts. Therefore, the PM
route is ideal to prepare copper matrix composites because of its efficient dispersion of fine particles [4].
In this study, the influences of the amount of the SiC on the properties of the both cemented and commercial copper composites were investigated and studied what sort of differences exist between commercial or cemented
copper-SiC composites.
2. EXPERIMENTAL DETAILS
Copper powder was precipitated from the CuSO4 solution by cementation method. 2-6m cemented copper powder and 10m commercial copper powder was mixed with 1m SiC particles at weight percentage of 1, 2, 3 and
5. Powder mixtures were cold pressed in metal die of 15 mm in diameter under an axial pressure of 280 MPa.
Compacted samples were embedded into the graphite powder and sintered at 700C in an electrical furnace. After
sintering samples were immediately pressed with a load of 850 MPa in order to increase the relative density and
electrical conductivity.
The microstructures of specimens were examined by Optic and SEM microscopy. The presence of phases formed
within the sintered samples was determined by x-ray diffraction using CuK radiation with a wavelength of 1.5418
A over a 2 range of 10 to 80o. In order to detect the Cu, SiC and any oxide of Cu and SiC particles EDS analyses
were performed. Relative densities of samples were determined according to Archimedes method. Microhardness
of both pure copper and composites were determined using a Leica WMHT- Mod model Vickers hardness instrument under an applied load of 50g. Electrical conductivity of polished samples was determined by GE model electric
resistivity measurement instrument.
SEM images of initial copper powders, obtained commercially and precipitated by cementation method, were given
in Fig.1. Commercial copper powders are in spherical morphology and 10m particle size. It can be seen from the
Fig.1b that there is a significant agglomeration in cemented copper powders. Size of these agglomerates is approximately 5-7m but real size of the cemented copper grains is submicron.

(a)
(b)

Fig.1. SEM micrographs of a) commercial and b) cemented copper powder.
Optic microstructures of commercial and cemented Cu-3wt.%SiC composites sintered at 700C for 2 hours were
shown in Fig.2. Dark grey and cornered particles indicate SiC particles and light grey regions show Cu matrix. It
is seen from the Fig.2 that SiC particles dispersed in copper matrix homogenously. For commercial Cu-SiC composites, it can be said that SiC particles located at the joining points of copper grains but for cemented Cu-SiC
composites more complex microstructure is said. This is related with the agglomerated grain structure of cemented
copper.
606

(a)
(b)
Fig.2. Optic micrographs of a) commercial and b) cemented Cu-3wt.%SiC composites sintered at

700C for 2 hours.
XRD patterns of cemented and commercial copper matrix-SiC composites, including 1 and 5wt.%SiC, are shown in
Fig. 3 and consist of Cu and SiC dominantly. In the XRD analysis of cemented Cu-SiC composites slight amount of
iron-oxide (Fe3O4) was detected and it probably results from the cementation process of copper powder. For both
Cu-SiC composites SiC peaks become clear with increasing weight percentage of SiC.
Dominant phases of Cu and SiC in composites were confirmed by EDS analysis. In EDS analysis, while dark and
relatively cornered components indicate SiC, grey components indicate Cu matrix (Fig. 4). In the analysis taken
from the SiC particles in commercial Cu-SiC composite, slight oxygen was detected together with Si and C. This
probably arises from surfaces of the SiC particles. In Fig. 4b iron reach areas seems as light grey and it probably
results from cementation process and oxidized at sintering temperature.
Fig. 5 reveals that the density of composites using Archimedes principle tends to decrease with increasing SiC
content. This is due to the density of SiC particles being much smaller than that of copper [7]. Relative densities of
commercial Cu and Cu-SiC composites are higher than cemented ones. This may be related with the morphology
and agglomeration of cemented copper grains. Commercial copper grains are more spherical shape and so can be
compacted easily. Hardness variation of Cu and Cu-SiC composites with increasing SiC content was given in Fig.
6. Hardness of sintered pure copper was determined as 133HVN for commercial copper and 127HVN for cemented
copper. These values are too high from the literature value of 37 HVN for copper and this may be related with hot
pressing applied after sintering. It can be seen from the Fig. 6 that hardness values of composites increased with
increasing weight percentage of SiC particles. Hardness of ductile copper generally improves with addition of hard
disperse phase [8, 9]. It is thought that the higher the amount of the ceramic particles in the matrix, the higher the
density of the dislocation, and as a result, the higher the hardness of the composite [10, 11]. The results of electrical conductivity values measured on the polished samples were given in the Figure 7. Electrical conductivity of
cemented and commercial coppers were measured as 95.6 % IACS (International Annealed Copper Standard)
and 91.7 % IACS respectively and the addition of SiC contents decreased the electrical conductivity of Cu-SiC
composites as expected. It is possible to claim that there is a linear relationship between SiC content and electrical
conductivity and electrical conductivity values of composites are coherent with relative density and hardness values
of composites. Irregular dispersion of SiC particles in cemented copper matrix probably caused lower electrical
conductivity than commercial copper matrix composites, because of the agglomerated grain structure of cemented
copper powder.
(a)
607

(b)
Fig. 3. XRD patterns of a) cemented, b) commercial copper matrix-SiC composites including 1 and 5wt.%SiC.
Fig. 4. SEM-EDS analysis of a) commercial Cu-2wt.% SiC and b) cemented Cu-2wt.% SiC composites sintered at
700C for 2h.
Fig. 5. Relative density variation of cemented and commercial Cu and Cu-SiC composites depending on SiC
weight percentage.
608

Fig. 6. Hardness variation of cemented and commercial Cu and Cu-SiC composites depending on SiC weight
percentage.
Fig. 7. Electrical conductivity variation of cemented and commercial Cu and Cu-SiC composites depending on
SiC weight percentage.
4. CONCLUSIONS
In conclusion Cu powders were produced by chemical precipitation method from CuSO4 salts and commercially
used for comparison. Cu-SiC composites with high electrical conductivity were produced by reinforcing cemented
and commercial copper with ceramics based SiC at different ratios by the PM method at 700C in the present
work. XRD patterns of commercial and cemented Cu-SiC composites are similar to each other and consist of Cu
and SiC peak dominantly. SiC peaks become clear with increasing of SiC content. It was found that SiC particles
distributed homogeneously in Cu matrix and generally they are concentrated at grain boundaries of Cu grains for
commercial Cu-SiC composites. For cemented Cu-SiC composites more complex microstructure was observed
related with the agglomerated grain structure of cemented copper. Related with this slightly higher relative density,
electrical conductivity and hardness were achieved for commercial Cu-SiC composites. For both cemented and
commercial Cu-SiC composites relative density and electrical conductivity was decreased and hardness increased
with increasing weight percentage of SiC particles. It can be said that cemented copper matrix can replace instead
of commercial copper matrix.
609

Acknowledgement
The authors thank to experts Fuat Kayis for performing XRD and SEM-EDS studies and special appreciation are
extended to technician Ersan Demir of Sakarya University for assisting with experimental studies. This work was
conducted a project supported by TUBITAK with contract number of 106M118.
REFERENCES
1. Barmouz, M., Givi, M. K. B., Seyfi, J., On The Role of Processing Parameters in
Producing Cu/SiC Metal
Matrix Composites via Friction Stir Processing: Investigating Microstructure, Microhardness, Wear and Tensile
Behavior, Materials Characterization, Vol. 62, pp. 108-117, 2011.
2. Barmouz, M., Asadi, P., Givi, M. K. B., Taherishargh, M., Investigation of Mechanical Properties of Cu/Sic Composite Fabricated By FSP: Effect of Sic Particles size and Volume Fraction, Materials Science and Engineering A, Vol. 528, pp. 1740-1749, 2011.
3. Zhan, Y., Zhang, G., The Effect of Interfacial Modifying on The Mechanical and Wear Properties of Sicp/Cu
Composites, Materials Letters, Vol. 57, pp. 4583-4591, 2003.
4. Tjong, S. C., Lau, K. C., Tribological Behaviour of SiC Particle-Reinforced Copper Matrix Composites, Materials Letters, Vol. 43, pp. 274-280, 2000.
5. Zhu, J., Liu, L., Hu, G., Shen, B., Hu, W., Ding, W., Study on Composite Electroforming of Cu/Sicp Composites,
Materials Letters, Vol. 58, pp. 1634-1637, 2004.
6. Zang, R., Gao, L., Guo, J., Preparation and Characterization of Coated Nanoscale Cu/Sicp Composite Particles,
Ceramics International, Vol. 30, pp. 401-404, 2004.
7. Tjong, S.C., Lau, K.C., Tribological Behaviour of SiC Particle-Reinforced Copper Matrix Composites, Materials
Letters, 43, pp. 274-280, 2000.
8. Efe, C.G., Altinsoy, I., Ipek, M., Zeytin, S., Bindal, C., Investigation of Some Properties of SiC Particle Reinforced Copper Composites, 5th International Powder Metallurgy Conference, Ankara-Turkey, October 08-12,
2008.
9. Efe, C. G., Altinsoy, I., Yener, T., Ipek, M., Zeytin, S., Bindal, C., Characterization of Cemented Cu-SiC Composites, Vacuum, Vol. 85, pp. 643-647, 2010.
10. Shu, K-M., Tu, G.C., The Microstructure and the Thermal Expansion Characteristics of Cu/SiCp Composites,
Materials Science & Engineering, Vol. 349, pp. 236-247, 2003.
11. Efe, C.G., Altinsoy, I., Ipek, M., Zeytin, S., Bindal, C., Some properties of Cu-SiC composites produced by powder metallurgy method, Kovove Metallic Materials, Vol. 49, No.2, pp. 131- 136, 2011.
610

AN INVESTIGATION ON Cu-Al2O3 COMPOSITES

PRODUCED BY PM METHOD
brahim ALTINSOY, Gzde F. elebi EFE, Tuba YENER, Mediha PEK, Sakin ZEYTN, Cuma BNDAL
Sakarya University, Engineering Faculty, Metallurgy and Materials Engineering Department, Esentepe Campus
54187, Serdivan-Sakarya, E-Mail: ialtinsoy@sakarya.edu.tr
ABSTRACT
This study reports on characterization of copper (40 m) composite reinforced with alumina (0.3 m) particle at
ratios of 5 and 7% by weight. Sintering was performed at 925C for 2h in graphite powder. The relative densities
of sintered samples are 98.8 and 97 % for reinforcements amount of 5 and 7 wt%, respectively. Optical and SEM
studies revealed that alumina particles were located homogenously around Cu grains. The presence of alumina and
copper were confirmed by EDS and XRD analysis. Depending on the amount of alumina, the electrical conductivity
of test samples ranged from 58.6 to 44.8 %IACS. There is a little change in the microhardness of test materials with
increment in the amount of reinforcement ratios.
Key Words: Sintering, Alumina, Copper, Conductivity, Composite.
1. INTRODUCTION
Although, Copper is widely used as an electrical conductor because of its high electrical and thermal conductivity,
but it has low tensile and yield strength. To solve this problem, copper has been strengthened by several different
ways. Conventional methods such as cold working and precipitation hardening as well as solid solution hardening,
which lower thermal conductivity, are not suitable for high-temperature applications. Metal matrix composite materials can be utilized at higher service temperatures than their base metal counterparts. There, the primary attention
is in dispersion strengthening (DS) of copper, i.e. in copper based metallic matrix composites and, oxide dispersion
strengthened Cu matrix composites (ODSC) present superior advantages and have been successfully used in a
good many aspects of industry such as automobile and wiring industries (MMC) [1-3]. Studies on the synthesis and
characterization of nanoscale alumina dispersed copper metal matrix composites have been attracting scientific
interest in recent years, since nanostructured-type materials are expected to have special physical and mechanical
properties.
Owing to the presence of uniformly-dispersed fine Al2O3 particles, which are hard and thermally stable at the elevated temperatures near the melting point of the copper matrix, the alumina-dispersion strengthened copper-based
composites afford high strength at elevated temperatures as well as at room temperature. A unique combination of
high strength and electrical conductivity at elevated temperatures enables the Al2O3/Cu composites to be the best
candidates for high-temperature electric material and the most attractive material of the international thermonuclear
experimental reactor (ITER) high-heat flux components, such as, electrodes, lead wires, connectors, diverters and
first wall [4,5]. In order to achieve high fracture toughness and low processing cost, the Al2O3 phase in the microstructure should be in particulate form, and the particle size should be as small as possible.
The particulate reinforced CuAl2O3 MMCs can be synthesized by using several routes which include mixing of
Cu melt and Al2O3 powder followed by casting, such as the Comalco process, and internal oxidation of CuAl alloy
powders. The casting process has the limitation that the Al2O3 size has to be large enough to allow effective mixing. Alternatively, powder metallurgy is fabrication method with its advantage of homogeneous mixing of constituent
materials which eventually gives good final mechanical properties to the composite with sufficient physical properties.[5-7].
The present paper aims to investigate the effect of high reinforcement amounts on the properties of copper-alumina
composites.
611

2. EXPERIMENTAL DETAILS
During this study, commercial Cu powder (99.9% puridity) as a matrix material and commercial Al2O3 powder as a
reinforcement agent (99% puridity) were used. At first, powders were mixed and then were compacted by unaxial
press. After compaction, the green body sintered at 925 C for 2 hours in an electrical furnace. Following sintering,
samples were hot pressed as fast as possible and finally, composites characterized by using optical microscope,
SEM, SEM-EDS, XRD, Vickers Indentation Technique, DC electrical conductivity instrument and by measuring
density using Archimeds principle. The preparation and characterization procedures of the samples were given
schematically in Fig. 1.
Fig.1. The schematical presentation of experimental procedure.

3. RESULTS and DISCUSSIONS
3.1. Optical-SEM Micrographs
It can be claimed that the reinforcement materials distributed homogenously into the matrix and they located among
the Cu grains. This phenomena results from the poor wettability between Cu and Al2O3. Dark grey regions indicate
Al2O3 particles, when bigger gray areas point out the Cu matrix (Fig. 2).
612


(a)
(b)
Fig.2. Optical micrographs of composites sintered at 925 oC for 2h. reinforced with:
a) Al2O3 wt.5% b) Al2O3 wt. 7% (Magnification: 500X)
SEM microstructures of the samples are similar to optical micrographs according to distribution and location of the
reinforcing agent. Same gray grains indicate the Cu, while white, small zones seen as Al2O3. Besides, there was no
remarkable grain grow in the Cu matrix after the sintering. This probably resulted from reinforcement agent formed
a barrier for possible grain growth (Fig. 3).

(a)
(b)
Fig.3. SEM microstructures of composites sintered at 925 oC for 2h. reinforced with:
a) Al2O3 wt.5% b) Al2O3 wt. 7%
3.2. XRD Analysis
XRD analyses revealed that the dominant phases in the composite bodies were Cu and Al2O3. Peak intensities of
the reinforcement material was shown very few contrast to Cu, because the ratio of them to matrix phase are very
little. Also, there was a little amount of copper-oxide (Cu2O) in both Cu- Al2O3 wt. 5% and 7% samples, but the
change in the amount of copper-oxides was no remarkable by increment in the ratio of reinforcement material (Fig.
4 and 5).
Fig. 4. XRD analysis of the Cu- Al2O3 wt.5% composite sintered at 925 oC
613

Fig. 5. XRD analysis of the Cu- Al2O3 wt.7% composite sintered at 925 oC
3.3. SEM-EDS Results
Fig. 6. SEM-EDS analyses of the Cu-Al2O3 wt. 5% and 7% samples.

The results of the SEM-spot EDS analyses were confirmed the optical, SEM examinations and XRD analyses. The
spots taken from the larger grey areas (spot #1 in Cu- Al203 wt. 5% and 7 %) indicated Cu matrix, while black regions
(spot #2,3 in Cu- Al203 wt. 5%; spot #2,3,4 in Cu- Al203 wt. 7%) between the copper regions pointed out reinforcement
agent in both composites samples. This clarifies why the reinforcements existed among the matrix grains. Further-
614

more, the oxygen element mostly resulted from the Al2O3. There is no oxygen evidence on the surface of copper
grains as well as detecting a little at the spots taken from the Cu-Al2O3 interface. This was probably resulted from
the both oxidation of starting Cu powder and oxidation during the sintering process.
3.4. Relative Density-Microhardness-Electrical Conductivity
The results of relative density, microhardness and electrical conductivity measurements were given in Table 1.
Microhardness measurements conducted by taking care of the indenter incorporates both matrix and reinforcement
phases, homogenously.
Table 1. The relative density, microhardness and electrical conductivities of the composite samples
sintered at 925 oC.
Sample
Cu (40)-Al2O3 (0.3 m)
Al2O3 wt. %
5
7
Relative Density (%)
Microhardness (HV)
Electrical Conductivity (%IACS)
98.78
97.04
156
159.4
58.62
44.83
From the Table 1, it can be seen that the relative densities and electrical conductivities of the composites decreased
by increasing of the reinforcement ratio, but this diminution was remarkable in the electrical conductivities other
than the relative density. This could result from the post compaction process eliminated the pores in the body. On
the other hand, the microhardness values increased slightly with the increment in the ratios of Al2O3. Due to the
small and uniformly distributed hard Al2O3 particles act as reinforcing phases and become obstacles to the movement of dislocations [1], the microhardness increased. Furthermore, post compaction (hot pressing) after sintering,
provides increment in the number of dislocations in the matrix and this contributed to the hardness increment. According to Mathiessen Rules, electrical conductivity is affected by resistivity due to impurities, since alumina is an
insulator and act as impurities in copper matrix and plastic deformation, the composites achieves lower electrical
conductivity [7].
4. CONCLUSIONS
Cu (40 m)-Al2O3 (0.3 m) composites were produced by PM method and the distribution of the reinforcements was
homogenously in the matrix. The reinforcements agent, Al2O3 located between the copper grains and this confirmed
by SEM-EDS results. The dominant phases were detected as Cu and Al2O3 and a little amount of copper-oxide existed in the composites by the XRD results. In the XRD results, the few amount of copper-oxides probably resulted
from the oxidation of starting Cu powder and/or oxidation during sintering process. SEM-EDS analyses confirmed
the XRD results and evidences as mentioned in optical, SEM micrographs. The microhardness of the composites
increased slightly by increasing of the amount of Al2O3, while the electrical conductivities and relative densities
of them decreased. In this paper, since the amounts of reinforcing agents are at some high levels for this type of
composites, the values of electrical conductivities are not enough in the applications which electrical conductivity
has primary importance. However, this composites possessed high microhardness values and reinforced with fine
particle size of reinforcement and thus, this samples (especially Cu-Al2O3 wt.5%) can be suitable for applications
which high hardness and high temperature resistance as well as certain electrical conductivity are required.
REFERENCES
1. Ritasalo, R., Liu, X. W., Sderberg, O., Keski-Honkola, A., Pitknen, V., Hannula, S-P., The Microstructural
Effects on the Mechanical and Thermal Properties of Pulsed Electric Current Sintered Cu-Al2O3 Composites,
Procedia Engineering, Vol: 10, pp: 124-129, 2011.
2. Efe, G. C., Yener, T., Altinsoy, I., Ipek, M., Zeytin, S., Bindal, C., The Effect of Sintering Temperature on Some
Properties of CuSiC Composite, Journal of Alloys and Compounds, Vol: 509, pp: 6036-6042, 2011.
3. Wang, Q. Z., Cui, C. X., Lu, D. M., Bu, S. J., Fabrication and Properties of A Novel ZnO/Cu Composite, Journal
of Materials Processing Technology, Vol: 210, pp: 497-503, 2010.
4. Motta, M. S., Jena, P. K., Brocchi, E. A., Solorzano I. G., Characterization of CuAl2O3 Nano-Scale Composites
Synthesized by In Situ Reduction, Materials Science and Engineering C, Vol: 15, pp:175-177, 2001.
5. Ruihua, L., Kexing, S., Shuguo, J., Xiaofeng, X., Jianxin, G., Xiuhua, G., Morphology and Frictional Characteristics Under Electrical Currents of Al2O3/Cu Composites Prepared by Internal Oxidation, Chinese Journal
of Aeronautics, Vol: 21, pp: 281-288, 2008.
6. Ying, D. Y., Zhang, D. L., Processing of CuAl2O3 Metal Matrix Nanocomposite Materials by Using High Energy
Ball Milling, Materials Science and Engineering A, Vol: 286, pp: 152-156, 2000.
7. Hussain, Z., Keong, K. H., Studies on Alumina Dispersion-Strengthened Copper Composites Through Ball Milling and Mechanical Alloying Method, Jurnal Teknologi, Universiti Teknologi Malaysia, Vol: 43(A), pp: 1-10,
2005.
615

DOAL VE YAPAY YALANDIRMANIN ALMNA TAKVYEL ALMNYUM

ALAIMI ESASLI KOMPOZT MALZEMELERN SERTLNE ETKS
M. Fatih AYCAN*, Mustafa BEYL**
* Gazi niversitesi, Mhendislik Fakltesi, Makine Mhendislii Maltepe-Ankara, Trkiye
** Osmaniye Korkut Ata niversitesi, Mhendislik Fakltesi, Makine Mhendislii Karacaolan Yerlekesi,
Osmaniye, Trkiye
ZET
Bu almada, toz metalurjisi yntemlerinden scak presleme yntemi kullanlarak Al2O3 takviyeli Al-5Zn-3,5Cu2,5Mg alam esasl kompozitlerin retimi yaplmtr. retilen numunelere doal ve yapay olmak zere iki farkl
yalandrma ilemi uygulanmtr. Yalandrma ilemleri sresince numunelerin sertlik deiimleri belirlenmitir. almann sonunda, doal yalandrma ileminde yalandrma sresine bal olarak sertlik deerlerinin balangta
ykseldii fakat daha sonra byk lde kararl davran sergiledii grlrken, yapay yalandrma ilemlerinde
farkl yalandrma scaklklarnda benzer sertlik deiim erileri elde edilmitir.
Anahtar kelimeler: Kompozit malzemeler, yalandrma ilemleri, sertlik
EFFECT OF NATURAL AND ARTIFICIAL AGING ON THE HARDNESS OF

ALUMINA REINFORCED ALUMINIUM ALLOY COMPOSITES
ABSTRACT
In this study, Al2O3 reinforced Al-5Zn-3.5Cu-2.5Mg alloy composites were produced using hot pressing method
which is one of the powder metallurgy methods. Natural and artificial aging processes were carried out to the samples produced. During the aging processes, the hardness behaviors of the composites were investigated in each
aging condition. According to the experimental results, it was determined that the hardness values increased at the
beginning of the process then they were stable substantially in natural aging, on the other hand similar hardness
behaviors were determined for all conditions in artificial aging processes.
Key words: Composite materials, aging process, hardness
1.GR
Uzun yllar mhendislik uygulamalarnda yaygn olarak kullanlan demir-elik malzemeler yerine, daha dk arlkta daha iyi mukavemet zelliklerine sahip olan metal esasl kompozit malzemeler tercih edilmeye balanmtr [1].
Metal esasl kompozitler sahip olduklar dk younluk ve genleme katsays, yksek dayanm, anma direnci ve
rijitlik gibi zellikleri ile n plana kmaktadr. Bu zelliklerin tek bir yapda birleimi mevcut geleneksel malzemeler
tarafndan karlanmas mmkn olmamaktadr. lerleyen teknolojiye paralel olarak gelitirilen kompozit malzemeler; gnmzde uzay-havaclk, otomotiv ve savunma sanayinde yaygn olarak kullanlmaktadr [2-4]. Kompozitlerde ana yap ve takviye eleman olarak kullanlacak malzemelerin doru seilmeleri, kullanmlar esnasnda
beklenen baarmn elde edilebilmesi iin son derece nemlidir. Ana yapnn sneklik ve tokluk deerlerinin iyi
olmasnn yannda slatabilirlii ve takviye eleman ile kimyasal ba oluturma kabiliyetinin yksek olmas istenir-
616

ken, takviye elemannn ise ana yap ierisinde znmeyecek ve ana yap ile uyumlu ara yzey oluturabilecek
btncl bir yap oluturabilmesi istenir [5]. Hafif metaller olarak nitelendirilen alminyumun ana yap, oksit grubu
seramiklerinden Al2O3 seramiinin takviye eleman olarak kullanld metal esasl kompozitler endstride yaygn
kullanm alan bulmaktadr. Ayrca, gemi dnemlerde yaplan bilimsel almalar incelendiinde; Al2O3 takviyeli
alminyum esasl kompozitlerin iyi ara yzey baarmna ve slatabilirlie sahip olduklar grlmektedir [6]. Seramik
takviyeli alminyum esasl kompozitler, zellikle anma dayanm ve dk arlk gibi zelliklerin gerekli olduu
uygulamalarda tercih edilmektedir.
Parack takviyeli metal esasl kompozitlerin retimlerinde toz metalurjisi, basnl dkm, ekstrzyon ve yar kat
kartrma yntemleri kullanlmaktadr [7]. Toz metalrjisi yntemi, ergimi metalin kullanld retim yntemlerine gre ksmen daha maliyetli olmasna ramen dk ilem scaklklarnda retime olanak vermesi nedeniyle
endstride geni kullanm alan bulmaktadr [2]. Kompozitlerde; retim ynteminin eidi de ana yap ve takviye
elemannn tr ve retim sonrasnda uygulanan sl ilemler gibi mekanik zelliklerin farkllk kazanmasnda etkili
olmaktadr.
Bu almada 7xxx serisi alminyum alam esasl seramik takviyeli kompozit malzemelerin sertlik deerlerinin
uygulanan fakl sl ilemler ile deiimleri incelenmitir. Al2O3 takviyeli kompozit numuneler scak presleme yntemi kullanlarak retilip farkl scaklklarda yalandrma ilemi uygulandktan sonra numunelerin sertlik deiimleri
belirlenmitir.
2.MALZEME VE DENEYSEL YNTEM

Bu almada %99,9 saflkta ve 20 m alt boyutlarda metal ve seramik tozlar kullanlmtr. Ana yap olarak arlka Al, %5 Zn, %3,5 Cu ve %2,5 Mg oranlarna sahip 7xxx serisi Al alam, takviye eleman olarak parack eklinde
Al2O3 seramik tr kullanlmtr. Takviye oran etkisinin incelenebilmesi iin takviyesiz olarak hazrlanan alam
ve %5, %10 ve %15 gibi farkl takviye oranlarnda hazrlanan numuneler ile birlikte toplamda drt eit numune
hazrlanmtr. stenilen karm oranlarnda hazrlanan tozlar, deirmen tipi kartrcda 2 saat sreyle kartrma
ilemine tabi tutulmulardr. almada; sktrma ve sinterleme ilemleri, 15 ton sktrma kapasitesi ve 11 kW
stma gcne sahip scak presleme cihaz kullanlarak gerekletirilmitir. Hazrlanan toz karmlarna 50x70 mm
ebatlarndaki scak pres kalbna konularak, ortalama 25 MPa basn altnda 535Cde 30 dakika sktrma ve
sinterleme ilemleri uygulanmtr.
Sonra numunelere kl frnnda 500C scaklkta 30 dakika sreyle zeltiye alma ilemi uygulanm hemen ardndan oda scaklnda su verme ilemi gerekletirilmitir. Daha sonra ise numunelere doal ve yapay olmak zere
birbirinden bamsz olarak iki farkl yalandrma ilemi uygulanmtr. Doal yalandrma ilemi 60 gn sreyle
25C oda scaklnda, yapay yalandrma ilemleri ise 120C, 150C, 180C ve 200C scaklklarda 300 dakika
sreyle ya banyosu kullanlarak gerekletirilmitir. Yapay yalandrma ilemleri sonunda numunelere oda scaklnda su verme ilemleri uygulanmtr.
Yalandrma ileminden sonra numunelerin iyaplar incelenmitir. Numunelerin yalandrma ilemleri boyunca
sergiledikleri sertlik deiimleri ise belirli zaman dilimlerinde alnan sertlik lmleri ile belirlenmitir. Sertlik deneyleri; ASTM E10-84 [8] standardna gre 187,5 kg yk ve 2,5 mm bilye ap ile Brinell sertlik yntemi kullanlarak
gerekletirilmitir. Doal yalandrma ilemlerinde gnde bir, yapay yalandrma ilemlerinde ise yarm saatte
bir alnan er sertlik lm ile numunelerin zamana bal yalanma davranlar elde edilmitir.
3.DEERLENDRME
3.1. Yap ncelemeleri
almada kullanlan metal ve seramik tozlarnn ortalama boyutlar toz boyut lm ilemleri ile belirlenmitir. Yaplan lm ilemleri sonucunda belirlenen ortalama ap lleri izelge 1de verilmitir. Toz boyutu, tozlarn ak
hzlar ve paketlenmeleri zerinde etkili olmasna bal olarak sinterleme sonrasnda retilen paralarn mekanik
zelliklerini byk lde deitirirken, daha yksek paketlenme zellikleri iin kk ve iri toz tanelerinden oluan
farkl toz bileimleri hazrlanmaktadr [9]. Ana yapy oluturan element tozlarnn farkl boyutlarda olmas daha iyi
zelliklerin elde edilmesinde yararl olduu dnlmektedir.
617

izelge 1 Kullanlan tozlarn ortalama boyutlar

Malzeme
Ortalama Toz Boyutu (m)
Al
3,41
Mg
14,75
Cu
15,55
Zn
2,45
Al2O3
12,24
almada takviye eleman olarak parack ekilli seramiklerin kullanlmasna bal olarak numuneler izotropik zellik sergilemektedir. Ana yap ierisinde takviye elemanlarnn dalmlar numunelerin mekanik zellikleri zerinde
dorudan etkilidir. Bu nedenle takviye elemanlarnn yap ierisinde homojen dalmalar daha iyi mekanik zelliklerin elde edilebilmesi iin istenen bir durumdur. ekil 1de verilen k mikroskobu grntsnde; %15 Al2O3 takviyeli
numunede seramik paracklarnn ana yap ierisinde byk lde homojen dalm sergiledikleri grlmektedir.
Bu sebeple numunelerde yne bal zellik farknn gzlemlenmemesi beklenmektedir.
ekil 1 Parack ekilli takviye elemannn ana yap ierisindeki dalm

3.2.Sertlik Davran
Alam ve farkl takviye orannda olmak zere toplamda drt farkl bileimde hazrlanan numuneler, doal ve yapay olmak zere farkl yalandrma koullarnda yalandrlm ve her bir koulda numunelerin sergiledikleri sertlik
deiimleri ve ulalan en yksek sertlik deerleri belirlenmitir. Oda scaklnda altm gn sreyle yaplan doal
yalandrma ilemi sonucunda elde edilen sertlik deiimleri ekil 2de verilmitir.
ekil 2 Numunelerin doal yalanma davran

Doal yalandrma ilemlerinde numunelerin benzer davrana sahip olmalarnn yannda farkl sertlik seviyelerine
sahip olduklar grlmektedir. Numunelerin farkl takviye oranlarnda benzer davran sergilemeleri, takviye ora-
618

nnn numunelerde doal yalanma karakterini etkilemediini, yalnzca ulalan sertlik seviyesini etkilediini gstermektedir. Bu durum, yalandrma ileminin oda scaklnda gereklemesine bal olarak ana yap ile takviye
elemanlar ara yzeylerinde kimyasal tepkimelerin gerekleme olaslnn dk olmas ile aklanabilir. Eriler incelendiinde zeltiye alma ve su verme ileminden sonra alnan sertlik deerlerinin, yalandrma ileminin
balang safhasnda alnan sertlik deerlerine oranla daha yksek olmasnn sebebi olarak malzemedeki kafes
rahatlamas gsterilebilir. Numunelere, doal yalandrma ileminden sonra 120C, 150C, 180C ve 200C olmak
zere drt farkl scaklkta yapay yalandrma ilemi uygulanmtr. Her bir numune iin zeltiye alma ve su verme
ilemlerinden sonra elde edilen sertlik deerleri doal yalandrma ilemleri sonunda ulalan en yksek sertlik
seviyesi ile birlikte ekil 3 ve 4de verilmitir. Yapay yalandrma ilemlerinde; artan yalandrma scaklna bal
olarak art gsteren ana yapnn sertlik deerleri, doal yalandrma ilemi sonunda elde edilen en yksek sertlik
seviyesine gre daha yksek seviyelere ulamtr.
ekil 3 Yapay yalandrma ilemleri sonunda alam numunenin sertlik davran

Artan yalandrma scaklklar ile birlikte sertlik deerlerinde azalma grlrken, yksek scaklklarda tane irilemesinin fazla olmasna bal olarak yksek scaklklardaki sertlik deerlerinin daha dk olduu belirlenmitir [10].
Ana yap zerinde takviye elemannn etkisi olmakszn farkl scaklklarda gerekletirilen yalandrma ilemlerinde
ana yapnn yalanma karakteristii belirlenmeye allmtr. Alam numunenin yalanma karakteristiine takviye
elemannn etkisi ise ekil 4de verilen erilerde grlmektedir. 300 dakika sreyle yaplan yalandrma ilemleri
sonunda elde edilen sertlik davranlar irdelendiinde; genel olarak artan yalandrma scaklklar ile birlikte sertlik
deiimlerinde azalma eilimi olduu ve doal yalandrma ilemi sonunda elde edilen en yksek sertlik seviyesine
hibir koulda ulalamad grlmektedir. zeltiye alma ve su verme ilemlerinden sonra belirgin biimde artan
sertlik deerlerinin, ilerleyen yalandrma sresine bal olarak azalma gsterdii ve bir sre sonra ise deimedii
belirlenmitir. Numunelerin yapay yalandrma ilemleri sonunda elde edilen sertlik davranlar karlatrldnda;
takviye elamannn ana yapnn ve yalandrma scaklklarnn yalanma karakteristiini belirgin biimde etkiledii
grlmektedir.
(a)
619

(b)
(c)
ekil 4 Yapay yalandrma ilemleri sonunda farkl takviye oranlarnda elde edilen sertlik deiimleri;
(a) %5, (b) %10, (c) %15
lem scaklnn, malzeme iinde yalanmaya bal oluan keltilerin yaps zerinde etkili olduu dnlmektedir [11]. Buna ek olarak sl genlemeye bal oluan dislokasyonlar ve yapda bulunan magnezyumun takviye eleman olarak yapya katlan almina ile etkileimine bal olarak oluacak kelti yapsn etkilemesi, alam numune
ile takviyeli numunelerin sertlik davranlar arasndaki farkllklarn nedenini aklamaktadr [12]. Numunelerin scak
presleme yntemiyle retilmeleri ile zeltiye alma ve su verme ilemlerinden sonra elde edilen ve uygulanan yapay
yalandrma ilemleri esnasnda ulalan en yksek sertlik deerleri ekil 5de verilmitir.
ekil 5 Farkl koullarda elde edilen sertlik deerleri
620

Ham olarak ifade edilen retim sonras sertlik deerleri, beklendii gibi en dk seviyede iken zeltiye alma ve su
verme ilemlerinden sonra art gstermitir. Artan yalandrma scaklklar ile ulalan sertlik seviyelerinde azalma
eilimi sz konusuyken, genel olarak btn numunelerin benzer sertlik davranna sahip olduklar grlmektedir.
4. SONULAR
Doal ve yapay yalandrma ilemleri karlatrldnda alam numune iin yapay yalandrma ilemlerinde
daha yksek sertlik deerlerine ulalrken, takviyeli numunelerde ise doal yalandrma ilemlerinde daha
yksek deerlere ulalmtr.
Artan yalandrma scaklklar, numunelerin sertlik deerlerinde azalmaya neden olmutur.
Takviye orannn ana yapnn yalanma karakteristiini etkilemedii, yalnzca ulalan sertlik seviyesini etkiledii belirlenmitir.
5. KAYNAKA
1. Akbulut, Hatem, Otomotiv fren diski ve balatalarn metal matriksli kompozitlerden retimi, DPT Proje No:
2003K120970.
2. Wu, Yan-Lin and Chao, Chuen-Guang, Deformation and fracture of Al2O3/Al-Zn-Mg-Cu metal matrix composites
at room and elevated temperatures, Materials Science and Engineering, A282, 193-202, 2000.
3. Rahimian, M et al, The effect of sintering temperature and the amount of reinforcement on the properties of Al/
Al2O3 composites, Materials and Design, 30, 3333-3337, 2009.
4, Shorowordi, K.M. et al, microstructure and nterface characteristics of B4C, SiC and Al2O3 reinforced Al matrix
composites: A Comparative Study, Journal of Materials Processing Technology, 142, 738743, 2003.
5, Kiourtsidis, Grigoris E. et al, Aging response of aluminium alloy 2024/silicon carbide particles (SiCp) composites,
Materials Science and Engineering A, 382, 351361, 2004.
6 S.Y. Oh, J.A. Cornie, K.C. Russel, Wetting of ceramic particulates with liquid aluminium alloys. Part II. Study of
wettability, Metall.Trans. A 20, 533541, 1989.
7 ahin, Y, Preparation and some properties of SiC particle reinforced aluminium alloy composites, Materials and
Design, 24, 671-679, 2003.
8 ASTM Standarts, Designation E10-84, Standard Test Method for Brinell Hardness of Metallic Materials, 1984.
9 German, R. M., Toz Metalurjisi ve Parackl Malzeme lemleri, Sarta, S.,Trker, M., Durlu, N.,Trk Toz
Metalurjisi Dernei Yaynlar: 05, Ankara, 15-500, 2007.
10 Aye, Shwe Wut Hmon et al, The effect of ageing treatment of aluminum alloys for fuselage structure-light aircraft,
Proceedngs of World Academy of Science, Engineering and Technology, Volume 36, ISSN 2070-3740, 2008.
11 Sheu, Cha-Yuan, Ln, Su-Jen, Ageing behaviour of SiCp-reinforced AA 7075 composites, Journal of Materals
Scence, 32, 1741-1747, 1997.
12. Gomez de Salazar, J.M., Barrena, M.I., Role Of Al2O3 Particulate Reinforcements on Precipitation in 7005 AlMatrix Composites, Scripta Mater.,44, 24892495, 2001.
621

Al-SiC-Grafit kompozitinin Tribolojik Davran

Hlya DURMU*, Salim AHN**, R. Onur Uzun***, Nilay Yksel**
Celal Bayar niversitesi, Turgutlu MYO, Makine ve Metal Teknolojileri Blm, Turgutlu-Manisa. hulya.kacar@
bayar.edu.tr
**
Celal Bayar niversitesi, Mhendislik Fakltesi, Malzeme Mhendislii Blm, Muradiye-Manisa. Salim.sahin@
bayar.edu.tr, nilay.yuksel@bayar.edu.tr
***
Celal Bayar niversitesi, Fen Bilimleri Enstits, Muradiye-Manisa. receponur@gmail.com
*
zet
Bu almada, toz metalrjisi (TM) yntemi ile retilen %96 saflktaki alminyum-SiC Grafit numunelerin anma
davran incelenmitir. Tribolojik zellikleri pin-on-disk anma cihaz ile belirlenmitir. Kar eleman olarak seramik
bilya kullanlmtr. 150 m, 300 m ve 450 m de anma kayplar llmtr. Anma srasnda numunelere 1, 2,
3, 4 ve 5 N yk uygulanmtr. Kayma hz 10 cm/s ve kayma mesafesi 450 m olarak belirlenmitir. Yaplan anma
deneyleri sonucunda grafitin, kayma hz ve ykn anma davranlarna etkisi byk olduu grlmtr. Anma
mekanizmas daha ok adheziv olduu grlmtr.
Anahtar kelimeler: Alminyum tozu, SiC, anma, grafit, mikroyap.
TRIBOLOGICAL BEHAVIOR OF Al-SiC-GRAPHITE COMPOSITE

Abstract
In this study, wear behavior of Aluminium at %96 grade-SiC-Graphite samples produced by powder metallurgy (PM)
method has been investigated. Tribological properties have been determined by pin-on-disc test machine. Ceramic
ball has been used as counter element. Wear loss has been measured at 150m, 300m and 450m. 1, 2, 3, 4 and
5 N loads have been applied on samples during wear test. Sliding speed and distance have been determined respectively 10 cm/s and 450 m. As a result of wear tests, it has been seen that graphite, sliding speed and load have
significant effect on wear behavior. It has been observed that, the mechanism of wear was mainly adhesive.
Keywords: Aluminium powder, SiC, wear, graphite, microstructure
1.GR
Kompozit, srekli bir faz (matris) ierisinde yaylm ayrk bileenlerden oluan ve ayrt edici zelliklerini bileenlerinin zelliklerinden, geometri ve yapsndan ve ayrca farkl bileenler arasndaki arayzlerin zelliklerinden alan
malzemelerdir. Alminyum matrisli kompozitler temelde birden fazla trde takviye iermektedir. Grafit parackl
alminyum matrisli kompozitler genellikle toz metalurjisi, karma dkm, sktrmal dkm, UPAL yntemi ve topak
yntemlerinden biriyle retilir [1].
Toz metalrjisi ok kk partiklleri birbirine balayarak para haline getirme ilemidir. Daha geni bir ifade ile toz
metalrjisi, toz eklindeki malzemelerin preslenmesi ve takiben yksek scaklkta sinterlenmesi ile para imalatn
kapsamaktadr. nce partikl eklindeki saf metaller, alamlar, karbon, seramik ve plastik malzemeler birbirleriyle
kartrlarak basn altnda ekillendirilirler. Daha sonra bu paralar ana bileenin ergime scaklnn altnda bir
scaklkta sinterlenerek partikllerinin temas yzeyleri arasnda kuvvetli bir ba oluturulur ve bylece istenilen zellikler elde edilir. Toz metalrjisi kk, karmak ve boyutsal hassasiyeti yksek paralarn seri imalatna son derece
uygundur. Malzeme kayb ok azdr, belirli derece porozite (gzenek) ve geirgenlik elde edilir [2].
622

Alminyum-grafit takviyeli kompozitler pistonlarda, silindirlerde, trbin rotorlarnda ve yatak burlarnda kullanlmaktadr. Grafitin ilavesi anma direncinin, ilenebilirliinin, snmleme kapasitesinin artmasn ve sl genleme
kapasitesinin dmesini salamaktadr. Ancak grafit partikl takviyesinin artmas kompozitin dayanmn drmektedir [3, 4, 5].
Srtnerek alan btn makine elemanlarnda kanlmaz olan kompleks bir sistem zellii gsteren anma,
sanayide bir ok tribolojik sistemlerde grlen korozyonun ve yorulmann yan sra nc byk problemdir. Bu
nedenden gnmz teknik sistemlerindeki aratrmalar srtnmeyi ve anmay azaltma ve kontrol etme almalar eklinde younlamtr. Srtnmenin ve anmann azaltlmasyla malzeme kayb nlenerek boyut hassasiyeti
salanrken enerji israf da nlenmi olur [6]. Kompozit malzemelerde anmay azaltmak iin en sk kullanlan yalayclardan biri grafittir. Birok alma alminyum/grafit kompozitlerinin uygulamalarna odaklanmtr [5]. zellikle
deniz tatlarnn dizel motorlarnda kullanlan yataklarda Al-Grafit kompozitlerin kullanm ile srtnme kayplar
ve anmay azaltt grlmtr [7]. SiC ilavesi ile kompozitlerin dayanm ve anma direnci artmaktadr [8, 5].
SiC n dezavantaj ilenebilirlii zorlatrmasdr. Dier taraftan grafitin ilavesi ilenebilirlii arttrmakta ve anmay
azalmaktadr [9]. Bu almada, Al-SiC-Grafit kompozitleri toz metalurjisi yntemiyle retilmitir. Anma dayanmna grafit miktarnn etkisi incelenmitir.
2.DENEYSEL ALIMALAR
2.1. T/M Para retimi
T/M numuneler Alminyum, SiC ve grafit kompozitidir. Tozlar 53 m-75 m arasndadr. Numuneler %90 Al-%10
SiC, %89.5 Al-%10 SiC0.5 Gr, %89 Al-%10 SiC%1 Gr, %88.5 Al - %10 SiC- %1.5 Gr eklinde hazrlanmtr.
ncelikle sktrlacak toz karmlar 5 saat kartrlmtr. apraz krlma testi iin retilen numuneler 60x10x10
mm boyutlarndadr. Anma testleri iin ise numunelerin boyutlar 20x10 mm dir. 400 MPa basnta preslenmitir.
Daha sonra hazrlanan numuneler 6200 C scaklkta 1 saat boyunca sinterlenmitir.
2.2. Younluk Testi
Numunelerin sinterleme ncesi ve sonras younluklar ekil 1de gsterilmitir. Ayrca sinterleme ncesi ve sonras
llen boyutlar izelge 1de belirtilmitir.
izelge 1 . Sinterleme ncesi ve sonras T/M numunelerin boyutlar
Boyut lm
%0 Gr
%0.5 Gr
%1 Gr
%1.5 Gr
Sinterlemeden nce
10 mm ykseklik
20 mm ap
10 mm ykseklik
20.1 mm ap
10.4 mm ykseklik
20.1mm ap
10 mm ykseklik
20.1 mm ap
Sinterleme Sonras
10.6 mm ykseklik
20.1 mm ap
10.2 mm ykseklik
20.15 mm ap
10.4 mm ykseklik
20.3 mm ap
10 mm ykseklik
20.2 mm ap
ekil 1. Sinterleme ncesi ve sonras numunelerin younluklar
623

2.3. apraz Krlma Deneyi

Krlma Deneyi TS 4222 EN ISO 3325 e gre gerekletirilmitir. Elde edilen dayanm deerleri ekil 2de verilmitir. Grafit miktar arttka dayanm azalmtr (%90 Al-%10 SiC (1), %89.5 Al-%10 SiC0.5 Gr (2), %89 Al-%10
SiC%1 Gr (3), %88.5 Al - %10 SiC- %1.5 Gr (4)).
Ted Guo ve Tsaonun almasnda test edilen malzemelerin mekanik karakteristikleri (sertlik, sl genleme katsays ve krlma tokluu), grafit katksnn artyla azalmtr. Bu almada da grafit miktar arttka apraz krlma
dayanm azalmtr [1, 5].
ekil 2. Numunelerin apraz krlma dayanm sonular.

2.4. Anma Testi
Anma srtnen yzeylerde malzeme kayb olarak tanmlanr. Anma miktar malzemenin trne, srtnen yzeylerin biimine, srtnme koullarna ve evrenin kimyasal etkilerine baldr. Anma testlerinde anma yk 1, 2,
3, 4, 5 N olarak seilmitir (izelge 2). Andrc bilya olarak seramik bilya kullanlmtr.
izelge 2. Anma test parametreleri.
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
Al %
90
89,5
89
88,5
90
89,5
89
88,5
90
89,5
89
88,5
90
89,5
89
88,5
90
89,5
89
88,5
Al-SiC-Gr kompozit
SiC %
Gr %
10
0
10
0,5
10
1
10
1,5
10
0
10
0,5
10
1
10
1,5
10
0
10
0,5
10
1
10
1,5
10
0
10
0,5
10
1
10
1,5
10
0
10
0,5
10
1
10
1,5
624
Anma Yk
1N
1N
1N
1N
2N
2N
2N
2N
3N
3N
3N
3N
4N
4N
4N
4N
5N
5N
5N
5N

ekil 3. Anma deneyi sonras numune arlklarndaki deiim
ekil 4. Anma deneyi sonras bilya arlndaki deiim

2.5. Mikroyap ncelemesi
Numunelerin mikroyaplar incelenmitir (ekil 5-8)
ekil 5. %0 grafit ieren numune (40x)
ekil 6. %0,5 grafit ieren numune (40x)
ekil 7. % 1 grafit ieren numune (40x)
ekil 8. %1,5 grafit ieren numune (40x)
625

3.SONULAR
1. En yksek younluk %1 Gr ieren numunelerde elde edilmitir.
2. Anma deneylerinde yk 4 ve 5 N kullanldnda grafit miktar arttka anma kayb artmtr. 1, 2 ve 3 N
kullanldnda ise anma kayb grafit miktar deiimlerinden fazla etkilenmemitir.
3. En dk anma kayb tm ykler iin % 0.5 grafit ieren numunelerde elde edilmitir. Grafit miktarnn artmas
mekanik zellikleri dreceinden dolay bu oran en uygun grafit orandr.
4. Kar eleman zerinde anma mesafesi arttka ok az kompozitten yapma olmutur. Kar elemann anma
kayb ok az olmutur.
5. Grafit miktar arttnda apraz krlma dayanmnda azalma meydana gelmitir.
4.Kaynaklar
1. A. Marinkovi , A. Vencl, Influence of the Solid Lubricant Particles Reinforcement on Composites Tribological
Properties, 11th International Conference on Tribology, 2009
2. S. Akgn Kayral, Plazma Pskrtme Yntemi ile BN, B4C ve SiC Takviyeli Alminyum Kaplamalarn retimi, Karakterizasyonu ve Anma Davrannn ncelenmesi, Celal Bayar niversitesi Fen Bilimleri Enstits, 2011.
Y.B. Liu, J.D. Hu, Z.Y. Cao, P.K. Rohatgi, Wear resistance of laser processed Al-Si-graphite composites, wear,
206, 1997, 83-86.
3. G. Rajaram, S. Kumaran, T. Srinivasa Rao, M. Kamaraj, Studies on high temperature wear and its mechanism
of Al-Si/graphite composite under dry sliding conditions, Tribology International, 43, 2010, 2152-2158.
4. Karam, M.B., Odaba, D., tektoid alt eliklerin kayma srtnmesinde adhesiv anma katsaysnn aratrlmas, 3. Ulusal Makine Tasarm Ve malat Kongresi, Ankara, 155-163, (1988).
5. Ted Guo ML, Tsao CYA., Tribological behavior of self-lubricating aluminium/ SiC/graphite hybrid composites synthesized by the semi-solid powder densification method, Composites Science and Technology
2000;60:6574.
6. H. Hocheng, S.B. Yen, T. Ishihara, B.K. Yen, Fundamental turning characteristics of a tribology-favored graphite/aluminum alloy composite material, Composites Part A, 28A, 1997, 883-890.
7. S.Suresha, B.K. Sridhara, Effect of addition of graphite particulates on the wear behaviour in aluminium-silicon
carbide- graphite composites, Materials and Design, 31, 2010, 1804-1812.
8. S. Suresha, B.K. Sridhara, Wear characteristics of hybrid aluminium matrix composites reinforced with graptite
and and silicon carbide particulates, Composites Science and Technology, 70, 2010, 1652-1659.
626

FORMING
PROCESSES
www.turkishpm.org
627

The effect of milling speed on particle morphology and

particle size of Al 2024 powders prepared by using high
energy ball milling
Aykut Canakci1, Temel Varol1, Recep Sen, Sinan Yildiz
1
Abstract
In the present work, the effect of milling speed on particle morphology and particle size of Al 2024 powders, prepared by high-energy ball milling, was investigated. The powder mixtures were milled in a planetary ball mill for
different milling times of 0.5, 1, 2, 4, 6, 8 and 10h. Milling speed was 250rpm and 350rpm and ball to powder weight
ratio was 10:1. Because of excessive cold welding for soft material such as Al, process control agent was used
to decrease the tendency of cold welding. Methanol was used as process control agent (PCA). Scanning electron
microscopy (SEM) was used to evaluate the morphological and microstructural evolution of the powder synthesized
by high energy milling. Particle size and powder morphology as a function of milling time were determined. The
results show that the increasing milling speed increases the work hardening and fracture occurrence in Al 2024
powder during the milling process, affecting the structural evolution of the powder.
1. Introduction
High-Energy ball milling was also known that metal powder particles could be fractured when subjected to heavy
plastic deformation. However, if ductile metal powder particles are used, cold welding among them would prevent
fragmentation of the particles. Hence, at same stage cold welding could be as rapid as fracturing. This welding
could be avoided or minimized by employing special chemicals that act as surfactants, such as stearic acid, methanol. Consequently, cold fracturing take place more easily and effectively to produce finer particles [1].

Mechanical alloying (MA) or high-energy ball milling (HEBM) is solid-state powder processing involving repeated
welding, fracturing and rewelding of powder particles in a high-energy ball mill. Process variables in this method
such as milling time, milling speed, ball to powder weight ratio and process control agent have effects on the final
structure and morphology of the powders [2-5]. High-energy ball milling (mechanical alloying) induces high energy
impacts on the charged powder by collision between balls and particles causing severe plastic deformation, repeated fracturing and cold welding of the particles leading to nano crystalline materials [6-9]. The main aim of this
study is to investigate the effect of different milling speeds on the morphology and particle size of Al2024 powders.
2. Experimental procedures
The as-atomized Al2024 powders (Gndodu Exotherm Company, Turkey) with an average particle size of 111m
which varies between 90 m and 125 m was used as raw materials. The chemical composition of as-atomized
Al2024 alloy (in wt.%) was 4.85 Cu, 1.78 Mg, 0.385 Si, 0.374 Fe, 0.312Mn, 0.138Zn, 0.042Cr, 0.005Ti and Al (balance). Fig.1 shows the morphology of as received Al2024 alloy powder. The Al2024 alloy powders are ligamental
like shape. Powders samples were withdrawn at time of 0.5, 1, 2, 4, 6, 8 and 10h with two different milling speeds of
250 and 350 rpm for morphological and microstructural analyses. The milling process was carried out in a planetary
ball mill (Fritsch Gmb, model Pulverisette Premium Line 7) at room temperature using tungsten carbide container.
The milling medium component was tungsten carbide balls with 10mm in diameter. The ball-to-powder weight ra-
628

tio (BPR) was selected as 10:1. A total of 2 wt % of methanol was added to the ball-mill as process control agent
(PCA). To prevent over heating, ball milling experiments were stopped for every 0.5h and then resumed when the
temperature of the container decreased to the room temperature. The particle size distribution of as-received and
milled powders was quantified by using a laser particle size analyser. The morphology evolution of the powders
during milling was investigated by SEM. Apparent density of powder samples were measured using a standard Hall
Flowmeter. The microhardness of as-received and milled powders was measured by a microhardness tester (struers microhardness tester) by applying 10g load [10].
Fig.1. Morphology of as-received powders.

3. Results and discussions
3.1 Effect of milling speed on milling process
Fig. 2 shows the used milling medium components (ball and vial) and Al2024 powders before and after milling. As
it can be seen, the Al2024 powders are little cold-welded to balls due to applied normal force between ball-ball and
ball-mill. In fact this phenomenon is due to locally increasing of temperature [11]. Vial and ball surfaces in Fig. 2c
are very much cold welded than vial and ball surfaces in Fig.2b due to high efficiency of ball-powder-vial collision.
As can be seen in Fig. 2, the Al2024 powders are very much cold-welded to balls and vials surfaces at milling speed
of 350rpm (Fig. 2c) than at milling speed of 250rpm (Fig. 2b) due to high efficiency of ball-powders-vial collision.
The powder yield could also be lower if the powder gets stuck to vial and ball surfaces due to increase in cold welding caused by the higher degree of plastic deformation [1]. However, morphology and particle size of Al2024 were
changed with different milling speeds of 250 rpm and 350 rpm (Fig. 2a, 2b, 2c). It is easy to realize that the faster
the mill rotates the higher will be the energy input into the powder. This is because the kinetic energy of the milling
medium is impacted to the powder being milled. Therefore, the kinetic energy supplied to the powder is higher at
higher relative velocities of the milling medium [1]. Particle size of Al 2024 powders at high milling speed of 350rpm
was smaller than at low milling speed at 250rpm due to high efficiency of ball-powder collision.
(a)
(b)

(c)
Fig.2. Used milling medium components (balls and vial) and Al2024 powders before and after milling.
(a) Before milling (b) At 250rpm, after milling (c) At 350rpm, after milling.
629

3.2. Powder morphology

The main process which takes place in a mill during the MA method to produce quality powders with controlled
microstructure is the repeated welding, fracturing, and rewelding of a mixture of powders. The morphology of the
initial powders is modified when they are subjected to ball collisions.
It is worth noting that the effects of collisions on the milled powders depend on the type of the constituent particles.
It has been shown that the initial ball-powder-ball collision causes the ductile metal powders to flatten and work
harder when they are cold welded and heavily mechanically deformed. They are brought into intimate contact,
forming layered structure of composite particles consisting of various combinations of the starting ingredients, as
schematically shown in Fig. 3. Further milling results in cold welding and deformation of the layered particles and a
refined microstructure is obtained.
Due to the initially low hardness of the starting elemental powders, the lamellar spacing of the agglomerated particles is quickly reduced upon further milling. Increasing the MA time increases the hardness and this leads to
fracturing of the agglomerated powders into smaller particles. In the following stage, the welding predominates,
causing the equiaxed particle formation. Then welding and fracture mechanism reach equilibrium and the formation of particles with randomly oriented interfacial boundaries. The final stage is characterized by the steady state
process, in which the microstructural refinement can continue, but the particle size and size distribution remain
approximately the same [12].
Fig. 3. Evolution of different stages of mechanical alloying of a ductile-ductile system according to [12].
The changes of in morphology of particles at 250rpm and 350rpm are showed in Fig. 4 and Fig. 5. It can be observed that different morphologies occurred during high energy milling. During high-energy milling, plastic deformation, cold-welding and fracture are predominant factors, in which the deformation leads to a change in particle
shape, cold-welding leads to an increase in particle size and fracture leads to decrease in particle size [13, 14].
Fracture is very low at the beginning of milling for both milling speed due to the lack of enough particles to deform.
Fig. 4b shows Al 2024 powder morphology after 0.5h of milling and Al 2024 particles have a flake like shape at this
stage. After this stage, until at end of 2h of milling, there is very little change in morphology (Fig. 4c).
However, some particles were fractured with increasing milling time particles get work hardened and after 2h of
milling, the tendency to fracture predominates over cold welding (Fig. 4d). In other words, work hardening of the
deformed particles reached a critical value which led to the activation of the fracture process [2]. Fig. 4e shows the
morphology of the powders fractured at the end of 4h of milling. Milled powders exhibited a shape changes from
flake-like to nearly spherical or angular shape. As can be seen, Fig. 4d, 4e, after this stage, powder morphology
almost unchanged but the fracture continued until the end of 8h of milling.
As can be seen Fig. 4f, at the end of 10h of milling, powders agglomerate seriously. There are various reasons for
this situation. The most important of these reasons is the low milling speed of vial. Therefore, methanol (PCA) could
not be absorbed by the surfaces and powders were agglomerated to each other [10]. In addition, decreasing particle
size is one other factor affecting agglomeration [9].
630

(a)
(b)
(c)

(d)
(e)
(f)
Fig. 4. Morphologies of Al 2024 powders after different milling time at vial milling speed of 250rpm:
(a) 0.5h, (b) 1h, (c)2h, (d) 4h, (e) 8h, and (f)10h [10].
(a)
(d)
(b)
(e)
(c)
(f)
Fig. 5. Morphologies of Al 2024 powders at milling speed of 350rpm:

(a) 0.5h, (b) 1h, (c) 2h, (d) 4h, (e) 8h, and (f)10h.
Fig. 5 shows the morphology of the powders of milled at 350 rpm. Similar morphologies are seen with Fig. 4 but
fracture is much more than previous procedure (250rpm). Milled powders exhibited a shape changes from flake-like
to nearly spherical or angular shape in a short time. Kinetic energy per collosion increases by increase of milling
speed from 250 to 350rpm and therefore, particles get more work hardened. Moreover, agglomeration is less than
the previous processes. This observation shows fracture is more than previous processes (250rpm).
3.3. Particle size
Fig. 6 shows the measurement of particle sizes of the Al 2024 powders for different milling speed and different milling time. The measurment shows that a light difference in particle size can be observed up to 1h of milling. With
631

increase in milling time, particle size show a significant change and particle size gradually decreased. As it can be
seen, the average particle size of both the process is almost the same at the end of 10h of milling. Meanwhile, there
is a significant difference between two different milling speeds (250 and 350rpm). It was reached steady state in first
speed of 250rpm but fracture is still continues in second speed of 350rpm at the end of 8h of milling. In other words,
ball-impact energy of balls increases because of increasing milling speed so work hardening of particles increases
and thus increasing the amount of fractured particles [12].
Fig. 6. The change of particle size with milling speed and milling time.
3.4. Particle microhardness
The change of microhardness of milled powders as a function of milling time is shown in Fig.7. In general, increasing the milling time increases the deformation and work hardening of milled powders. In this study, there is a continuous increase in hardness of powders with increasing milling time. Moreover, increasing milling speed increases
microhardness of powders due to increasing work hardening.
Fig.7. The change of microhardness with milling speed and milling time.
3.5. Apparent density
The first point observed in the high-energy process is the dependence of milling speed and time on apparent density. Fig. 9 shows this dependence for the Al 2024 powders. The predominantly ligamental or irregular morphology
of the initial (as received) powders causes bad powder packing, which results in the low initial apparent density values. The ligamental morphology of the shorter-time mechanically milled powders brings good powder packing due
to convert into semi-spherical from ligamental powder, and consequently increases in the apparent density values.
Then, the laminar morphology of the shorter-time mechanically milled powders brings poorer powder packing, and
consequently decreases in the apparent density. After longer milling, the apparent density of the Al 2024 powders
reaches a steady value [12].
632

Fig. 8. Apparent density changes versus time of mechanical alloying for Al 2024 powders.
4. Conclusion
The results indicate that milling speed occurs considerable effects on the milling process, powder morphology and
particle size as well as on the structural behaviour of the as milled powder.
1. The Al 2024 powder particles submitted to high energy ball milling are in good agreement with the model description proposed for ductile-ductile systems.
2. Fracture effectiveness of high energy ball milling increases with increasing milling speed.
3. Particle size distribution of Al 2024 powders was homogenous after 8h of milling process and particle size reduction increases with increasing milling speed.
4. Apparent density of Al2024 were changed with different milling speeds and apparent density of 350rpm speed
was higher than 250rpm speed for milled Al2024 powders.
5. Microhardness measurements of milled powders indicate their increase in comparison to the initial values of Al
2024 powders for the two different milling speeds and microhardness of 350rpm speed was higher than 250rpm
speed for milled Al2024 powders.
Acknowledgement
providing Al 2024 powders.
References
1. C. Suryanarayana, Mechanical alloying and milling, Marcel Dekker, New York, 2004
2. Kh. Gheisari, S. Javadpour, J.T. Oh, M. Ghaffari, Journal of Alloys and Compounds 472 (2009) 416420.
3. I. Estrada-Guel, C. Carreno-Gallardo, D.C. Mendoza-Ruiz, M.Miki-Yoshida, E.Rocha-Rangel, R. MartinezSanchez, Journal of Alloys and Compounds 483 (2009 173177).
4. J.B. Fogagnolo, D. Amador, E.M. Ruiz-Navas, J.M Torralba, Materials Science and Engineering A 433 (2006)
45-49.
5. Syed Nasimul Alam, Materials Science and Engineering A 433 (2006) 161-168.
6. M.M. Rajath Hedge, A.O. Surendranathan, Front. Mater. Sci. China 4(1) (2009) 310-318.
7. R. Daly, M. Khitouni and N. Njeh, Physics Procedia 2 (2009) 685-691.
8. Hafeez Ahamed, V. Senthilkumar, Journal of Alloys and Compounds 505 (2010) 772782
9. L. Lu, M.O. Lai, S. Zhang, journal of Materials Processing Technology 67 (1997) 100-104
10. R. Sen, S. Yildiz, Karadeniz Technical University, Department of Metallurgical and Materials Engineering,
Trabzon, Turkey, Graduation Thesis, 41 pages, 2011.
11. S.M. Zebarjad, S.A. Sajjadi, Materials & Design 27 (2006) 684-688.
12. M. Adamiak, Journal of A Achievements in Materials and Manufacturing Engineering, 31(2008) 191-196.
13. C. Suryanarayana, Prog. Mater. Sci., 46 (2001) 1-184.
14. Li. Lu, Y.F. Zhang, Journal of Alloys and Compounds 290 (1999) 279-283.
633

The effects of parameters on the synthesis and the

piezoelectric properties of PLZT ceramics by sol-gel and
mechanical milling methods
Shahab Khameneh Asl *, Shahin Kh. Asl
Department of materials science and engineering, Faculty of Mechanical Eng., University of Tabriz, Tabriz, IRAN
Abstract
PLZT ceramic powders were successfully prepared from the mixture of zirconium (IV) propoxide, titanium (IV)isopropoxide and lead and lanthanum acetate trihydrate by modified sol-gel synthesis and ZrO2, PbO, TiO2 and La2O3
by high energy mechanical alloying under different conditions. The formation of perovskite phase in the calcined
PLZT powder has been investigated by X-ray diffraction (XRD) techniques. The morphology evolution was determined by scanning electron microscopy (SEM) technique.
The PZT powders with nanometer grain size were synthesized at a temperature lower than that required in the
conventional process. In the present work, PLZT samples were prepared by a sol-gel and mechanical activation
methods at a temperature as low as 700C with the particle size in the range of 20-30 nm. Fully dense PZT ceramics
with 98% of the theoretical density have been achieved from powders at a sintering temperature of 1200C for 2 h.
The good dielectric and ferroelectric properties of the sintered PLZT ceramic were measured for both methods.
Keywords: A. PLZT powder, B. sol-gel, C. mechanical activation, D.electrical properties
Introduction
Lead zirconate titanate PZT with morphotropic phase boundary is one of the most widely used piezoelectric materials with the perovskite structure [1-2]. Other oxides can be added to improved PZTs properties. Substituting the Asites of Pb2+ with La2+ leads to a considerable improvement in the electrical properties of PZT. As the electric valence
of the added cations is larger than the electric valence of the original cations, the crystal cell contains a vacancy in
the A-site (Pb2+) , As an average , the substitution of two A-site Pb2+ ions with two aliovalent La3+ ions will result in
one valance of an Asite in the crystal lattice, This substitution change the material properties, such as dielectric
constant, dielectric loss, elastic modulus, etc [3].
PLZT powders traditionally prepared by solid-state reaction processing oxides as the starting materials [4] the
conventional method requires a high sintering temperature. This leads to poor microstructure and properties of
piezoelectric. One of efforts to avoid this problem is to use ultra fine PLZT powder.
This powder can be synthesized by wet-chemical process [5] sol-gel process [6] and hydrothermal reaction [7] and
mechanical milling [8]. Reaction sintering is a promising fabrication technique for PZT ceramics in which reaction
between constituent phase, take place during sintering process at high temperatures.
It is simple process procedure and enhanced densification progress. Shrout et al [9] found that reactive sintering
process occurred during the final stages of perovskite formation. Preparation of PZT ceramics via a reactive sintering from their chemically coprecipiated precursors were reported by Xue and Wang [10]. In the present work,
ultrafine PLZT powders via sol-gel and mechanical activation processes were synthesized and these mixtures
showed a very high sinterability from which the PZT ceramics could be derived at temperatures from 1100oC to
1200oC.
634

EXPERIMENTAL PROCEDURE
The starting materials were commercially available PbO(99.9%, Merck), ZrO2 (99.9%,Merck), TiO2(99.9%,Merck),
La2O3 for solid state methods and Trihydrated lead acetate [Pb(CH3COO)2-3H2O]( analytical grade, Merck), zirconium n-propoxide [Zr(OCH(CH3)2)4](assay 70% in propanol, Fluka), hydrated Lantanium acetate and titanium
iso-propoxide [Ti(OCH(CH3)2)4] (for synthesis, Merck )for sol gel method.
According to chemical formula Pb1.1(Zr0.53_sLasTi0.47)O3; x = 0.010.05, approximate amounts. of starting materials
were weighed. In solid state methods, oxides mixed in an alumina jar for 24 h in ethanol and for activation further
milled in planetary ball mill.
Milling conditions were the following: stainless steel jar and balls, ball to powder weigh ratio was 20:1, powder
quantity was 20 g, air atmosphere, rotation speed of discs was 350 min-1, and milling time was 900 min. In the sol
gel method, lead acetate trihydrate and hydrated lanthanum acetate were dissolved in heated acetic acid.
The solution was dehydrated at 105C for 2 h and after cooling to 80C it was mixed with the acetate solution of zirconium and titanium propoxide in the required ratio of compounds. By polycondensation of the orange lead zirconyl
titanyl acetate after adding a hydrolyzing agent [ethylene glycol, H2O and NH3(aq)] with the temperature of 80C,
an yellow sol was formed, which was converted to a gel at the given temperature11. Polycondensation took place in
closed flasks. After polycondensation (12 h), it was dried at 100C in 8 h.
All powders calcinated in optimum calcinations conditions for the manufacture of perovskite PZT powder. Calcinated powders were subsequently examined by room temperature X-ray diffraction (XRD; SIEMENS D500), using
CuK radiation, to identify phase formation.
Crystal size and phase formation were analyzed by Sheruder low [12] and standard JCPDS files. The mixtures were
pressed in to grain pellets and sintered at 1100C- 1300oC for 2h. The density of PZT ceramics was measured by
using Acheron method. The dielectric property of the sintered samples was measured by using impedance analyzer. The ferroelectric properties of the PLZT powders were measured using an RT 66A ferroelectric tester.
RESULTS AND DISCUSSION
Fig.1 illustrates the XRD patterns of calcined PLZT prepared by mixed oxides and mechanical activation, and solgel methods at 850, 650, 600oC respectively. The patterns for the calcined powder suggest that the phase is mainly
perovskite. However, there exist some extra peaks for conventional powders and the broaden peaks with small tail
and low crystallinity appeared at 2 at 45 for other methods.
After sintering all compositions have the single perovskite phase. It illustrated that there is no secondary phase
against La contents will. PLZT derived by sol gel and mechanical activation formed completely in lower temperature
than conventional method.
Fig. 1. XRD patterns of calcined (a) mixed oxides 850 C, (b) sol gel600 C, (c) mechanical actived 650 C PLZT
at suitable temperatures for 2 h (xxx: PZT, p:PbO, precursors).
635

The theoretical density of sintered PZT (52:48) doped with 1.0 5.0% La varied from 8.07 to 7.78 g/cm3 and it slightly
deceases with increasing La content for all methods. As illustrated in Table1, The bulk density of samples that ultra
fine powders have a good sinterablity than conventional powders at lower temperature. The density of mechanical
powders is rapidly increased in low temperature because of its stored stress that can be change to chemical force
and its high grain surface that can be released by sintering. The loss of PbO had another effect that caused the
decrease in density at high temperatures.
Table 1. Some physical properties of PLZT sintered at various conditions

Table 2 summarizes the dielectric constants and some piezoelectric parameters of the ceramics. It was observed
that the dielectric constant remarkably increased with increasing sintering temperature initially. It can be found that
the dielectric constant of PLZT increases with increasing density but with increasing grain size at high temperature
reduces its rate.
Table 2. Dielectric and piezoelectric of PLZT (1%La)

Results imply that control of La content and sintering temperature for each process to minimize grain size increases
dielectric constant. The value of kp for all conditions reached the maximum (0.47) at 1.00 mol% La before declining steadily for higher La concentration. The value of kp tends to increase with increasing sintering temperature.
In contrast, the values of Qm dramatically declined from 225 to 96, and increased slightly for higher La content.
Moreover, the Qm tended to decrease with decreasing average grain size for PLZT. The mechanical quality factor,
Qm is reduced because of a reduction in the concentration of domain stability.
Scanning electron micrographs of the surface morphology of PLZT samples sintered at 1100OC to 1300OC at various
compositions are shown in Fig.4. In general, sol gel and mechanical PLZT samples show dense and homogeneous
microstructures, it can be seen from Fig. 3 that the grain size significantly decreases when La content is increased
from1.0 to 3.0 mol%, and relatively small changes occur for a higher La concentration. SEM images show that an
increase in La content and using the sol gel and mechanical methods decease grain size and porosity of samples.
636

Fig.4. SEM microstructure of sol-gel PLZT ceramics by 1.00 mol%La sintered for 2 h (a) 1100 (b) 1200 (c) 1300OC
CONCLUSION
In this study, lanthanum-doped lead zirconate titanates (PLZT) in the area around the morphotropic phase boundary (MPB) have been investigated. The microstructure showed dense grains which tended to become smaller
when either increasing La3+ content, or using the activation methods to decreasing sintering temperature. The
dielectric constant tended to increase with the activation methods, giving the maximum value of 2000 for 3.0 mol
percent La3+ sintered at 1200OC. As the average grain size decreased, the dielectric constant increased. The
value of planar coupling factor (kp) was fluctuated and reached the maximum of 0.47 at 1.00 mol% La3+. In addition, the mechanical coupling factor (Qm) of the doped ceramics showed a significant decrease in all cases. The
overall results showed that PLZT prepared by sol gel method with 1.0 mol% La sintered at 1200OC have the best
properties.
REFERENCES
[1] B. Jaffe, W.R. Cook Jr., H. Jaffe Piezoelectric Ceramics Academic Press, New York, 1971.
[2] Moulson A.J., Herbert J.M. Electroceramics Second Ed.,Wiley Press, 2003.
[3] Yang Wein-Duo PZT/PLZT ceramics prepared by hydrolysis and condensation of cetate precursors Ceramic
International, 27 (2001) 373-384.
[4]. Satter N.,Colla E.L. Ferroelectric Ceramics. Tutorial reviews, theory, Processing, and applications Birkhauser
Verlag Basel, 1993
[5] R.N. Das, A. Pathak, P. Pramanik, Low-temperature preparation of nanocrystalline lead zirconate titanate
and lead lanthanum zirconate titanate powders using triethanolamine J. Am. Ceram. Soc. 81 12 1998 3357
3360.
[6] N. Okada, K. Ishikawa, T. Nomaru Low hysteresis actuator of alkoxide-prepared Pb0.96Sr0.04(Zr0.51Ti0.49)
O3 Jpn. J. Appl. Phys. 30 (1991) 22672270.
[7] T.R.N. Kutty, R. Balachandan, Direct preparation of lead zirconate titanate by the hydrothermal method Mater.
Res. Bull. 19 1984 14791488.
[8] Kong L.B., Ma J. PZT ceramics formed directly from oxides via reactive sintering Materials Letters 51(2001),
95100.
[9] T. R. Shrout, P. Patant, S. Kim, G.S. Lee conventionally prepared submicrometer Lead- Based provskite powders by reactive calcinations J. Am. Ceram. Soc. 73 (7) (1990) 1862- 1867.
[10] J. Xue, J. Wang Lead zrconate titanate via reactive sintering of hydroxide precursors J. Mater. Res. 14 (4)
(1990) 1503- 1509.
[11] T. Tunkasiri Properties of PZT ceramics prepared from aqueous solution Smart. Mater. Sci. 3 (1994) 243
247.
[12] Suryanarayana c.,Mechanical Alloying and Milling, Progress in Materials Sci. USA, 46(2001)1-184.
637

THE IMPLEMENTATION OF RESPONSE SURFACE METHODOLOGY

FOR THE OPTIMIZATION OF MILLING PARAMETERS IN THE
SYNTHESIS OF Cu-Al2O3 POWDER
Ali DORYAB*, Nader PARVIN** and Davoud HAGHSHENAS FATMEHSARI***
* Department of Mining and Metallurgical Engineering, Amirkabir University of Technology, Tehran,
Iran, doryab.aut@gmail.com
** Department of Mining and Metallurgical Engineering, Amirkabir University of Technology, Tehran,
Iran, nparvin@aut.ac.ir
*** Department of Mining and Metallurgical Engineering, Amirkabir University of Technology, Tehran,
Iran, davoudhaghshenas@gmail.com
ABSTRACT
In the present work copper-alumina powder has been successfully produced by mechanical milling.
Response Surface Methodology (RSM) was employed to study and optimize the effect of four factors,
namely as aluminum solubility in copper, milling time, ball powder ratio (BPR) and milling speed (RPM).
The response of the system was the difference in lattice parameter of copper after milling process.
Results demonstrated that among all the four factors, only rpm had statistically minor effect on the difference in lattice parameter of copper. The most statistically significant interactions were found to be BPR,
solubility of aluminum in copper, and milling time respectively. The proposed model predicted that the
maximum value of lattice parameter is 0.356 where solubility of aluminum in copper, BPR, and RPM are
1.1, 10.2, and 1.1 h respectively. X-ray diffraction patterns, verified the RSM values.
Keywords: copper-alumina powder, mechanical alloying (MA), response surface methodology (RSM),
optimization
1. INTRUCUCTION
Mechanical alloying (MA) is a solid-state powder processing technique involving repeated welding,
fracturing, and rewelding of powder particles in a high-energy ball mill. Mechanical alloying is a complex process and hence involves optimization of a number of variables to achieve the desired product
phase and/or microstructure.For many applications such as electronic packaging or manufacturing of
electrodes and contact materials [1], it is required that the materials must have a good combination of
electrical conductivity, wear resistance, and resistance to erosion and welding [2]. Mechanical attrition
of copper powders with ceramic particles has allowed the uniform introduction of small strengthening
phases and also promotes a microstructural grain refinement [3]. Copper-alumina metal matrix composites (MMCs) combine the high electrical and thermal conductivity of the copper phase and high strength
and high thermal and chemical stability of the alumina phase. Thus copper-alumina MMCs have the
potential to offer both high strength and high electrical conductivity. In order to achieve high fracture
toughness and low processing cost, the Alumina phase in the microstructure should be in particulate
form, and the particle size should be small. Several techniques can be used to synthesize copperalumina MMCs. Casting is one of the options [4] which has its own problems such as low toughness.
This limitation can be avoided by using the powder metallurgy (PM) process. As a way to improve the
mechanical properties at low temperatures, the matrix must be strengthened with particles, which have
a low diffusivity in the [5-6]. Type of mill, milling container, milling speed, milling time, type, size, and
size distribution of the grinding medium, Ball-to-powder weight ratio, extent of filling the vial, milling atmosphere, process control agent (PCA) and temperature of milling [7]. All these process variables are
not completely independent.Distribution of reinforcing particles during ball milling is not only dependent
on ball milling parameters but also on initial particle sizes [8, 9]. The optimum milling time depends on
638

the type of mill, size of the grinding medium, temperature of milling, ball-to-powder ratio and desired
phase formation [10]. Another technique is a combination of oxidation and mechanical alloying Cu-Al
alloy powder is milled under an oxidizing atmosphere to produce the composite powder.[11] With this
technique, Cu powder is first partially oxidized, and then the partially oxidized powder is mechanically
alloyed with Al powder to facilitate reactions between CuO (or Cu2O) and Al, forming Al2O3 particles.
Also we can use in situ process; the Al2O3 particles were also produced in-situ by the reaction between
CuO and Al [12].
Identification of the correct optimum value of the effective parameters in mechanical alloying system is
a prerequisite for their successful exploitation. Different parameters identified in previous research as
significantly influencing the mechanical alloying system are Al %, time, BPR and RPM [6, 7, 8 and 12].
There are extensive literatures on mechanical alloying systems but an answer to the question of what
is the optimum level of processing parameters cannot be reliably found from these studies. This is because in previous studies one-factor-at-a-time methodology has been used to optimize the abovementioned parameters. This methodology is very inefficient and furthermore gives absolutely no information
about interactions between parameters in a process. The only methodology capable of providing an answer to this question is factorial design of experiments (DOE). The use of techniques such as Response
Surface Methodology (RSM) - is able to simultaneously consider several factors at different levels, and
give a suitable model for the relationship between the various factors and the response [13]. The aim of
the present work is to evaluate and quantify interaction between important parameters in a mechanical
alloying system by using an appropriate methodology, namely RSM. A half fractional factorial central
composite design, was chosen as the design matrix since it allows reliable identification of first order
interaction between factors and provides a second order polynomial model which can be used to predict
optimum level of these parameters [13].
2.1. Materials
The materials used in the experiments were Cu powder, purity 99.5%, average particle size 63m), Al
(purity 99.5%, average particle size 45 m) and CuO (purity 99%, particle size 63m) powders.
2.2. Experimental Methods
Table 1 presents the lists of 28 combinations of factor levels. Hardened steel vial containing tungsten
carbide (WC) balls, Ethanol 96 as PCA and the powders were sealed in a glove box filled with high purity Argon. The ball milling was performed in a planetary ball mill. The Cu-Al powder mixture was milled
for up to 8 h. In the stage two, CuO powder was added to the optimized Cu(Al) solid solution for up to
8h and mechanically alloyed with ball to powder weight ratio of 4:1.
Samples (28 samples) were taken out from the vial and the amount of difference in lattice parameters
were studied by X-ray diffraction which was performed in a Philips PW1800 X-ray diffractometer with Cu
K Ni filtered radiation.
Experiment
Number
Al %
1
2
3
4
5
6
7
8
9
10
11
12
13
14
Table1. Central composite design arrangement and response

Factors
1.0
10.0
1.0
10.0
1.0
10.0
1.0
10.0
1.0
10.0
1.0
10.0
1.0
10.0
time
1.0
1.0
8.0
8.0
1.0
1.0
8.0
8.0
1.0
1.0
8.0
8.0
1.0
1.0
BPR
4
4
4
4
16
16
16
16
4
4
4
4
16
16
639
rpm
50
50
50
50
50
50
50
50
250
250
250
250
250
250
Response(A)
0.261
0.168
0.210
0.210
0.279
0.279
0.169
0.279
0.298
0.150
0.279
0.184
0.298
0.279

15
16
17
18
19
20
21
22
23
24
25
26
27
28
1.0
10.0
1.0
10.0
5.5
5.5
5.5
5.5
5.5
5.5
5.5
5.5
5.5
5.5
8.0
8.0
4.5
4.5
1.0
8.0
4.5
4.5
4.5
4.5
4.5
4.5
4.5
4.5
16
16
10
10
10
10
4
16
10
10
10
10
10
10
250
250
150
150
150
150
150
150
50
250
150
150
150
150
0.216
0.245
0.253
0.215
0.295
0.257
0.122
0.174
0.300
0.297
0.245
0.295
0.250
0.260
2.3. Experimental Design for RSM

A central composite design (CCD) was adopted to study four factors at three levels. Twenty eight experimental runs consisting of 8 star points (star distance was 0) and 4 center points were generated with
4 factors and 3 levels by the principle of RSM using MINITAB Release 15. The levels employed for the
different factors, according to CCD design, are listed in Table 1.
The quadratic polynomial regression model (Equation 1) was used for predicting the response variable
in terms of the four independent variables:
(1)
Y is the response variable lattice parameter, b0, bi, bii, and bij are the coefficients of the intercept, linear,
quadratic and interaction terms, respectively, and Xi and Xj represent the four independent variables
(Al %, time. BPR and RPM).The experiments were carried out with two replicates and conducted in a
randomized order to avoid systematic bias.
The statistical significance of the full quadratic models predicted was evaluated by the analysis of variance (ANOVA). The significance and the magnitude of the effects estimates for each variable and all
their possible linear and quadratic interactions were also determined. . Unless otherwise stated, the
significance level employed in the analyses was 5% (p<0.05). Finally, the model was used to predict the
optimum value of the factors which result in maximum or fairly high lattice parameter (a).
2.4. Measurements and Analysis
Samples were analyzed by X-ray diffraction. Three major peeks were selected and from the Braggs
law (Equation 2) and using the least square root method, the lattice parameter of the samples was
calculated.
Braggs law
(2)
The difference between lattice parameter of samples (secondary) and lattice parameter
of copper (primary) determined. If the amount of this difference was positive that means aluminum had
diffused into copper under these condition and a solid solution of Cu( Al) was formed..
3. Results and Discussions
3.1. Model Fitting
In the design of experiments for estimating statistical models, optimal designs allow parameters to be
estimated without bias and with minimum-variance. A non-optimal design requires a greater number of
experimental runs to estimate the parameters with the same precision as an optimal design. In practical
terms, optimal experiments can reduce the costs of experimentation. RSM, reduces the costs of experimentation by allowing statistical models to be estimated with fewer experimental runs. The following
discussion shows how the response surface methodology helps in this regard. Table 1 lists the values
of difference of lattice parameters at each of the 28 combination of Factor levels with the values ranging
640

from 0.122 A to 0.300 A. The values of the regression coefficients are presented in Table 2. The linear
terms, except RPM, as well as the second order terms of the independent parameters, apart from Al
%, are significant. The statistical analysis of the interaction terms showed that, at 5% significance level,
there are significant interactions between Al %, time and BPR.
Based on the calculated values of the regression coefficients (Table 2) a polynomial regression model
equation that fitted 88.8% of the variation in the data is proposed as follows (coded values):
Response = 0.256 - 0.0141 Al% - 0.0143 time + 0.0188 BPR + 0.053 time time
- 0.075 BPR BPR + 0.019 Al% time + 0.0.285 Al% BPR - 0.0145 time BPR
(3)
The low values of P determined for the regression (P < 0.001), as well as the fact that the lack of fit of
the model was not significant (P > 0.05), revealed the suitability of the model (Table 3).
Table 2. Values of calculated regression coefficients (coded values).
Table 3.ANOVA table
3.2. Study of Interactions

In the cases where interaction between factors is statistically significant, surface plots give more complete information regarding the effect of a factor on the response. Examination of the surface plot is
presented in Figure 1.
641

Figure 1 Surface plots for difference of lattice parameter (a) respect to BPR and Al solubility in
Copper (%wt) (a), time and Al solubility in Copper (%wt) (b), BPR and time (h) (c) (other parameters
are fixed at their middle values).
According to the results presented in Table 2,. BPR is the most effective parameter compared to the
amount of Al and time, due to higher regression coefficient. Figure 2 illustrates the contour plots of difference of lattice parameter versus the variation of the three significant parameters (Al %, BPR and time).
It can be observed that the highest value of response, occurs at a BPR of around 10(dark green regions
in Figures 2 a and b).
Figure 2.Contour plots for difference lattice parameter with respect to BPR and Al solubility in
Copper (%wt) (a) and BPR and time(h) (b)(Other parameters are fixed at their middle values)
642

Also, by increasing of Al% or time, response (difference of lattice parameter) was declined. In red region
response is in lowest value where Al% and time are at their highest level and the level of time and Al%
should be around 1.
The rapid decrease in lattice parameter occured at the very beginning of the milling process, then the
change in lattice parameter decreases slowly with the prolonged milling. The decrease in lattice parameter is assumed to be due to the oxidation of dissolved aluminium, which forms as alumina dispersoids.
High diffusion rate of oxygen through the deformed copper matrix accelerated the process of oxidation
during milling.
This result is in agreement with a previous research that investigated the relationship between Cu-3.5
wt. % Al [7]. Lattice parameter and milling time relationship is shown in Figure 3.
Fig. 3. Lattice parameter vs. milling time for Cu-3.5 wt.% Al powder.
The BPR has a significant effect on the time required to achieve a particular phase in the powder being
milled. The higher the BPR, the shorter is the time required.
At a high BPR, the number of collisions per unit time increases and consequently more energy is transferred to the powder particles and so alloying takes place faster.
3.3. Optimization of parameters in the mechanical alloying
Initially, optimization of the factors for achieving maximum response was carried out using the proposed
second order polynomial model (Equation 3). This exercise The following conditions: Al % = 1.1(%wt),
BPR = 10.2, time = 1.1h. To confirm this prediction, and therefore the applicability of the proposed second order model for further optimization exercises, confirmation runs (i.e. runs at the predicted optimum
level of the factors) were carried out in triplicate. The 90% confidence interval for deference lattice
parameter under optimized conditions was obtained as 0.335 A. (Fig.4)Since the value predicted by
the model is within this interval, this can be taken as the confirmation of the suitability of the regression
model for predictive purposes [12].
Figure 4. XRD pattern of the Copper-Aluminum powder (optimized variable parameters)
643

4. Conclusions
It was investigated that Response Surface Methodology has been successfully optimized mechanical
milling factors and to examine the effect of four most effective parameters namely as aluminum solubility
of copper, time, ball powder ratio and rpm in the mechanical milling of copper-alumina powder. It was
shown that BPR is the most effective parameter in compared other variable and It was also found that
RPM had statistically insignificant effect on the difference of lattice parameter. A polynomial regression
model equation is proposed as follows:
Response = 0.256 - 0.0141 Al% - 0.0143 time + 0.0188 BPR + 0.053 time time
- 0.075 BPR BPR + 0.019 Al% time + 0.0.285 Al% BPR - 0.0145 time BPR
This exercise predicted that the maximum deference of lattice parameter is 0.356 which Aluminum solubility in Copper, BPR, and time were obtained 1.1(%wt), 10.2, and 1.1 h respectively.
Acknowledgements
The authors would like to thank Sahand Mirzaei, Reza Bahrami for their assistance in the experimental
work.
References
1. ASM Handbook, Powder Metal Technologies and Applications, vol. 7. ASM, USA, pp. 1020-1030.
1997
2. Chen, W., Kang, Z., Shen, H., Ding, B., Arc erosion behavior of a nanocomposite W-Cu electrical
contact material. Rare Met. 25, 37.2006
3. Lopez, M., Jimenez, J.A., Corredor, D., Precipitationcstrengthened high strength- conductivity copper
alloysccontaining ZrC ceramics. Composite: Part A 38, 272- 279.2007.
4. M.J. Couper, K. Xia, in: N. Hansen, D. Jnul Jensen, T. Leffers, Proceedings of 12th Ris Symposium
on Metal Matrix Composite, Ris National laboratory, Roskilde, Denmark, p. 291.1991
5. Lopez, M., Corredor, D., Camurri, C., Vergara, V., Jimenez, J., 2005.Performance and characterization of dispersion strengthened Cu-Tib2 composite for electrical use. Mater. Charact. 55, pp.252262.2005
6. Omer G uler, The investigation of contact performance of oxide reinforced copper composite via
mechanical alloying, journal of materials processing technology, 209,pp.1286-1290,2009.
7. Viseslava Rajkovic, Properties of copper matrix reinforced with nano- and micro-sized Al2O3 particles, Journal of Alloys and Compounds 459,177-184, 2008
8. Suryanarayana, C., Mechanical alloying and milling. Progr. Mater. Sci. 46, 1-184.2001
9. J. Corrochano, The effect of ball milling on the microstructure of powder metallurgy aluminium matrix
composites reinforced with MoSi2 intermetallic particles, Composites: Part A, 2011.
10. Ovecoglu, M.L., Ozkal, B., Mechanochemical synthesis of WC powders by mechanical alloying. Key
Eng. Mater.pp. 264-268,89-92.2004.
11. E. Bobrova, M. Besterci, Powder Metall. Sci. Tech. 6 (1994) 7
12. D.Y. Ying, Processing of Cu-Al2O3 metal matrix nanocomposite materials by using high energy ball
milling, Materials Science and Engineering A286, 152-156, 2000.
13. John Wiley & Sons, Montgomery, D.C. Design and Analysis of Experiments (6th Edition), 2006.
644

EFFECT OF MANUFACTURING PARAMETERS ON PHASE GROWTH AND

HOMOGENIZATION OF A PM Al/Ni3AL COMPOSITE
Maziyar AZADBEH*, Maryam ABBASI*
*Department of Materials Engineering, Sahand University of Technology,
P.O. Box 51335-1996, Tabriz, Iran,
Corresponding author. Tel.:+98 412 3459446; fax: +98 412 3444333, azadbeh@sut.ac.ir
Maryamabbasi86@gmail.com
ABSTRACT
Aluminum reinforced with intermetallics present a special behavior due to the reaction between matrix and reinforcement. This reaction forms interphases that influence the physical and mechanical properties of Al composites.
In this work an approach was made to study of produced interphases in a PM Al/Ni3AL composite, under varying
time of mechanical alloying and sintering conditions. To obtain different types of interphases and more homogenization, aluminum powder was mixed with 5 wt.% Ni3Al particles (Intermetallics were obtained by mechanical alloying)
followed by uniaxial compacting of a preform, and subsequent sintering at different temperatures (580, 625 and
650C) accomplished.
A microstructural study, quantitative and qualitative analysis were carried out by SEM and XRD, showing the
chemical gradient formed at the interphase between Al matrix and intermetallic particles under different manufacturing parameters. As well as raising sintering temperature and time of mechanical alloying for producing Ni3Al
particles increased diffusion of Ni through intermetallic particles to matrix. At higher temperatures, dissolution of
Ni3Al particles occurred with formation of concentric layers of Al3Ni and Al3Ni2 phases.
Keywords: PM Al composite, intermetallic Ni3Al, mechanical alloying, manufacturing parameters, homogenization.
1. INTRODUCTION
Intermetallics of the Ni-A1 system would be excellent candidates for reinforcement of Al-base because they exhibit
a high level of hardness and melting temperature. However, aluminum intermetallic compounds are so brittle that it
alone cannot serve as a structural material. Attempts have been made to compensate the brittleness by embedding
it in a ductile matrix material. These metal matrix composites (MMCs) are currently being investigated because of
their superior properties as compared to those of most conventional materials [1, 2, 3, 4].
The interfacial characteristics in metal matrix composites play an important role in determining the resultant composite properties. This is because superior material properties in MMCs are attributed to the efficiency of the load
transfer from the matrix to the reinforcements through the matrixreinforcement interface [5]. The degree of property
enhancement depends also on morphological factors such as volume fraction, size and spatial distribution of the
reinforcement phase arising from manufacturing parameters.
The major obstacle to the application of such materials is chemical reaction and interfacial bonding at reinforcement/
matrix interfaces during materials processing [6], that affecting mechanical properties and corrosion resistance.
In order to solve this problem, some special techniques, such as adjustment of the chemical composition of the matrix and manufacturing parameters such as sintering temperature in PM route are used therefore optimum sintering
temperature in PM route can be the main key in attaining improved properties.
645

However deleterious reaction products at intermetallic/matrix interfaces may form during sintering or solid solution
treatments giving rise to brittle interphases and modifications in matrix composition, which result in the worsening
of mechanical properties.
In some cases such as Al/NiAl, better bonding of the reinforcement to matrix gives better mechanical behavior of
composite, while the produced reinforcement is more brittle [7,8].
As well as the mechanical alloying process changes dramatically the powder characteristics, the more refined
microstructure improved dispersion of the reinforcement particles and improved mechanical properties can be
achieved with this process route.
The aim of this study was investigation on the effect of manufacturing parameters such as different sintering temperatures and MA exposure time on characterization of the microstructure of aluminum matrix/Ni3Al interface in Al/
Ni3Al composite where aluminides have been formed as the effect of diffusion and interaction between Ni and Al.
Depend on type and amount of created intermetallics at reinforcement/matrix interfaces, varying physical and mechanical properties will be achieved. Therefore main role of manufacturing parameters on obtained properties of
composite should be considered.
Aluminum matrix composites were produced employing pure aluminum as metal matrix when nanostructure Ni3Al
intermetallic particles were used as reinforcement. Aluminum powder from Merck Co. (Germany) was used as a
matrix material. Reinforcement particles used were the nanostructure Ni3Al Nickel aluminide (particles size less
than 100 nm) produced in mechanical alloying process with the conditions given in Table 1.
To investigate the effect of starting intermetallic reinforcement size on interfacial bonding and more homogenization
two different sizes of reinforcement were produced by selecting two appropriate mechanical alloying times (15 and
55 h).
The powders of Aluminum and Ni3Al were mixed to give the nominal composition Al5wt.%Ni3Al. The obtained
mixed powders were cold compacted uniaxially in the cylindrical matrix 14mm in diameter with floating die and oil
graphite die wall lubricated.
The compacting pressure was chosen equal to 400 MPa for 300 second. To investigate the effect of sintering temperature on homogenization and interphase reaction, the compacted samples were sintered at 580, 625, 650C in
a vacuum furnace for 30 min followed by furnace cooling. Densities of the sintered parts were determined using
Archimedes principle (DIN ISO 3369).
Microstructural observations were made by optical microscopy (OM) and scanning electron microscopy (SEM).
The produced layers through diffusion of Ni at matrix/reinforcement interfaces were identified by energy-dispersive
X-ray (EDX) analysis. As well as the produced interphases under different sintering temperatures were obtained by
XRD examinations.
To determine macro-microhardness values, Vickers tests were performed in the carefully sectioned and polished
specimens. Vickers macro-microhardness values were the average of at least 10 indentations by applying 30 kg
and 25 g load for 15 s respectively.
Table1. Parameters of mechanical alloying for producing Ni3Al
646

3. RESULTS AND DISCUTION

In order to evaluate the effect of mechanical alloying on the reinforcement grain size, XRD analysis was performed
(see Figure 1).
Figure 1- X-ray diffraction pattern of elemental mixture powders and after 15 h and 55 h mechanical alloying for
the composition Ni75Al25, used as nanostructure reinforcement in fabrication of Aluminum matrix composite
Peak line broadening represented a decrease in the crystalline size of nanostructure Ni3Al and accumulation of
lattice strain with increasing time of mechanical alloying. The analysis of the XRD peaks was performed via the
WilliamsonHall method.
The evolution of matrixreinforcement interface and spatial distribution of the reinforcement in the matrix in Al/5
wt% Ni3Al composite during sintering at three different sintering temperatures (580, 625 and 650C) was followed
by optical microscopy and SEM observations on specimens prepared by embedding the sintered samples in epoxy
resin followed by conventional metallographic polishing.
Sintering Temperature=580C
Figure 2. Microstructure of sintered Aluminium matrix composite particle reinforced with 5 wt.% Ni3Al particles
after 15 h of mechanical alloying
Figure 2 shows low sintering temperature (e.g. 580C) can not eliminate the void around intermetallic that originated at particle matrix interface and generated primarily by decohesion of the matrix-particle interface. Therefore
the bonding between the matrix and intermetallic particles is not strong and thickness of diffusion layer around the
intermellic is negligible. Microstructure of the composite sintered at 580 shows that Ni3Al particle reinforcements
remain approximately intact.
With increasing sintering temperature diffusive layers will be extended and reaction phases improve the bonding.
An analysis of the chemical composition by the energy dispersive X-ray (EDX) method in vicinity of the interface
with the matrix of sintered composite at 625C, has shown the following contents: 24.37 at.% of Al and 75.63 at.% of
647

Ni in the inner layer of reinforcement, 60.11 at.% of Al and 39.89 at.% of Ni in the middle layer of reinforcement and
75.22 at.% of Al and 24.78 at.% of Ni in the outer layer of interface (Figure 3). The EDX results and XRD patterns of
sintered composite at different sintering temperatures (Figure 4), confirm OM and SEM observations of the formation of a multilayer at matrixreinforcement interface in Al/Ni3Al composite, sintered at 625C for 30 min.
Figure 3. EDX measurements in the diffusion zone around interface for Al+ 5wt.%Ni3Al, sintered at 625C for 30
min
As it can be seen in Figure 2, higher sintering temperatures help more the diffusion of elements at matrix-reinforcement interfacial. The spatial distribution of the reinforcement phase in matrix arising from sintering at 650C is larger
than it created at 625C. As well as pores in the microstructure of sintered composite at 650C are more rounded
with respect to other samples that sintered at lower temperatures.
Exothermic reaction due to the formation of Ni-Al intermetallic compound [9] during sintering of Al/5 wt.%Ni3Al composite at 650C causes heat flow through the Aluminum matrix that contribute to eliminate pores and make them
round.
Comparison of the microstructure in Figure 2 shows that the thickness of interfacial layer increases with rising
sintering temperature.
Comparing the microstructure of sintered composite at different temperatures in Figure 2 shows that the new phases at interface also have the effect of increasing volume locally, compressing the matrix around the intermetallic
particles, which is due to the different densities of the three Ni-aluminides [10] (7.45, 4.75 and 3.95 g/cm3 respectively
for Ni3Al, Al3Ni2 and Al3Ni).
The Obtained microstructures under different manufacturing parameters are in a good coordination with measured
sintered density. Density was determined by Archimedes principle (DIN ISO 3369) since this method is more precise than calculating the density from the dimensions. The sintered density values for Al/ 5 wt.%Ni3Al composite
sintered at 580, 625 and 650C are 2.79, 2.88 and 2.89 g/cm3, respectively.
648

Figure 4. X-ray diffraction pattern of Al/Nickel aluminide composite as green and assintered at different
temperatures. The peaks are labeled accordingly
It can be concluded that at higher sintering temperature (625 and 650C) dissolution of the Ni3Al intermetallic in
Al/5wt.%Ni3Al composite occurs with formation of concentric layers of Al3Ni and Al3Ni2 reaction products according
to the following sequence:
Firstly the Al3Ni phase nucleates and grows enveloping the dissolving Ni3Al nucleus. This can be attributed to solidstate inter-diffusion that occurs between aluminum and nickel at temperatures below the eutectic temperature and
form predominantly aluminum-rich compounds. Then the Al3Ni2 phase nucleates and grows between the remaining
Ni3Al nucleus and the growing Al3Ni layer. These phase transformation are exothermic which subsequently heat the
compact and thus triggering a reaction as well as it can be act as a driving force for diffusion of Ni and Al. Finally,
the Ni3Al and Al3Ni2 phases completely dissolve and the equilibrium Al3Ni phase remains.
Constituent phases of interfacial layer created in Al/Ni3Al that sintered at 625C for 30 min were studied by microhardness measurements. The results of these measurements on the inner, middle, outer layer of diffusion bond and
matrix are shown in Figure 5. The microhardness of the produced intermetallic in the inner, middle and outer layers
and Aluminum matrix are of about 922, 1100, 770 and 59 HV0.025 respectively
Figure 5. Microhardness values (HV 0.025) of constituent phases at matrix reinforcement interface in Al + 5
wt.% Ni3Al, sintered at 625C for 30 min
The results of macrohardness measurements with a load of 30 kg (HV 30) for sintered samples are graphically depicted in Figure 6. With increasing sintering temperature, the hardness of sintered samples increases. This behavior
is a consequence of the formation of diffusion reaction phases and better bonding of the reinforcement to matrix at
higher sintering temperature that affects the hardness of composite
649

Figure 6. Macrohardness of sintered Al + 5 wt.% Ni3Al particles (15 h MA) at different temperatures
In order to investigate the effect of time of mechanical alloying process on interfacial bonding at reinforcement/
matrix interfaces, sticking reinforcement to matrix and more homogenization, Ni3Al particles that produced after 15
and 55 h mechanical alloying were used as reinforcement component in aluminum matrix composite (Figure 7). To
reveal the effect of reinforcement grain size on thickness of diffusion layer, specimens were sintered at 625C for 30
min. At this sintering temperature, multilayer interface is seen obviously in the microstructure (see Figure 2 and Figure 3). Figure 7a shows Ni3Al particles (15 h MA) that surrounding by diffusion layers and Ni-Aluminide components
have been created. In the meanwhile it is seen in Figure 7b that Ni3Al particles (55 h MA) change to Al3Ni, due to
diffusion Ni to the Aluminum matrix and Aluminum to reinforcement particle and more dissolution of Ni3Al occurs.
Increasing time of mechanical alloying generate more defects such as vacancy besides more stored strain energy
in the powders due to large plastic deformation. The stored elastic energy, small volume to surface ratio are the
main parameters in creating the condition which led to the increase of reaction rate by providing short circuit diffusion path.
The numerous interfaces provide a high density of short-circuit diffusion paths hence very enhanced diffusion rates
are expected for Ni3Al particles after 55 h of mechanical alloying in comparison with particles proceed after 15 h
of mechanical alloying. This enhanced diffusivity can have significant effect on spreading intermetallic phases at
interfacial. The increased diffusivity leads to increased sinterability and sticking reinforcement to matrix.
As well as the formation of Al3Ni leads to swelling of the compact and Kirkendall porosity due to unbalanced diffusivities of nickel and aluminum. This phenomenon is more obvious in the case of composite with fine intermetallic
reinforcement because of rapid reaction between intermetallic and Aluminum matrix.
Figure 7. Microstructure of sintered Aluminium matrix composite particle reinforced with 5 wt.% Ni3Al particles
after 15 h and 55 h of mechanical alloying, sintered at 625C for 30 min
650

4. CONCLUSION
1. Sintering temperature is one of the critical parameters in manufacturing of PM composite, which influence
interfacial characteristics in metal matrix composites, sintered density and obtained physical and mechanical
properties.
2. At higher sintering temperature (625 and 650C) dissolution of the Ni3Al intermetallic in Al/5 wt.%Ni3Al composite occurs with formation of concentric layers of Al3Ni. The Al3Ni phase nucleates and grows enveloping the
dissolving Ni3Al nucleus. Then the Al3Ni2 phase nucleates and grows between the remaining Ni3Al nucleus and
the growing Al3Ni layer; finally the Ni3Al and Al3Ni2 phases completely dissolve and the equilibrium Al3Ni phase
remains.
3. The fine Ni3Al reinforcements produced from prolonged mechanical alloying procedure promote the diffusion
process owing to large deformation of powder particles and hence more stored strain energy. Consequently,
thicker diffusive layers formed around the fine reinforcements during sintering and produce a composite with
decreased porosity percentage in comparison with the coarse intermetallic reinforcements at the same sintering temperature.
4. Powder metallurgy is the most suitable method for processing Aluminum matrix composite reinforced with
intermetallic particles, because of its capacity to control reactions between matrix and reinforcement by proper
selecting of sintering temperature, exposure time in sintering process, size of intermetallic particles in other
words mechanical milling time and other manufacturing parameters applied to production procedure of starting
powder and other sequences of composite synthesis. Therefore importance of manufacturing parameters on
achieved properties of composite should take into account.
5. REFERENCES
1. - C. Di.Az, J.L. Gonzalez-Carrasco, G. Caruana, and M. Lieblich, Ni3AI Intermetallic Particles As Wear-Resistant Reinforcement for AI-Base Composites Processed by Powder Metallurgy, Metallurgical and Materials
Transactions A, Vol. 27A, OCTOBER 1996, 3259-3266.
2 - W.H. Xu, X.K. Meng, C.S. Yuan, A.H.W. Ngan, K.L. Wang, Z.G. Liu, The Synthesis and Mechanical Property
Evaluation of Ni/Ni3Al Microlaminates, Materials Letters, 46 (2000) 303308.
3 - L. DAngelo, G. Gonzalez, J. Ochoa, Phase Transformations Study on Ni75Al25 and Ni50Al50 During Mechanical Alloying and Sintering, Journal of Alloys and Compounds, 434435 (2007) 348353.
4 - M. Krasnowski, A. Antolak, T. Kulik, Nanocrystalline Ni3Al Alloy Produced by Mechanical Alloying of Nickel
Aluminides and Hot-Pressing Consolidation, Journal of Alloys and Compounds, 434435 (2007) 344347.
5 - I.G. Waston, P.D. Lee, R.J. Dashwood, and P. Young, Simulation of the Mechanical Properties of an Aluminum Matrix Composite using X-ray Microtomography, Metallurgical and Materials Transactions A, Vol. 37A,
March 2006551.
6 - M. Adamiaka, J.B. Fogagnolo, E.M. Ruiz-Navas, L.A. Dobrzaski, J.M. Torralba, Mechanically Milled
AA6061/(Ti3Al)P MMC Reinforced with Intermetallics The Structure and Properties, Journal of Materials
Processing Technology, 155156 (2004) 20022006.
7 - Hiroshi Okada, Yasuyoshi Fukui, Ryoichi Sako, Noriyoshi Kumazawa, Numerical Analysis on Near Net
Shape Forming of AlAl3Ni Functionally Graded Material, Composites, Part A 34 (2003) 371382.
8 - H.A. Pour, M. Lieblich, A.J. Lopez, J. Rams, M.T. Salehi, S.G. Shabestari, Assessment of Tensile Behaviour
of an AlMg Alloy Composite Reinforced with NiAl and Oxidized NiAl Powder Particles Helped by Nanoindentation, Composites, Part A 38 (2007) 25362540.
9 - L. Lu, M. O. Lai and S. Zhang, Thermodynamic Properties of Mechanically Alloyed Nickel and Aluminum
Powders, Materials Research Bulletin , Vol. 29, No. 8, 1994, 889-894.
10 - H.A. Pour, M. Lieblich, A.J. Lopez, J. Rams, M.T. Salehi, S.G. Shabestari, Assessment of Tensile Behaviour
of an AlMg Alloy Composite Reinforced with NiAl and Oxidized NiAl Powder Particles Helped by Nanoindentation, Composites, Part A 38 (2007) 25362540.
651

TOZ METAL PSKRTME YNTEM LE BORU YZEYLERNN

KAPLANMASI VE KARAKTERZASYONU
Erdal KARADENZ*, smail CEYLAN**, Uur ZSARA***, Azim GKE***
*
Sakarya niversitesi, Mhendislik Fakltesi, Makine Mhendislii Blm, Sakarya

**
PETKM, Aliaa, zmir
***
Sakarya niversitesi, Teknik Eitim Fakltesi, Metal Eitimi Blm, Sakarya
ZET
Bu almada, 4, 6 ve 10 ASTM A106 Grade A dikisiz elik borularn i yzeyleri bronz tozlar ile toz alev pskrtme yntemiyle kaplanmtr. Deneysel almalarda, toz pskrtme mesafesi ve hava basnc, deiken kaplama
parametreleri olarak alnmtr. Pskrtme mesafesi olarak 50 mm, 100 mm ve 150 mm mesafe ve hava basnc
olarak da 0, 0.5, 1 ve 2 bar deerleri kullanlmtr. Standartlarda 150 mm- 250 mm aras toz pskrtme mesafesi
tavsiye edilmektedir. Daha kk apl yataklarn i yzeylerinin kaplanmas iin, pskrtme mesafesi azal ile
kaplamann gerekletirilebilirlii aratrlmtr. Bunun iin pskrtme hava basnc deerleri deitirilerek allmtr. Deneylerde elde edilen numunelerin ara yzeyleri, mikrosertlik deerleri, yzey przllkleri ve balanma
mukavemetleri incelenerek deiken parametrelerin bunlara olan etkileri tespit edilmitir.
Anahtar kelimeler: Toz metal, Bronz, Alev pskrtme, Dikisiz boru
INVESTIGATION AND CHARACTERIZATION OF INNER SURFACES OF

PIPES COATED BY POWDER SPRAY PROCESS
ABSTRACT
In this study, 4, 6 and 10 ASTM A106 GRADE A-seamless steel pipes inner surfaces were coated with bronze
metal powders by powder flame spraying method. Spray distance and air pressure were chosen as variable parameters. Spray distances were chosen as 50, 100 and 150 mm and air pressures were chosen as 0, 0,5, 1 and 2
bar. The recommended powder spray distance is 150-250 mm in standards, so the investigation of the coating of
smaller diameter pipe inner surfaces was aimed. Therefore, spray air pressure values were changed variously. The
interval surface images, micro hardness measurements, surface roughness and bonding strengths of specimens
were investigated to see how they were affected by these parameters.
Keywords: Surface Coating, Thermal Spray, Flame Spray, Compressed air pressure, Spray distance
1. GR
Ar evre artlarnda alacak gerekli dayanklla sahip ana metalleri, bu artlarn zararl etkilerinden korumak iin ok daha ucuz bir yntem olan, dayankl ana metalin yzeyini evre artlarndan etkilenmeyen zellie
sahip malzemelerle kaplama teknolojisi gelitirilmi ve yzey kaplama teknolojisi olarak isimlendirilmitir. Burada
kaplanan yzeyler genellikle metal olmakla beraber, nadir durumlarda baz metal olmayan yzeylerin kaplanmas
da olasdr. Nispeten ucuz olan ve asl yk tayan ana malzemeler, uygun kaplama malzemeleri ile kaplanarak
anmaya, korozyona ve sya dayankl hale getirilebilir [1]. letmelerde karlalan en byk sorunlardan biri de
anan veya krlan makine paralardr. Krlan makine paralar eitli kaynak yntemleriyle tamir edilebilir. Anma
nedeniyle isletme toleranslarnn dna km paralar ise eitli kaplama yntemleriyle kaplanarak tekrar orijinal
l deerlerine getirilebilir. alma ortamndaki artlardan dolay ortaya kan bu problemin nne gemek iin
652

anan makine paralarnn yzeylerinin neden andnn doru olarak belirlenmesi ve bu anma faktrne dayankl bir malzeme ile kaplama yaplarak parann alma mrn uzatlmas mmkndr [2].
Metaller zerine uygulanan kaplamalar, iki temel prensibe gre yaplmaktadr:
(i) Kaplama ile metal arasnda bir difzyon ba oluturarak ve (ii) Kaplama ile metal arasnda herhangi bir difzyon
ba olmakszn metal-kaplama arasndaki mekanik yapma ile balanmas. Difzyonlu kaplamalarda, metal ile
kaplama arasndaki ban zellikleri, malzeme bileimleriyle dorudan ilikilidir (rnein; galvaniz kaplama). Toz
pskrtme gibi difzyonsuz kaplamalarda ise, kaplama ve metal arasndaki mekanik yapma tamamen kaplama
prosesi artlarna baldr [3].
Difzyonsuz kaplama yntemlerinden Termal sprey genel bir ifadeyle benzer prosesler vastas ile metalik ve metalik olmayan kaplamalarn uygulanmas iin yaygn olarak kullanlan bir gurup prosesi ifade etmektedir. ok sayda
termal sprey ilemi mevcut olmakla birlikte ticari olarak kullanlan drt temel metot: 1- Alev Pskrme (Toz alev
pskrtme ve tel alev pskrtme), 2- Ark Pskrtme, 3- Detanasyon Alev Pskrtme ve 4- Plazma Pskrtmedir. Bu
teknikler ile yumuak metallerden son derece sert seramiklere kadar ok geni bir aralktaki malzemeler ile hemen
hemen tm altlk malzemelerin kaplanmas mmkn olmaktadr. Ayrca bir malzemenin yzeyine ince bir tabakann
spreylenmesi anmaya, korozyona ve sya kars direnci artrmakta ve ayrca altlk malzemenin zelliklerini etkilememektedir [4].
Bu almada ASTM A106 Karbon elik boru malzemesinin i yzeyine toz alev pskrtme yntemi kullanlarak
bronz kaplama tozu pskrtlm ve malzeme yzeyi souk pskrtme yntemiyle kaplanmtr.
2.1. Materyal ve Yntem
Toz Alev Pskrtme ynteminde toz halindeki ilave metal bir sevk gaz ve sevk dzenei ile iletildii oksi-asetilen
alevi iinde eritilir ve asetilen-oksijen karmnn yanmas ile oluan genleme yardmyla hzlandrlr (kinetik enerji) ve kaplanacak para yzeye pskrtlr. Sekil 1,1de toz alev pskrtme yntemi ematik olarak grlmektedir.
ekil 1. Toz alev pskrtme ynteminin gsterimi [5].

Deneysel almalar iin 4, 6 ve 10 aplarnda izelge 1de kimyasal kompozisyonu verilen ASTM A106 GRADE
A dikisiz karbon elik borularn i yzeyleri toz pskrtme yntemiyle Castolin firmasna ait Xuper Frixtec 19850
Bakr-Alminyum alaml toz ile kaplanmtr. Borularn i aplarndaki farkllk nedeniyle pskrtme mesafesi 4
borularda 50 mm, 6 borularda 100 mm ve 10 borularda 150 mm olarak tasarlanmtr.
izelge 1. Altlk olarak kullanlan elik boru malzemenin kimyasal kompozisyonu.
Element
%
C
0,25
Mn
0,61
Si
0,09
P
0,025
S
0,32
Cu
0,32
Ni
0,31
Cr
0,28
Mo
0,11
V
0,07
2.2. Hazrlk
Drt adet 4, adet 6 ve iki adet 10 boru tornada 100 mm boylarnda kesilerek hazrlanmtr. Daha sonra borularn i yzeylerinden ve d yzeylerinden korozyonlu tabakalar tornada alnmtr. 4 borularn i ap 90mmye,
6 borularn i ap 143 mm.ye, 10 borularn i ap 247 mmye islenmitir. Malzeme ieriindeki nemden
653

arndrlmak iin 60 C ye kadar n tavlamaya tabii tutulmutur. Kaplama ilemi esnasnda malzeme scakl Raytek PM Plus Model RAYPM30L2ISG termal tabanca ile kontrol edilmitir (ekil 2).
ekil 2. Termal tabanca ile scaklk kontrol.
ekil 3. Kaplama ncesi iine di alm boru
n tavlamadan sonra borunun iine tornada 0,75 mm adma sahip di almtr (ekil 3). Ardndan hemen kaplama ilemine balanmtr.
2.3. Toz Metal Pskrtme ile Kaplama lemi
Kaplama ilemi PETKM A.S. Merkez Bakm Atlyesinde yaplmtr. Kaplamalar Castolin firmasna ait ROTOTEC
80 Toz pskrtme tabancas ile yaplmtr. Borunun i yzeyine kaplama yapld iin kaplama uzatma nozulu
kullanlarak yaplmtr. (ekil 4).
ekil 4. Toz pskrtme tabancas i ap kaplama ( uzatma ) nozulu.

Aada ekil 5te gsterildii gibi asetilen ve oksijen deerleri Castolin firmasnn verdii deerlere gre ayarlanm ve ntr alev kullanlmtr. Asetilen basnc 0,7 bar, oksijen basnc 4 bar olarak ayarlanmtr. ROTOTEC 80
cihaznn zelliinden dolay toz besleme debisi sabittir. Tm kaplamalarda ayn toz debisi ile kaplama yaplmtr.
Malzemeye M 0,75 di aldktan sonra balayc toz olarak Xuper Ultrabond 51000 tozu ile 0,1 mm kalnlnda
astar kaplama yaplmtr. Btn kaplamalarda astar kaplama esnasnda 0 bar basncnda hava kullanlmtr. 4
borularda 50 mm uzaklktan pskrtme yaplarak, hava basnlar 0, 0,5, 1 ve 2 bar olacak ekilde 4 adet boru i yzeyine 1,5 mm kalnlnda kaplama ilemi yaplmtr. 6 borularda 100 mm uzaklktan pskrtme yaplarak, hava
basnlar 0, 1 ve 2 bar olacak ekilde 3 adet boru i yzeyine 1,5 mm kaplama ilemi yaplmtr. 10 borularda
150 mm uzaklktan pskrtme yaplarak, hava basnlar 1 ve 2 bar olacak ekilde 2 adet boru i yzeyine 1,5 mm
kaplama ilemi yaplmtr (ekil 6). Kaplamalar esnasnda malzeme scakl termal pirometre ile kontrol edilerek
malzeme scaklnn 260 Cyi gememesi salanmtr. Malzeme bu scakla ulatnda bir mddet soumaya
braklm sonra tekrar devam edilmitir. Kaplama yaplan numuneler ak havada soumaya braklmtr. Souyan
malzemelerin i aplarndan 0,5 mm tala alnarak kaplama kalnlklar 1 mm ye drlmtr.
ekil 5. Toz pskrtme tabancas ve gaz ayarlar.
ekil 6. Alev toz pskrtme yntemiyle kaplama.
654

3. DENEYSEL SONULAR
Yaplan kaplamalarda deiken parametreler olarak hava basnc ve pskrtme mesafesi kullanlmtr. Dier parametreler tm kaplamalarda ayn tutulmutur. Deiken parametrelere gre numunelere verilen kodlar izelge 2de
verilmitir.
izelge 2. Kaplamalar iin pskrtme parametreleri
Numune Kodu
A1
A2
A3
A4
B1
B3
B4
C3
C4
Hava Basnc
(bar)
0
0,5
1
2
0
1
2
1
2
Pskrtme Mesafesi
(mm)
50
50
50
50
100
100
100
150
150
3.1. Mikroyap
Ara Yzey Mikroyaplarnn ncelenmesi optik mikroskopta yaplm, elde edilen mikroyaplar aadaki ekillerde
verilmitir. Btn mikroyap grntleri 50x bytmede ekilmitir.
ekil 7. A1 kaplamas optik mikroskop grnts.
Yukarda ekil7 deki A1 kaplamas incelendiinde kaplama ara yzeyinde astar tabakas ak renkte grnmektedir. Ortalama 0,1 mm kalnlnda ince bir astar tabaka varl sz konusudur. Kaplama tabakasnda ba tabakas
ile st kaplama arasndaki ara yzeydeki siyahlklar boluklar temsil etmektedir. Bu grnt iki tabakann birbirine
iyi tutunmadn gstermektedir. Kaplamann grnts, dalgal klasik termal sprey grntsdr. Fakat homojen
byklkte olmayan porozite varl gze arpmaktadr. Byklkleri ok farkllk gstermektedir. Sekil 8de 50 mm
pskrtme mesafeli 0,5 bar pskrtme basnl A2 numunesinden elde edilen mikroyap fotoraf grlmektedir.
A2 numunesi mikroyap fotoraflar incelendiinde, basncn arttrlmas kaplamada A1 numunesine gre daha
youn bir yap olumasna sebep olmu grlmektedir. Fakat porozite dalm ve bykl hala homojen deildir.
Yapma mukavemetine ynelik, ara yzeyde esas metal-ba tabakas ve st katman balants gayet iyi grnmektedir.
655

Sekil 9da 50 mm pskrtme mesafeli ve 1 bar pskrtme basnl A3 numunesinden elde edilen mikroyap fotoraflar grlmektedir. Basncn 1 bara karlmas porozite dalmnn daha homojen olmasna yol am grnmektedir. Ara ba ile altlk ve st katman aras balanmann iyi olduu grlmektedir. Mikroyapda dikkati eken nokta,
kaplama iinde yuvarlak formda ergimemi partikllerin varldr. Bu durum basncn yksek olmasndan dolay
tozlarn ergimek iin alev ierisinde fazla kalamadn gstermektedir. Sekil 10da 50 mm pskrtme mesafeli ve 2
bar pskrtme basnl A4 numunesinden elde edilen mikroyap fotoraflar grlmektedir. Basncn 2 bara arttrlmas, porozitenin arttn gstermektedir. Ayrca tozlar ergimeden mikro yap bnyesine girmitir. Byk boluklar
sz konusudur ve bu boluklar iin porozite tabiri dahi yetersiz kalmaktadr.
ekil 11. B1 kaplamas optik mikroskop grnts.
ekil 12. B3 kaplamas optik mikroskop grnts.
Yukarda Sekil 11de 100 mm pskrtme mesafeli ve 0 bar pskrtme basnl B1 numunesinden elde edilen mikroyap fotoraflar grlmektedir. B1 numunesi mikroyap fotoraflarnda
porozite miktar daha az ve genel olarak iyi bir kaplama yaps
grlmektedir. Pskrtme mesafesinin 100 mmye karlmas kaplama yapsna olumlu yansm durumdadr. 50 mmden
pskrtme yaplan A-grubu kaplamalar ile kyaslandnda, pskrtme mesafesinin 100 mmye karlmasnn kaplama yapsna
olumlu yansd grlmektedir. Seki 12de 100 mm pskrtme
mesafeli ve 1 bar pskrtme basnl B3 numunesinden elde edilen mikroyap fotoraflar grlmektedir. B3 numunesi mikroyap
fotoraflarnda baz ergimemi partikllerin varl gze arpmaktadr. Yapsal olarak normale yakn bir kaplama
yaps gze arpmaktadr. Ba tabakas burada daha ince grnmektedir. Sekil 13de 100 mm pskrtme mesafeli
ve 2 bar pskrtme basnl B4 numunesinden elde edilen mikroyap fotoraflar grlmektedir. B4 numunesi mikroyap fotoraflarnda, dier B-grubu kaplamalarna gre daha poroziteli bir kaplama yaps grnmektedir. Hava
basncnn artrlmasnn poroziteye sebep olduu gzlemlenmektedir. Dier B-grubu kaplamalarna nazaran daha
az erimemi partikl olduu gze arpmaktadr.
ekil 14. C3 kaplamas optik mikroskop grnts.
ekil 15. C4 kaplamas optik mikroskop grnts.
Yukarda ekil 14te 150 mm pskrtme mesafeli ve 1 bar pskrtme basnl C3 numunesinden elde edilen mikroyap fotoraflar grlmektedir. C3 numunesi mikroyap fotoraflarndaki kaplama grntleri incelendiinde, klasik
alev pskrtmenin mikroyap grnts ( baloncuksu yap ) elde edilmitir. Ba tabakasnn altlk malzemeye ve
kaplamaya nfuziyeti gayet iyi grnmektedir. Porozite homojen olarak dalm grnmektedir. Baz ergimemi
partikller sz konusudur. Pskrtme mesafesinin 150 mm ye karlmasnn kaplama yapsna olumlu etkileri ak
bir ekilde grlmektedir. Sekil 15te 150 mm pskrtme mesafeli ve 2 bar pskrtme basnl C4 numunesinden
elde edilen mikroyap fotoraflar grlmektedir. C4 numunesinde pskrtme mesafesinin 150 mmye karlmasnn kaplama yapsna olumlu etkileri grlmektedir. Homojen dalm bir porozite sz konusudur. C3 numunesinden farkl olarak bir miktar erimemi partikl gze arpmaktadr.
656

3.2. Mikrosertlik
Btn numunelerin mikrosertlik deerleri, arayzeyden itibaren 0,15 mm aralklarla llm, sonra her bir numune
iin ortalama deer alnarak aadaki ekil 16daki grafik oluturulmutur.
ekil 16. Numunelerin ortalama sertlikleri.
ekil 17. Hava basncna bal sertlik deiimi (50 mm)
ekil 18. Hava basncna bal sertlik deiimi (100 mm)

Yukardaki ekil 17 ve ekil 18de ise mikrosertlik deerinin 50 mm ve 100 mm toz metal pskrtme mesafelerinde
hava basncna gre deiimi grafikleri verilmitir. Elde edilen deney sonular incelendiinde genelde hava basnc
artrldnda sertliin de artt grnmektedir. Dk pskrtme mesafelerinde hava basnc ok artrldnda
bu kural tersine dnebilmektedir. Burada dk pskrtme mesafelerinde hava basnc artnca kaplamada oluan
yksek poroziteden dolay mikro sertlik lmlerinde salkl deerler elde edememi olmamz olasdr. Pskrtme
mesafesi olarak optimum deerler ierisinde kabul edilen 150 mm deeriyle kaplanm C numunelerinde, kullanlan
tozun literatrdeki sertlik deerine yakn deerler elde edilmitir. Burada da hava basnc artrldnda sertlikte
artma tespit edilmitir.
3.3. Yzey Przll Deerleri
ekil 19. Yzey przll sonular.
ekil 20. Hava basnc- yzey przll ilikisi(50mm)
ekil 21. Hava basnc- yzey przll ilikisi(100mm).
657

Yzey przll lmlerinde optik mikroskop grntlerinde elde edilen grntlerle paralellik gsteren deerler elde edilmitir. Syle ki; yakn mesafeden pskrtme yaplan A1 ve A2 numunelerinde optik mikroskopta grlen
heterojen porozite bykl yzey przllne de yansm ve daha homojen byklkte poroziteye sahip
A3 numunesinden daha przl bir yzey elde edilmitir. Basncn artrlmasyla oluan A4 numunesindeki byk
boluklar ok daha yksek bir yzey przll oluturmutur. B1 numunesinde kullanlan sfr hava basnc tozun
hzn ok drdnden yzeye ge gelen toz bu sre zarfnda souyarak yzeyde erimemi partikllere sebep
olmu ve B3 ve B4 numunelerine nazaran daha przl bir yzey olumasna sebep vermitir. C numunelerinde
ise yksek hava basnc kullanlan C4 numunesinde C3 numunesine nazaran ok daha fazla przl bir yzey elde
edilmitir. Buradan su sonucu karmak mmkndr ki; hava basncnn ok dk olmas da ok yksek olmas
da yzey przlln artrmaktadr. Her pskrtme mesafesinde de 1 barlk hava basnc en dzgn yzey
przlln vermektedir. Bu deerin altndaki basnlar tozun yzeye yava gelmesine ve bu sre zarfnda souyarak yzeyde erimemi partikller olumasna sebep olmaktadr. Bu deerin stndeki basnlar da tozun yzeye
ok hzl arpmasna ve yzeyde dalgal bir grnt oluturmasna sebep olmaktadr.
3.4. Kaplama Ba Mukavemeti
Kaplamalarda ba mukavemeti ASTM C633 Isl Pskrtme Kaplamalar Yapma Mukavemeti lm Standardna
gre llr [13]. 25 mm apndaki test ubuunun u yzeyine kaplama yaplr. Ayn aptaki dier bir test ubuuna epoksi srlerek kaplama yaplm ubua yaptrlr. Kullanlan epoksinin sertleme sresi dolunca bu
ubuklar ekme deney cihazna balanarak ekme kuvveti uygulanr. ekme sonucu kaplamann koptuu gerilme
deeri kaydedilir ve bu deer yaplan kaplamann ba mukavemeti olarak nitelendirilir. Bu almadaki kaplama
numuneleri boru malzemesinden yapldndan dolay, yapm olduumuz ekme deneyi ASTM C633 standardna
bire bir uygun yaplamamtr. Kaplama yaplm halkalardan kesilen 10 mm x 10 mm kare kesitli test paralarnn
kaplama yaplm yzeyleri, yine 10 mm x 10 mm kare kesitli ekme deney ubuklarnn ucuna yaptrlm ve
kaplamalara ekme deney cihazyla ekme kuvveti uygulanmtr. Kaplamalarn esas metalden ayrld gerilme
deerleri kaydedilmi ve bu deerler kaplamalarn birbirleriyle mukayese edilmesi iin kullanlacak ba mukavemeti
olarak deerlendirilmitir. Bu deerler yaplan kaplamann gerek ba mukavemeti olarak deerlendirilmemelidir.
Bu deneyde btn numunelere ayn artlar altnda (fakat ASTM C633 standardna tam uygun deil) ekme deneyi
uygulanm ve bulduumuz kopma deerleri birbirleri arasnda mukayese amacyla kullanlmtr.
Kaplama prosesi sonras malzemede iki tr ba kuvveti olumaktadr. Esas metal ile kaplama malzemesi arasnda
oluan Adhezyon Balar ve kaplama malzemesinin kendi moleklleri arasnda oluan Kohezyon Balardr. ekil
22de numunelere uygulanm ekme deneyleri sonucu elde edilen ba mukavemetleri verilmitir.
ekil 22. Numunelerin ba mukavemetleri.
ekil 23. Hava basnc-ba mukavemeti ilikisi (50 mm).
ekil 24. Hava basnc-ba mukavemeti ilikisi (100 mm).

Ba mukavemetleri deerlendirildiinde yakn mesafeden yaplan pskrtmenin ba mukavemetine olumsuz etkisi
grlmektedir. Yakn mesafeden pskrtme esnasnda hava basncnn sfra indirilmesi adhezyon ba kuvvetini
olumsuz etkilemekte ve kaplama esas metale yapmamaktadr. 0,5 bar hava basncnn kullanld A2 numunesinde ise adhezyon ve kohezyon ba kuvvetlerinin optimum pskrtme mesafesi olan 150 mm den yaplan pskrtme sonucu elde edilen ba kuvvetleri kadar iyi olduu grlmektedir. Basn 1 bar ve 2 bar seklinde artrldnda
658

daha dk kohezyon ba deerleri elde edilmektedir. 100 mm ve 150 mm pskrtme mesafeli B ve C numunelerinde de hava basncnn 2 bara karlmas ba mukavemetinde zayflamaya sebep olmaktadr.
4. TARTIMA
Toz alev pskrtme yntemi ile ASTM A106 karbon elik boru i yzeylerinin Xuper FrixTec 19850 tozu ile kaplanmas deneylerinden elde edilen sonulara gre;
1- Kaplamada kullanlan farkl pskrtme mesafeleri ierisinden en optimum deer 150 mm bulunmutur.
2- Optimum pskrtme mesafesinde yaplacak kaplamlarn sertlii artrlmak istendiinde hava basnc biraz artrlabilir.
3- 4 ve 6 borularn i aplarnn bu deerden daha kk olmas gibi yakndan pskrtme yapmak zorunda kalnd durumlarda, kaplamada oluacak poroziteyi azaltmak iin dk deerlerde hava basnc seilmelidir.
4- Yzeyde erimemi partikllerin grnmesi halinde, hava basnc artrlarak tozun ivmesinin artrlmas ve tabancadan ktnda erimi halde olan tozun daha ksa srede yzeye ulamas salanmaldr. Aksi takdirde
alev pskrtme ynteminin dk pskrtme hzndan dolay kaplama tozunun yzeye ulasana kadar ergimi
formdan bir miktar kat forma dnt grlmektedir.
5- Pskrtme mesafesi ile hava basnc arasnda ba mukavemeti asndan dorusal bir iliki bulunmamakta,
basn ok drldnde de, ok ykseltildiinde de ba mukavemeti zayflamaktadr. 50 mm pskrtme
mesafesi iin 0,5 bar, 100 ve 150 mm pskrtme mesafesi iin 1 bar hava basnc ba mukavemeti asndan
optimum deer olarak grlmektedir. Dolaysyla ksa mesafeden pskrtme yapma zorunluluunun olduu
durumlarda hava basncnn optimum basn deeri olan 2 barn daha altlarnda bir deer seilmelidir.
KAYNAKLAR
[1] TRKES, ., Metal Makine Paralarnda Yzey Kaplama Teknolojisi, Petkim Petrokimya Holding A.S., Yayn
No: 93-MB-002.
[2] NURSOY, M., NER, C., CAN, ., Wear behavior of a crankshaft journal bearing manufactured by powder
spraying, Materials and Design 29 (2008), 20472051.
[3] STEL, F., Plazma Sprey Kaplama Teknolojisi, Yksek Lisans Tezi, T Fen Bilimleri Enstits, stanbul,
1995.
[4] PAMUK, U., Plazma Spreylenmi Cr3C2-NiCr ve Al2O3-TiO2 Kaplamalarn Abraziv Anma Davranlarnn
ncelenmesi, Yksek Lisans Tezi, T Fen Bilimleri Enstits, stanbul, 1996.
[5] http://www.twi.co.uk/j32k/protected/band_3/ksrdh001.html.
659

TME ZAMANININ PERLT TOZ TANE BOYUTUNA ETKS

Yusuf KILIN*
*Seluk niversitesi Ereli Kemal Akman Meslek Yksek Okulu, 42320, Konya,
ykilinc@selcuk.edu.tr
ZET
Bu almada 500, 700 ve 900 dev/dak dnme hzlarnda olmak zere farkl hzda alabilen; 3/2, 2 ve 3 litre
deiebilir tme tank kapasiteli, titreimli yatay bir atritr tasarlanm ve imal edilmitir. Bu atritrle mikronize
perlit malzeme 9.52 mm apl elik bilyelerle 1:5 ,1:10,1:20 toz/bilye arlk oranlarnda 6,9 ve 12 saat srelerle
tlmlerdir. tme zaman arttka toz tane boyutunun azald grlmtr.
Anahtar Kelimeler: Atritr, Perlit, Deirmen, tme, Toz Boyutu.
THE EFFECT OF MILLING TIME ON THE GRAIN SIZE OF

PERLIT POWDERS
ABSTRACT
.
In this study, 500, 700 and 900 rpm rotational speeds to operate the mill was designed and manufactured. With
this mill 500,700 and 900 rpm rotational speeds to operate in three different speed. In this grinding mill the micronized perlite material grinded by 9 mm diameter steel ball used at 1:5,1:10,1:20 powder/ball weight ratio. Three
different grinding time was used which6,9 and 12 hours. Powder particle size decreased with increasing grinding
time
Keywords: Attritor, perlit, grinding, milling, particle size
1.GR
Toz metalrjisi teknolojileri paracklarn bir araya gelmesiyle oluan tozlarla balar. Younlatrma ileminde
nemli bir girdi olmas nedeniyle tozun iyi anlalmas gerekir. Parack, tozun blnemeyen en kk birimi olarak
tanmlanr. Toz ileme teknikleri genellikle dumandan daha byk (0,01-1m), fakat kumdan daha kk (0,1-3mm)
paracklarla ilgilenir. Kullanlan tozlarn ou insan sa lsndedir(25-200m).
Toz metalrjisi ve parack malzemelerde en yksek retim hacimleri elektronik, mikro elektronik ve elektrik alanlarndadr. Elektrik temas elemanlar byk lde preslenmi ve sinterlenmi W-Cu veya W-Ag tozlar kullanlarak
retilmektedir. Ylda 150-200 milyon kiisel bilgisayar retilmekte ve bunlarn her biri sinterleme ile retilmi eitli
kilitler, disk src balanslar, balantlar ve yataklar ierirler.
Uzay mekii zerindeki sl koruma sistemi silikadan (SiO2) sulu amur dkm ve sinterleme teknikleri ile retilir.[1]
Bir metal tozu retim teknii olmakla birlikte, dier tekniklerle retilmi ancak kmelemi tozlarn krlmas iinde
kullanlan tme, en ok bilyal deirmenlerde yaplmaktadr[2].
Perlit malzemesi tarm. naat, sanayi, gda, filtre retimi, tekstil ve kriyojenik perlit olarak hemen hemen btn
sektrlerde farkl boyutlarda kullanlmaktadr. Tarmda perlit, %92nin zerindeki toplam gzeneklilii ve %68 do-
660

layndaki havalandrma gzeneklilii ile topran havalanmasn salar, drenajn ykseltir. naat uygulamalarnda
perlit, izolasyon malzemesi olarak kullanlr. Sanayi sektrnde, gda, ila ve kimya sanayi katk maddesi olarak, s
yaltmnda, metalurji, cam ve seramik retiminde youn olarak kullanlmaktadr. Tekstik sektrnde kuma retiminde perlit ieren polyester iplik retimi ve perlikt kullanmnn kuma performans zelliklerine etkisi zerine bilimsel
almalar yaplmaktadr [3].
Bu almada 500, 700 ve 900 dev/dak dnme hzlarnda olmak zere farkl hzda alabilen; 3/2, 2 ve 3 litre
deiebilir tme tank kapasiteli, titreimli yatay bir Atritr tasarlanm ve imal edilmitir. Bu atritrle, Uluda niversitesi Tekstil Blmnden temin edilen mikronize edilmi perlit malzeme 9.52 mm apl elik bilyelerle 1:5,1:10
ve 1:20 toz/bilye arlk oranlarnda 6,9 ve 12 saat srelerle tlmtr. Atritrn perlit tme davran, farkl
tme sreleri ve toz/bilye oranlar iin aratrlmtr.
Bu deirmenle Perlit tozlar farkl deneylerle farkl toz/bilye oranlarnda ve zaman aralklarnda tlmlerdir. Tozlarn orijinal boyutlarnn tme sreleriyle deime sreci takip edilmitir. Optimum tme artlarnda elde edilen
toz boyutlarnn lm yaplarak minimum toz boyutu elde edilmeye allmtr. Atritr altrldnda yksek
enerji ile bilyeler birbirine arpar ve arpmann etkisi ile arada kalan tozlar ezilir. Bu ilem devam ettike tozlarda
pekleme, krlma ve kaynama devam eder. ok ksa srede dahi karm elde edilir, ancak ok homojen deildir.
Saf tozlarn tlmesinde ise tme devam ettike toz boyutlar klmeye devam eder.
2.TOZ TME TEKNKLER
2.1 Toz tme mekanizmas
Bir metal tozu retim teknii olmakla birlikte, dier tekniklerle retilmi ancak kmelemi tozlarn krlmas iin de
kullanlan tme, en ok bilyeli deirmenlerde yaplmaktadr. tlecek metal, iinde byk apl, sert ve anmaya kar dayankl bilyelerin bulunduu kaba yerletirilir. Kap dndrlerek veya titretirilerek bilyeler harekete
geirilir (ekil. 2.1). Eer tlen paracklar gevrek ise, bilyelerle arpma neticesinde ok kk tozlara blnr.
Snek paracklar ise, arpma sonucunda ekil deitirerek yasslarlar (ekil 2.3) ve ancak ar i sertlemesi
neticesinde gevrekleerek kk tozlara blnebilirler [4].

ekil 2.1 Toz tme Mekanizmas
ekil 2.2 Bilyeli Atritr
ekil 2.3 tmede arpmann Etkisi [3]
661

tmenin su, alkol ve heptan gibi bir hidrokarbon sv iinde yaplmas hem tme sresini ksaltr, hem de ince
tozlar retilmesini salar. Bir tcnn verimliliini tme ortamnn arpma hz ve tc iindeki malzemenin hareketlilii belirler. tmenin ok yava bir dn hz ile yaplmas, bilyelerin kabn zerinde yuvarlanmasna;
ok yksek bir dn hz ise merkezka kuvvetinin etkisiyle bilyelerin kap yzeyinde dmeden durmalarna sebep
olur. Ayrca bilyelerin hacmi kap hacminin yaklak yars ve tlecek metal miktar kap hacminin yaklak %25i
olmaldr. Silindirik deirmenler metal tozlarnn tlmesinde yaygn olarak kullanlmakla birlikte, dk hzlarda
altklarndan tme sresi uzundur. Bu sreyi ksaltmak iin titreimli deirmenler ve atritrler (ekil 2.2) gelitirilmitir. Atritrler dier tclere gre daha ksa zamanda kartrma-tme zelliine sahip, yksek enerjili
ve en verimli tclerdir. Silindirik deirmenlerde optimum bir dnme hz sz konusu iken, atritrlerde kartrc
kollarn hz ne kadar yksek ise tme verimlilii de o kadar yksek olmaktadr. Bu almada, titreimli yatay tip
bir atritrn tasarm ve imalat yaplarak almina ve perlit tozlarn tme davran incelenmitir.
Toz tme deirmenleri ok eitli modellerde ve serilerde retilmektedir. Union Process Firmas tarafndan retilen tipik aratrma ve laboratuar almalarnda kullanlan tipik atritr ekil 2,4.de verilmitir. Szeguari marka
krc tc deirmenleri yksek enerji ile alan bilyeli deirmenlerdir. Bunlarda bilyelerin ve tozun yklenmesi
sabit, dik konumda, su soutmaldr. Dnen bir merkez aft ile malzemeler kartrlr. Spex shaker deirmenleri az
miktardaki tozu (10 gdan az) toz tmek iin kullanlan titreimli deirmenlerdir. Aslnda spektrografik rnekleri
arptrarak toz retme amacyla gelitirilen Spex deirmeni (55.10-3 m3 ) lk kk bir tme kabn dik yne
yaklak 20 Hz (1190 dev/dak) ile sallayarak alr. Merkez yatay bir aksn yrngesinde dnen geleneksel top
deirmenleri, 1mden byk apl ve yksek enerjilidirler. Bu deirmenler toplar i duvarlara yaptracak ve toz ykne bal top yknn arln drecek olan kritik hzn altnda altrmay gerektirir. Toz tmede genellikle
5000 den fazla AISI E 52100 standart tc bilyeler kullanlr.
ekil 2.4 Ticari Olarak retilen Toz tme Deirmeni (Atritr)

ekil. 2.5 ve ekil 2.6da grlen Titreimli Yatay Atritr tasarmlanm ve imalat yaplmtr[5]. Sistem 0.75 kw
gcnde 1800 d/d motor mili dnme hznda bir elektrik motoru ile tahrik edilen 700, 900, 1400 d/d dnme hzlarna
ayarlanabilen kademeli V kay kasnakl olarak almaktadr. Atritrn iskeletini muhtelif kebent, kare profil sa
malzemeler oluturmaktadr. Deneyler iin 3/2 , 2 ve 3 litrelik paslanmaz elik tanklar ile tankn evresinde soutma
suyunun dolamas iin elik borudan imal kazan kullanlmtr. Kartrc kollar ve merkez aft paslanmaz elik
malzemeden yaplm ve kollar gvdeye TIG kayna ile kaynatlmtr. Kollar motor supaplarndan imal edilmitir.
Bilyelerin ve tozlarn kartrc kol yzeylerinde anma ve oyuk oluturmalar sert dolgu kayna ile giderilmitir.
malat yaplan titreimli yatay atritr ekil.2.5te gsterilmitir. Atritr, bir elektrik motorundan kay-kasnak sistemi
ile tahrik edilmektedir. Motor mili 1800 dev/dak hza sahiptir. Bu hz, kademeli kasnaklar ile 700,900 ve1400 dev/
dak hzlara ayarlanabilmektedir. tmenin yapld tank, drt adet bask yay zerine oturtulmutur. Yay sabitleri
Probat-Werke marka cihazda llmtr. Serbest boy Lo = 61,5 mm, L = 51 mm (4,95 kg ykleme), L2=41 mm
(9,75 kg ykleme) ve Lmin = 25 mm (16 kg ykleme) lm deerleridir. Elektrik motoru mili, atritr miline ift akuple
bir kardan kavramas ile irtibatlandrlmtr. Motor alt anda serbest dnen mil esnek hareketle atritr yaylar
zerinde titretirmektedir. Bylece tc tank, elik bilyeler ve toz malzeme ok eksenli olarak titremektedir.
Atritrde tme, 3/2, 2 ve 3 litre hacimli Cr-Ni paslanmaz i elik tanklarda yaplmaktadr. ekme dikisiz borudan
d tank yaplmtr. tanklar deitirilebilmektedir. Her iki tank arasnda soutma suyu dolaabilmektedir. Kartrc kollar Cr-Ni paslanmaz elikten yaplmtr. Atritrn almas srasnda meydana gelebilecek snmadan
kaynaklanabilecek reaksiyonlarn nlenmesi iin,tme tank ile d tank arasnda soutma sistemi mevcuttur.
Sistemin montaj ve demontaj kolaylkla yaplabilmektedir.
662

ekil 2.5 Yatay Titreimli Artritr ematik Resmi
ekil 2.6 Tasarm Yaplan ve mal Edilen Yatay ve Titreimli Toz tme Deirmeni
3.DENEYLER
3.1 almann amac
Bu almada ama, mikronize Perlitin atritrde tlerek tane boyutunun kltlmesi ve tme parametrelerinin toz boyutlarnn kltlmesinde etkilerinin incelenmesidir. Boyutlar 14 mikron civarnda olan mikronize toz
perlit,1 mikron seviyesine indirilmesi amacyla muhtelif deneyler yaplmtr. Minimum toz boyutunun elde edilebilecei alma parametrelerinin belirlenmesi ve atritrn verimlilii zerinde yaklamlar sergilenmitir.
3.2 almann nemi
Mikronize edilmi tozlarn ticari kullanmlar ok nemlidir. Mikronize perlit ham perlitin tlerek ticari kullanmlar iin en kk boyuta getirilmi eklidir. Perlitin mevcut uygulamalar iin 10 mikron civarnda boyutlar yeterli
olmaktadr.Ancak bu almadan elde edilecek daha kk boyutlu perlit tozlarna da ihtiya duyulmaktadr.Yatay
663

Titreimli olarak tasarlanan Atritrn perlit tme performans bir dizi deneyle llecek ve sonu olarak tasarm
asndan makine deerlendirilecektir.
3.3 Deney Malzemeleri
Deneylerde Uluda niversitesinden elde edilen mikronize Perlit farkl parametrelerde tlmlerdir. Perlit tozlar
ortalama toz boyutu: 14.04 mdur.
3.4 Perlit tme deneyleri
Deneyde Uluda niversitesi Tekstil Blmnden temin edilen ve ortalama toz boyutu d(0.5) 14.04 d(0.1)3.44
d(0,9) 44.09 mikron olan mikronize perlit kullanlmtr. elik bilyeler 9.52 mm apndadr ve ORS (Ortadou Rulman Sanayi)den temin edilmitir. alma devri 900 d/d olarak ayarlanmtr. Deneyler 6, 9 ve12 saat srelerle
1:5,1:10,1:20 toz/bilye oranlarnda ayr ayr yaplmtr.Deneyler kuru tme ortam ve sulu ortamda yaplmtr.
tme tank kapasitesi 2 litre hacimli seilmitir. tlen perlit tozlarnn boyut analizleri Gazi niversitesi Mhendislik Mimarlk Fakltesi Makine Mhendislii Blm Toz Metalrjisi Laboratuarnda bulunan Malvern Mastersizer E lazerli toz boyutu lme cihaznda yaplmtr. Yaplan tme ilemlerine ait deney artlar ve tme
neticesinde elde edilen tozlarn boyut analizlerine ait d(0,5), d(0,1) ve d(0,9) deerleri izelge 3.1de gsterilmitir.
3.5 Perlit Boyut lm
izelge 3.1. Farkl tme artlarnda Elde Edilen Perlit Tozu Boyutlar
Deney
no
Toz/Bilye
Oran
tme
sresi(saat)
tme
Ortam
d(0,5)m
d(0,1)m
d(0,9)m
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
1:5
1:5
1:5
1:10
1:10
1:10
1:20
1:20
1:20
1:5
1:5
1:5
1:10
1:10
1:10
1:20
1:20
1:20
6
9
12
6
9
12
6
9
12
6
9
12
6
9
12
6
9
12
Kuru
Kuru
Kuru
Kuru
Kuru
Kuru
Kuru
Kuru
Kuru
Sulu
Sulu
Sulu
Sulu
Sulu
Sulu
Sulu
Sulu
Sulu
4.66
5.62
7.52
8.02
9.72
14.72
8.89
11.10
7.63
3.60
3.28
3.14
3.51
3.52
3.39
4.78
4.99
5.20
0.75
0.88
1.09
1.10
1.02
1.37
1.09
1.19
0.99
1.07
1.04
0.94
1.00
0.90
0.84
1.00
0.95
0.97
43.73
33.39
39.42
37.38
95.84
166.41
36.18
70.43
39.79
11.38
9.72
18.72
10.85
19.58
17.48
17.00
23.75
27.26
Orijinal veriler verilmeli

3.6 Perlit tme Sonular
Mikronize perlit tme ncesi ortalama boyutu (14,04 ) dr Ancak ayn perlitlerin boyutlar arasndaki azda olsa
fark olabilmektedir. Ham perlitten mikronize perlit elde edilirken homojen boyutlar elde edilemedii biliniyor. Deneylerde kullanlan mikronize perlitin iinde deien boyutlarda perlit tanecikleri var. Gazi niversitesinde yaplan boyut
lm sonularndan da bu grlebiliyor. Farkl zamanlarda yaplan ortalama lm sonular arasndaki fark perlit
retimi srasnda olumaktadr.
Sonulardan izelge 3.1de kuru ortamda 1:5 ve 1:10 ve su ortamnda 1:20 ile yaplan tmelerde ilgin bir ekilde tme sresi artka ortalama perlit boyutunun artt grlyor. Beklenen sonu tme sresi arttka toz
664

boyutunun dmesidir. Toz boyutunun, su ortamnda 1:5 ve 1:10 ile yaplan tmelerde dt grlyor. O da
kk deiimlerle. Kuru ortamda 1:20 ile yaplan almada ise baka ilgin bir durum sz konusu: 6 saatten 9
saate knca boyut artarken 12 saatte boyut byk oranda klm. Bu farkn sebebi zerinde dnmek gerekecektir. Perlitin ilk tme sresince topaklanarak katmerlemesi beklenilmelidir. Daha sonraki tme srecinde
yeniden krlmalar ve ufalanmalar toz boyutunu kltecektir.12 saatlik srede beklenen olmutur. Kuru ortamlarda
yaplan tmeler iin tozlarn kaynaklamas ve zamanla tekrar ufalanmas daha da olas bir durum olarak gzlemlenmitir.
izelge 3.1de deney 9 daki durumu hari tutarak ayn alma srelerinde toz/bilye orannn boyut zerine etkisi
dikkate alndnda; en kk orandan (1:5) en yksek orana (1:20) kldka ortalama perlit boyutunun artt
grlyor.Tm toz/bilye oranlar ve alma sreleri dikkate alndnda; su ortamnda almann kuru ortama gre
ok daha kk boyutlarda tme salad grlyor. Tm tme oranlar iin 12 saat su ya da alkol benzeri sv
ortamlarda tme yapmak daha kk boyutlara ulamak asndan faydal olacaktr.
4. SONULAR
Tasarm ve imalat yaplan Yatay Titreimli ATRTR yukarda belirtilen toz tme mekanizmasna uygun tasarmlanmtr. Atritrden beklenen, tme ortamnda herhangi bir kimyasal reaksiyona meydan vermeden tozlar istenen boyutlara kadar tmesidir. Bu nedenle atritr laboratuar iin tasarmlanm ve kk kapasiteli tutulmutur.
Elektrik motoru yeterli gte seilmitir. Titreim iin Atritr drt adet yay zerine oturtulmu. tme tank ayrca
mafsall bir mil ile de salnmakta ok ynl hareket edebilmektedir.
4.1 tme Zaman - Toz tme sresi Toz Boyutu likisi
Perlit tme ilemlerinde tme ortam olarak kuru ve sulu ortam tercih edilmitir. Perlit yumuak bir malzeme
olup tme mekanizmasna anma bakmndan herhangi bir zarar vermemektedir. Kuru ortamlarda perlit toz
boyutu tme sresinin artmas ile bymektedir. Bu durum istenmeyen bir sonutur. Kanaatimize gre kuru ortamlarda tozlar ezilerek katmerlemekteler. izelge 3.1 de 1:20 tme orannda bu durum farkl kmtr. Deneyin
tekrar ve ya toz boyutunun yeniden llmesi gerekebilir. Perlit tozunun sulu ortamda 1:5 toz/bilye orannda 12
saatlik sre sonunda 3.14 mikron deerine ulat grlmektedir. Bu durum beklenen bir sonutur.
4.2 neriler
Tm deneylerde sabit tutulacak olan alma devri yeniden seilebilir. tme tank kapasitesini deitirmek mmkndr. Perlit iin 9,52 mm bilye ap seildi. Kk apl bilye kullanmann tme zerine daha olumlu etkisi
olaca dnlebilir ve bilye ap olarak 6,35 mm perlit iin yeniden denenebilir.
Yaptmz almalar gsteriyor ki; Perlit iin almay tamamen alkol ortamnda yapmak deney saysn 27ye
karacaktr. Byle bir almann daha doyurucu olmas mmkndr. Perlit iin su ortam yerine alkol ortam da
seilebilir. Kuru ortamda tmenin zellikle kalmasn tercih edilmelidir. nk alkoll tme sonrasnda alkoln
perlitten uzaklatrlmas iin ek ilem gerekmektedir. Bu nedenle perlit iinde yukarda belirtilen farkl seviye
1:5,1:10 ve 1:20 (toz/bilye oran) yeterli olacaktr. alma sresi olarak 6,9 ve 12 saatler allmtr. 12 saatten
sonra yaplacak bir dizi almada toz boyutlarnn kltme salanaca dnlmektedir.
5. KAYNAKLAR
1. German, R.M., Powder Metallurgy Science, MPIF, Princeton, NJ, USA, 1994
2. Sarta, S., Toz Metalrjisi, Makine Mhendislii El Kitab, MMO, 1994
3.Karaca, E., Perlit eren Poliester plik retimi ve Kullanmnn Kuma Performans zelliklerine Etkilerinin
Aratrlmas TBTAK aratrma projesi, 109M269, 2009
4. Da Silva, A.G.P., Da Silva, N.F. and Gomes, U.U., Efects of Milling Technique on the Dispersion, Sintering and
Hardness of WC-Co Hard Metals Int. J. Powder Metallurgy, Vol.37, no.6, pp57-66,2001
5.Kln, Y.,Speralam retimi in Yatay ve Titreimli Mekanik Alamlama Deirmeni (Atritr) Tarsarm, malat
ve Denenmesi, S. Bilimsel Aratrma Projeleri, 2009
665

2014 ALMNYUM ALAIM TOZU LE %2 GRAFT TOZUNUN HIZLI

DERMENDE LENMES VE PRESLEME SONRASI UZUN TAVLAMA
SRECNDE MKRO-YAPISAL GELMELER
Sinan AKSZ, A. Tamer ZDEMR, B. BOSTAN
Gazi niversitesi Teknik Eitim Fakltesi, Metal Eitimi Blm, Beevler, 06500, Ankara,
sinanaksoz@hotmail.com, tozdemir@gazi.edu.tr , bostan@gazi.edu.tr
ZET
2014 alminyum alam tozu ve %2 grafit, koruyucu argon atmosferi altnda 7 s sre ile mekanik alamlama (MA)
ilemine tbi tutulmutur. Elde edilen harmanlanm karm 600 MPa basn altnda souk preslenmitir. Numuneler, Ar gaz altnda srasyla 5500C ve 6000C de uzun sre tavlanmlardr. Elde edilen malzemeler incelendiinde;
tavlama srasnda taneler irileirken, gzenekliliin nce artt, daha sonra ise azald tespit edilmitir. Gzeneklilikteki bu deikenliin sebebinin, yapdaki atomik magnezyumun scakln etkisiyle hzla tane snrlarnda kmeleirken, ardnda boluklar brakmas olduu dnlmektedir. Bakr ise daha sonra bu boluklar kapatmaktadr.
6000Cde, 196 s tavlanan numunelerde ise ksmi yeniden kristalleme tespit edilmitir. Bu bulgu, yapda youn
olarak ince dalml Al4C3 paracklarnn olduunu ve yeniden kristallemeyi bastrdn iaret etmektedir.
Anahtar Szckler: 2014 Al alam, MA, uzun sreli tavlama, gzeneklilik, yeniden kristalleme.
HIGH SPEED MILLING OF 2014 ALUMINUM POWDERS TOGETHER WITH

2% GRAPHITE AND PROGRESS IN MICRO-STRUCTURE DURING LONG
TERM ANNEALING AFTER COLD COMPACTION
ABSTRACT
2014 Al alloy powders and 2% graphite by weight were mechanically alloyed (MA) about 7 h under gas tight conditions of argon athmosphere. Blended powders were later cold pressed at 600 MPa and then long term annealed at
5500C and 6000C, respectively under the same controlled atmosphere. It was deduced that, during annealing, while
grains were slowly coarsening, porosity of the samples first decreased but later increased progressively. For this,
Mg atoms primarily diffuse towards grain boundaries and then evaporate, leaving pores behind. Atomic copper later
occupies these openings. Particularly, at about 196 h of annealing at 6000C, an evidence of the onset of recrystallization was observed at several areas within the microstructure. This result in fact confirms a dense formation of fine
Al4C3 precipitates, which are very effective depressing the recrystalization of the micro-structure.
Key words: 2014 Al alloy, MA, long term annealing, porosity, Recrystallization.
1. GR
Yap malzemelerini srekli gelitirebilmek iin mhendislik alannda almalar duraksamadan devam etmektedir.
Kimyasal, mekanik ve fiziksel zelliklerin geliiminde, kimyasal yap ve termo-mekanik ilem metotlar srekli olarak
gzden geirilip, yenilenmektedir. Bu yeni ilemlerle, yap malzemelerinin tasarm ve geliiminde eitli zelliklerle
beraber, dayanma karn hafiflik artmakta ve geleneksel metotlarla retilen malzemelerden daha stn nitelikte
yeni malzemeler gelitirilmektedir [1]. Toz Metalurjisi (TM) de, yaygn olarak ileri malzeme ve teknolojileri gelitirmede en fazla rabet gren sahalardan biridir [2].
TM ile retilen tozlarn zelliklerini artrmak iin eitli mekanik yntemler de uygulanmaktadr. Bunlardan en nemlisi ve etkin olan, MA tekniidir. MA ilemi birbirinden ok farkl tozlarn birlikte tlmesi ilemidir. MA ilemi
666

nce tozlarn doru oranlarda kartrlmas ile balar ve sonra toz karmnn tme haznesine elik bilyalarla
birlikte yerletirilmesiyle devam eder. Bu karm daha sonra kararl bir duruma ulaana kadar uygun grlen srede tlr. MA ilemindeki tme sreci bileimdeki toz parack boyutlarnn eitlenmesi ve balangtaki toz
boyutlarna ulalmasna kadar devam edilir [3]. Tozlarn son mikro yaplar atomizasyon yntemi ile elde edilen
tozlardan ve ayn tane boyutuna sahip hzl katlama ilemine tbi tutulmu tanelerden genelde daha iyidir. Ayrca,
toz paracklarnn devaml olarak bilyelerin ve bilye hazne arasnda sktrlp, paralanmas nedeniyle mikro yapsal gerilmeler artmakta, buna bal olarak, sonuta mekanik zellikleri gelimi, adeta birbirlerine yedirilmi, farkl
kombinasyonlu yeni alam tozlarnn olumas gereklemektedir [4].
eitli karbr ve dier kat paracklarn ilavesi ile malzemelerin zellikle mekanik zellikleri ve buna bal performanslarnda ciddi artlar kaydedilmitir. Bilhassa, karbrler alminyumda yaygn olarak kullanlmaktadr. Al
karbr (Al4C3) ierii Al metal teknolojisinde nemli bir bileen ve elmas bal seramiklerin (Al2O3Al4C3AlN) retimi
balangcnda ilk kullanlan malzemelerden olup, bu yap oda scaklnda yksek termal iletkenlikle birlikte yksek
elektrik direncine sahiptir. Ayrca, Al4C3 ilavesi metal kompozit ve alamlarnn mukavemetlemesini arttrmaktadr
(AlAl4C3, AlSiCAl4C3, AlAl3TiAl4C3, v.b.) [5].
2xxx serisi alamlar uzun zamandr havaclk sektrnde rabet gren malzemelerdir ve arlkl olarak uak yzeylerinde, perinlerde ve ekme aralarnda kullanlmaktadrlar. Yeni nesil 2014 Al alam, havaclk sektrnde
geleneksel olarak tercih edilen 2024 alamnn yerini alm bir alamdr. Bu alam zellikle scak ekstrzyon ve
scak haddeleme sonras elde edilmektedir. Genellikle ieriinde bulunan Cu, Mg ve Mn oranlar daha rafine edilmitir. Ayrca, retimden gelen dier kalnt elementlerin azaltlm olmas, sonraki kat hal ilemleri ve buna bal
yapsal tasarm kabiliyetini artrmaktadr [6]. 2014 alminyum alamnn elastikiyet modl ve dayanm 2024 alamnnkine gre daha yksektir. Bu almada gaz atomizasyon yntemi ile retilmi 2014 tozlar, Grafit (C) tozlar
MA ilemine tbi tutulmu, hem MA hem de MA sonras ilemlerle yapsal gelimeler incelenmitir.
2. DENEYSEL ALIMALAR:
2.1. Mekanik Alamlama:
2014 alam tozlar, yksek saflktaki Ar gazyla 15 bar basn altnda gaz atomizasyon yntemi ile retilmitir.
Daha sonra, elek analizi ve parack boyut analiz cihazlarnda ayrtrlan tozlarn ortalama boyu 95 m dir. Alam
tozlar, (20-180 m boyut aralnda) %2 grafit tozlaryla harmanlandktan sonra, yksek enerjili dikey Atritrde
MA ilemine tbi tutulmulardr. Atritr ierisinden yksek saflkta Ar gaz geirilerek toz karmnn oksitlenmesi
engellenmeye allmtr.
Bir nceki almada, MA ilemi bir kimyasal kullanmadan saf Al ve C tozlar ile gerekletirilmi ve ilemin 2 s sonunda baaryla tamamland belirlenmiti [7]. Benzer ekilde, bu almada da MA iin bir yalayc kullanmadan
AA2014 tozlar ve %2 C, 500 dev. / dak. ve 20: 1 bilye toz orannda tlmek istenmitir. Ancak, sistemin kilitlendiinin fark edilince, ilave yalayc olarak % 0,5 inko sterat katlm ve sorun almtr. Daha sonra, deneylerle
uygun MA sresinin en fazla 7 s olabilecei tespit edilmitir. Bu sre sonucu elde edilen kompozit tozlarnn ortalama tane boyutu 54, 50 m ve toz boyut aral 1,60-331 m arasnda deimektedir.
ekil 1de, MA sresine bal olarak ortalama toz boyutu ve buna bal olarak sertlik deerleri verilmitir. Alamlanm toz boyutun yaklak 5 s kadar artt ve bundan sonra tekrar azald grlmektedir.
ekil 1. MA ilemi srasnda, ortalama toz boyu ve sertlik deiimleri.
667

eitli srelerde MA yaplan tozlar XRD ile incelenmi ve ilemin sonunda beklenen Al4C3 faznn olumad anlalmtr (ekil 1). Benzer sonular, dier baz almalarda da grlmtr [7-11].
ekil 2. 7 s MA ilemi gren tozlarn XRD analizi.

2.2. Presleme ve Sinterleme:
MA sonras tozlar, 600 MPa altnda izo-statik presleme ile sktrlarak tablet haline getirilmitir. Daha sonra tabletler, 550 Cde 2-24 s arasnda, 600 Cde 2-196 s olarak belirli zaman aralklarnda uzun sreli sinterleme ilemlerine tbi tutulmutur. Bu sre ierisinde, gerek MA sonras tozlar, gerekse sinterleme sonras elde edilen kompozit
malzeme yaplar eitli karakterizasyon ilemlerine tbi tutulmulardr. Srasyla: toz boyutu analizlari iin; Malvern
Mastersizer E cihaz, XRD analizleri iin; Cuk =1.5406 ve 2/dakika tarama hznda Bruker D8 cihaz kullanlmtr. Ayrca, mikro yap incelemeleri Joel JSM-5600 taramal elektron mikroskobunda (SEM), sertlik lmleri ise,
Shimadzu Mikro Sertlik cihaznda 100g yk kullanlarak gerekletirilmitir.
MA sonras preslenen kompozit tozlar, preslenip tablet haline getirildikten sonra, 550 Cde uzun sreler tavlanarak, sinterlenmitir. Tavlamann balangcnda (4 s), tane yaps kk ve gzeneklilik azalma eilimi gsterirken,
zamann artmasyla (12 s) tanelerin iriletii, buna karn gzenek saysnda bir art grlmtr (Resim 3).
ekil 3. 550 Cde uzun sre tavlanma sonras mikro yaplar.

a) 4 s (X 1500) b) 12 s (X 1500)
5500C de, 4 s tavlanan numunelerde element dalm taramas (EDS) yaplarak, mikro yap iersindeki alam
elementleri ve miktarlar belirlenmitir. Resim 4 te iaretlenen 3 ayr blgede EDS analizi yaplmtr. lk 2 analiz,
ana matris zerinden alnm, bu iki farkl blgenin sl ilem sonras element dalm farkllklar belirlenmitir. 3.
analiz ise parlak renkli blgeden alnmtr. 1. blgenin analizi gre; Alminyum %93,2, Cu %0,85 ve Oksidin %5,94
olduu, 2. blgede, Cu %1,59 olarak artarken, O deerinin %1,69 oranna dt tespit edilmitir. 3. blgede ise,
Cu %4,6 deerlerine ularken, O deerinin % 3 civarnda olduu tespit edilmitir.
ekil 4. 550 Cde 4 s tavlama sonras mikro-yap ve EDS iin seilen blgeler (X 1500).
668

Ksaca, yap ierisinde element dalmlarnn homojen olmad, blgesel farkllklarn baskn olduu anlalmaktadr. ekil 4te, 3. noktadan alnan analiz sonularnda, parlak yerlerin Cu bakmndan zengin alanlar (Al2Cu) olduu
anlalmaktadr.
te yandan, ekil 5teki genel EDS sonucu incelendiinde, yaplan uzun sreli tavlamalar sonras mikro yapda
oksitlenme olmadn gstermektedir. Ayrca, genel Cu dalm seviyesinin beklenen miktardan (%5) daha dk
(%2,56) kmaktadr. Bu sonuca gre, Cu belli blgelerde ar younlaarak, kmelenmektedir. Sv faznda sinterlemenin etkin olduu bu durumda, tane snrlarnda kelen Al2Cu faz, tane iinde azalan Cu miktarnn sebebini
aklamaktadr.
ekil 5. 550 Cde 4 s tavlama sonras genel EDS sonular.

550C de yaplan uzun tavlama srasnda zamana bal olarak nce gzeneklilikte bir artn olduu, bunun tersi
olarak ta younlukta bir azalma meydana geldii grlmektedir. Tavlamann 24 s zerine kmasyla, olayn terse
dnd ve younluun artmaya balad fark edilmitir. Ksaca, 24 s dnm noktas olduu ve etken mekanizmann zayflad veya terse dndn anlalmaktadr. Genelde, Al alamlarnda bulunan Cu elementinin
malzemenin younluunda bir azalmaya sebep olduu bildirilmektedir [2,12,13]. Esasen, hem Cu, hem de Mg, Al
ierisinde hzla yaynabilmekte ve bylece, kk tane veya toz ara-yzeylerine hzla kabilmektedirler. zellikle
Mg, scakln etkisiyle Cua gre yaklak 5 kat daha hzl yaynp, buharlaarak ardnda boluk brakmaktadr [14].
Daha yava ilerleyen Cu ise daha sonra ara-yzeylere gelip, younlaarak Al2Cu fazn oluturmakta ve sv haldeki
bu faz zamanla tm ara-yzeyi kaplama eilimi gsterdii iin gzeneklilikte bir azalma balamaktadr. Bu yzden
yaplan element analizlerinde, mikro yaplarda Mg elementine rastlanamamtr [14].
ekil 6. 600 Cde 196 s tavlama sonras mikro yaplar.

a) (X 1000)
b) (X 1500)
6000Cde yaplan uzun sinterleme ilemlerinde, mikro-yaplarda az da olsa ksmi olarak yeniden kristalleme (YK)
balanglar grlmektedir (Resim 6). Saf Al istif hatas enerjisi (HE) yksektir ve bu yzden yaklak 300-3500C
gibi scaklklarda, Al hzl toparlanma ve YK eilimindedir [15]. Ancak bu almada, YKnn, 6000C de ok uzun
sren tavlama sonrasnda belli belirsiz olumaya balamas, alam elementlerinin etkisinden daha ok, yapda
youn olarak ince dalml Al4C3 paracklarnn bulunduunu ve YK balangcn nemli lde telediini gstermektedir. Tavlama srasnda oluan bu nano boyda, ok sk dalml ve kararl paracklar, MA sonras souk
deformasyondan gelen alt yap taneleri vs zerinde yerleerek, onlarn geliimini engellerken, toparlanma srecini
ar derecede geciktirmektedirler [14-18].
669

4. SONULAR
Sonu olarak, yap ierisinde youn dalma sahip Al4C3 faz YK balangcn nemli lde etkilemektedir. YK baz
belli blgelerde ok zor ve yava olarak geliim gsterme eilimindedir. nceki almalardan, Al4C3 paracklarnn
youn olarak yapda olutuu ve yaplarda hibir YK oluumunun gzlenmedii bilinmektedir [7]. Bu almada ise,
eldeki malzemenin YKya kar gsterdii ar diren, zellikle yksek scaklk dayanmnn iyi olabileceini iaret
etmektedir. retilen bu kompozit malzemede, hem MA sonras sinterleme ve hem de yalandrma ilemleriyle
yksek dayanml bir mikro-yap elde edilmitir. Malzeme, uzun sre yksek scaklklara maruz kalmasna ramen,
mekanik olarak eritii dayanmdan bir ey kaybetmemekte ve bylece yksek scaklk uygulamalarnda srnme
dayanm yksek malzemeler arasnda yer bulma potansiyeline kazanmaktadr.
KAYNAKLAR
1. Suryanarayana C., Mechanical Alloying and Milling, Progress in Materials Science, 46 (2001) 1-184.
3. Suryanarayana C., Mechanical Alloying, Pergamon Materials Series, 2 (1999) 49-85.
4. Ruiz-Navas E.M., Fogagnolo J.B., Vlasco F., Ruiz-Prieto J.M., Froyen L., One Step Production of Aluminium
Matrix Composite Powders by Mechanical Alloying, Progress in Composites, 37 (2006) 2114-2120.
5. Solozhenko V.L., Kurakevych O.O., Equation of State of Aluminum Carbide Al4C3, Progress in Solid State
Communications, 133 (2005) 385-388.
6. Kaar H., Atik E., Meri C., The Effect of Precipitation-Hardening Conditions on Wear Behaviours at 2024
Aluminium Wrought Alloy Progress in Materials Processing Technology, 142 (2003) 762-766.
8. Arslan G., Kara F., Turan S., Quantitative X-ray Diffraction Analysis of Reactive Infiltrated Boron CarbideAluminium Composites Journal of the European Ceramic Society 23 (2003) 12431255.
9. Wu, N. Q., Wu, J. M., Wang, G.X., Li, Z. Z., Amorphozation in the Al-C System by Mechanical Alloying, J. of
All. And Comp. 260 (1997) 121-126.
(2006) 107-122.
12. K.S. Dunnett, R.M. Mueller, D.P. Bishop, Development of AlNiMg(Cu) Aluminum P/M Alloys, Journal of
materials processing technology 198 (2008) 3140.
13. Zhou, J., Duszczyk, J., 1999. Liquid Phase Sintering of an AA2014-Based Composite Prepared from an Elemental Powder Mixture. J. Mater. Sci. 34, (2008) 545550.
14. imir, M., Gngr, ., gel, B., Al-Cu ve Al-Cu-Mg Toz Karmlarnn Azot Atmosferi Altnda Scak Presleme
almalar, 10. Uluslararas Metalurji ve Malzeme Kongresi Bildiriler Kitab Cilt III, 24-28 Mays, stanbul,
1781-1788 (2000).
15. Cotterill P., Mould P.R., Recrystallization and Grain Growth in Metals, Surrey University Press, London, UK,
(1976).
16. Doherty R.D., The Deformed State and Nucleation of Recrystallization, Metal Science, 8 (1974) 132-142.
17. Higgins G.T., Grain Boundary Migration and Grain Growth, Metal Science, 8 (1974) 143-150.
18. Hoyt J.J., On the Coarsening of Precipitates Located on Grain Boundaries and Dislocations, Acta Metall.
Mater., 39 (1991) 2091-2098.
670

TOZ METALURJS YNTEMYLE Ag-B2O3 ESASLI KONTAK MALZEMES

RETM VE ZELLKLERNN NCELENMES

Serkan BIYIK1 , Fazl ARSLAN2

1
Karadeniz Teknik niversitesi, Mhendislik Fakltesi, Metalurji ve Malzeme Mhendislii
Blm, 61080,
Trabzon, e-mail: serkanbiyik@ktu.edu.tr
2
Karadeniz Teknik niversitesi, Mhendislik Fakltesi, Metalurji ve Malzeme Mhendislii Blm, 61080, Trabzon, e-mail: farslan@ktu.edu.tr

zet
Bu almada TM yntemiyle retilen Ag-B2O3 esasl kontak malzemelerinin zelliklerine B2O3 orannn etkisi incelenmitir. Gm ve bor oksit tozlar retildikten sonra homojen bir ekilde kartrlp 1000 MPada preslenmitir.
Preslenen numuneler 800Cde sinterlenmitir. Bor oksit % 0 ile % 15 orannda ilave edilmitir. Sabit ve hareketli
kontak iftlerinin malzemeleri ayn trden seilmitir. Numunelerin belirli evrim saylar sonunda arlklar llm ve yzeyleri metal mikroskobu ve SEMde incelenmitir. Deneyler 220 V, 50 Hz ve 5 A alternatif akm altnda
yaplmtr. evrim says dakikada 60 ama-kapama olacak ekilde seilmitir.
Ama-kapama says 40.000
evrime kadar kartlarak, evrim says ile arlk kayb arasndaki ilikiler aratrlmtr. Belirli evrim saylarnda
kontaklarn yzeylerinde yaplan incelemelerde ark etkili blge, gei blgesi ve ark etkisiz blge olmak zere
farkl blgenin olutuu gzlenmitir. Ark etkili blgeler evrim saysnn artmasyla genilemitir. Saf gm ve
B2O3 orannn dk olduu kontak malzemelerinde ark etkili blge yzeyinde ergime sonucu nispeten kaba girinti
ve kntlar oluurken, artan B2O3 oranyla ark etkili blgede belirgin ergime izleri azalmtr. B2O3 orannn yaklak
% 8 kadar artmasyla arlk kaybnda azalmalar tespit edilmitir. Bu azalma zellikle % 10 orannda B2O3 ieren
kontaklarda olduka belirgindir.
Anahtar Kelimeler: Elektrik Kontak Malzemeleri, Ag Esasl Kontak Malzemesi, Ark Erozyonu, Bor Oksit
InvestIgatIon of PropertIes of SIlver - BorIc OxIde Based

Contact MaterIals Produced by Powder Metallurgy
ABSTRACT
In this study, the effects of boric oxide content on the properties of Ag-B2O3 based contact materials which were
produced by PM were investigated. Silver and boric oxide powders were uniformly mixed and pressed at 1000 MPa.
Compacts were sintered at 800C. The boric oxide content was changed between 0 % and 15 %. Both the fixed
and the movable contacts were selected from the same material. The contact surfaces and the weight losses were
examined after certain cycles. Arc erosion experiments were carried out at 220 V, 50 Hz, 5 A AC and cycled at 60
operations per minute. The number of cycles were increased up to 40.000 and the relationship between weight loss
and cycle number were investigated. It was observed that all the samples were loosing weights rapidly up to 20.000
cycles and after that point, the weight losses were slow up to 40.000 cycles. The effects of B2O3 was not significant
at low contents of B2O3 but reached to minimum weight loss at about 8 % contents of B2O3. Examinations of contact
surfaces using metal microscope and SEM after certain cycles showed that the arc affected zones enlarged with
increasing number of cycles. Arc affected zone was almost diminished in 10 % B2O3 containing materials, this was
attributed to cooling effect of B2O3 particles which was melted at 450C.
Key Words: Electrical Contact Materials, Silver-Based Contacts, Arc Erosion, Boric Oxide
671

1. Giri
Kontaklar, elektrik uygulamalarnn ounda kullanlan ve bir ya da daha fazla saydaki devrenin elektrik akmn
ap kapamak suretiyle ayn anda bu devreleri kumanda edebilen kontaktr ve rle gibi elektromanyetik anahtarlarn en nemli elemanlarndan birisidir. Karlkl olarak alan, akm tama ve akm kesme grevlerini stlenen
kontaklar, alp-kapanma srasnda oluan ark ile ar ekilde snmakta ve hem ergime hem de buharlama yolu
ile nemli miktarlarda malzeme kaybna uramaktadrlar. Buna ek olarak kontaklarn yzeyleri bozulmakta ve bir
kontaktan dierine malzeme transferinin meydana gelmesiyle kontaklar alamaz hale gelmektedirler. Bu olumsuz
durumlar en aza indirerek kontaklarn mrlerini uzatmak iin seilecek kontak malzemelerinin, akmn geii srasnda oluan yksek sy ileterek kontaklarn ar snmasn nleyecek yksek elektriksel iletkenlie, ortaya kan
ark ssn iletecek yksek sl iletkenlie, kontaklarn yzeylerinde birikerek yaltkanla sebep olan oksit, slfit ve
dier bileiklere kar yksek reaksiyon direncine, ark erozyonunu, malzeme transferini ve kaynak olmay (yapmay) snrlayacak yksek ergime noktasna ve dk buhar basncna, iyi bir anma direnci iin yksek sertlie
sahip olmas gerekir. Fakat hibir malzeme sralanan btn bu zelliklere tek bana sahip olmadndan emniyet,
elde edilebilirlik, mr ve maliyet gz nne alnarak belirlenen her uygulama iin uygun bir malzeme seimi yaplmal ve farkl zelliklere sahip malzemeler bir araya getirilmelidir.
Kontak malzemelerinin seiminde, elektrik devresinin karakteristikleri (akm, gerilim v.b.), ykn eidi, kapasite,
kontaklara uygulanan kuvvet, kontaklarn alp-kapanma says,
alp-kapanmann skl ve gvenilirlik gz
nne alnmas gereken faktrlerin
balcalardr [1-4]. Kontaklardan geen akmn alternatif ya da doru akm,
yksek ya da dk deerli, ykn indktif, kapasitif, diren ya da bir motor yk olmas da malzeme seiminde
nemlidir.
Metallerin mrn nemli oranda azaltan atmosfer etkisi, kirlilikler, gazlar, tozlar, nem ve organik buharlar gibi evresel faktrler de kontak malzemesinin seiminde nemli rol oynamaktadr.
Saf gmn dier metaller iinde en yksek sl ve elektrik iletkenliine sahip olmas, kontak malzemesi olarak
kullanmn cazip klmasna karn, ark erozyonuna kar mukavemeti arttrmak, kaynama veya yapmay en aza
indirmek; oksit ierikli birok malzeme ile birletirilmesini gerekli klmtr. Dkm yolu ile retilemeyen bu malzemeler, toz metalurjisi ve i oksidasyon yntemleri ile elde edilmektedir. oksidasyon iin gerekli zamann ok
uzun olmas, oksit dalmnn, byklnn, eklinin dzensiz olmas ve oksit ieriinin snrl oranda olmas, toz
metalurjisi tekniinin i oksidasyona tercih edilmesinin balca sebeplerini oluturmaktadr.
Toz metalurjisi yntemi kullanlarak istenilen zelliklerde rnlerin elde edilebilmesi, aadaki proses deikenlerinin doru olarak seilmesine ve kontrolne baldr [5]:
Toz zellikleri,
Tozun hazrlan yntemi,
Sktrmann nasl uyguland,
Sktrmann yapld kalp ve aletlerin tasarm,
Sinterleme frnnn tipi,
Sinterleme atmosferinin bileimi,
Sinterleme scakl ve zaman da dahil olmak zere retim ak,
kincil uygulamalar ve sl ilem.
Kontaklardan beklenen yararl kullanm mrleri, fzelerde birka operasyondan, otomobil titretiricilerinde yz
milyon evrime (ama-kapama) ve telefon rlelerinde krk yla kadar deimektedir.
Bu almann amac yeni kontak malzemeleri bulmak ve gelitirmektir. Bu amala K.T.. Fen Bilimleri Enstits
Metalurji ve Malzeme Mhendislii Anabilim Dal Toz Metalurjisi Laboratuarnda toz metalurjisi yntemiyle deiik
oranlarda B2O3 ieren gm esasl kontak malzemeleri retilmi ve ark erozyon deneylerine tabi tutulmutur. Ark
erozyon davranlar incelenen kontak malzemelerinde B2O3 in ark erozyonuna ve arkn kontaklarda oluturduu
yzey bozunumuna etkileri incelenmitir.
Bu almada hacimsel olarak %5, %10 ve %15 B2O3 (bor oksit) ieren Ag (gm) esasl elektrik kontak malzemeleri toz metalurjisi yntemi kullanlarak retilmitir. retilen bu kontaklar tasarm ve imalat yaplan deney
dzeneinde ark erozyon testlerine tabi tutulmulardr. Deneylerde kontaklarn 10.000, 20.000, 30.000 ve 40.000
kez alp-kapanmas (evrim) sonunda, kontak yzeylerinde meydana gelen ark bozunumlar incelenmitir. Her
evrim aral sonunda sabit ve hareketli kontaklarn arlklar llerek, ark erozyonu ile kontak iftleri arasndaki
malzeme transferleri deerlendirilmitir. Elde edilen bulgular ile de, test edilen drt deiik kontak arasnda karlatrmalar yaplarak B2O3 orannn kontak erozyonuna etkisi incelenmitir.
672

2.1. Kullanlan Malzemeler ve Toz retimi

Kontaklar retmek iin gerekli olan gm tozu, ticari saflktaki gm (%99,7) bir parann mekanik eelenmesiyle elde edilmitir. B2O3 ise Etibank tesislerinde retilmi olup, piyasadan toz halinde alnmtr. retilen tozlar 250
mlik elekten elenerek, elek alt tozlar kontak malzemesi imalinde kullanlmtr. Deneyde kullanlan tozlarn SEM
grntleri aada verilmitir (ekil 1 ve ekil 2).
ekil 1. Gm tozu
ekil 2. Bor oksit tozu

2.2. Toz Metalurjisi Yntemiyle Ag B2O3 Kontak Malzemesi retimi
lk olarak Ag ve B2O3 tozlar srasyla %5, %10 ve %15 olmak zere, belirli hacim oranlarnda kartrlmtr. Karmn homojen olabilmesi iin kartrlma esnasnda tozlara etil alkol pskrtlmtr. Elde edilen bu toz karm
ekil 3 ve ekil 4de grnleri verilen kalpta sktrlmtr. Sktrma ilemi 15 ton kapasiteli hidrolik bir pres ile
yaplmtr. Sktrma basnc 1000 MPa olarak alnmtr.
ekil 3. Ag B2O3 tozlarnn preslenmesinde kullanlan kalbn grn
673

ekil 4. Ag B2O3 tozlarnn presleme kalbnn teknik resmi

Sktrlan toz karm, baka bir ifadeyle ham kompaktlar sinterlenmek zere ii odun kmr ile doldurulmu olan
bir elik tp iine (ular kapal) yerletirilmitir. Bu suretle indirgeyici atmosfer oluturularak oksitlenme nlenmitir.
Sinterleme ilemi sinter frnnda 800Cde 1 saat sre ile gerekletirilmitir. Sinterlenmi olan bu paralar biri sabit
kontak, dieri de hareketli kontak olacak ekilde bakr levhalara lehimlenmilerdir. Lehimleme ileminin ardndan
kontak yzeyleri ilenip en son 800 numaral zmpara ile zmparalama ilemi yaplmtr. Elde edilen kontaklarn
ykseklii yaklak 2.50 mm olarak llmtr. Hem alt hem de st kontaklarn aplar 5 mmdir. Btn lmler
dijital kumpas kullanlarak yaplmtr.
st kontaklar hareketli, alt kontaklar ise sabit olarak kullanlmtr. Kontaklar iin kullanlan retim metodunun i ak
diyagram ekil 5de gsterilmitir. ekildeki ak diyagramna gre imal edilip son ekline getirilen Ag - %5 B2O3,
Ag - %10 B2O3, Ag - % 15 B2O3 ve ayrca saf gm kontaklar ark erozyon testlerine tabi tutulmutur. Testlerden
sonra numunelerin yzeyleri metal mikroskobunda ve SEMde incelenerek fotoraflar ekilmitir.
ekil 5. Kontak malzemesi retiminde izlenen i ak diyagram
674

2.3. Deney Dzenei Elektrik Devresi

Ag B2O3 kontaklarnn test edilmesinde kullanlan deney dzenei ekil 6da grld gibidir.
ekil 6. Kontaklarn test edilmesinde kullanlan deney dzenei

Deney dzenei elemanlar rle, ift ayarl flr, reosta, varyak ve doru akm kaynandan olumaktadr. Rlenin bobini 24 voltluk doru akm ile almaktadr. Bobin ilevi, akm getiinde mknatslanarak hareketli konta
kendine doru ekmesi ve akm kesildiinde ise konta brakmas eklindedir. Bu ekilde hareketli kontan sabit
kontak zerine kapanp almas salanmtr. Kontaklarn belirli frekanslarda alp kapanmalarn salamak iin
ift ayarl flr kullanlmtr. Bylelikle kontaklarn ne sklkla alp kapanaca ve evrim sonras bekleme sresi
kolaylkla ayarlanabilmitir. Devreden geen akm artrmak veya azaltmak iin dzenee varyak dahil edilmitir.
Rlenin kontaklar 220 V gerilim ve 50 Hz frekans deerindeki alternatif akm ebekesine balanmtr. Ayrca kontaklar zerinden 5 A lik akmn ekilmesi iin de devreye reosta eklenmitir.
Kontaklar retilip bakr levhalara lehimlendikten sonra kontak sistemine monte edilmilerdir. Kontak sistemi ekil
7de grld gibidir.
2.4. Deneylerin Yapl
Gm ve bor oksit tozlar elek sisteminden geirilmi ve 250 mlik elek alt tozlar kontaklarn retiminde tercih
edilmitir. Ortalama parack boyutu arttka, sinterleme ilemi kt ynde etkilenecektir [6]. Bu nedenle 250 mlik
elek alt tozlar presleme ve sinterleme asndan uygun grlmtr. Hacimsel olarak %5, %10 ve %15 orannda
B2O3 ieren Ag B2O3 kompozitleri daha nce bahsedilen ak emasna uygun olarak imal edilmilerdir. ekil 6da
gsterilen deney dzeneindeki devreye monte edilen sabit ve hareketli kontaklar belirli
ama kapama saylarnda alnarak arlklar llm ve daha sonra da yzeyleri metal mikroskobu altnda incelenmitir.
ekil 7. Kontak sistemi
675

Deneylerden nce ortamn scakl ve nemi higrometreyle (nem ler) llmtr. Deneylerde nem orannn % 41
RH % 60 RH arasnda olduu grlmtr.
Sistemin almas esnasndaki scaklk artlar ise kzltesi termometre araclyla belirlenmitir. Yzeylerin incelenmesinde ise metal mikroskobu kullanlmtr.
ift ayarl flr ile kontaklarn saniyede bir kez alp-kapanmas salanmtr. Aratrmaclarn yapt almalarda da deneylerin salkl olmas asndan ama-kapama says dakikada 60 olarak alnmtr [7]. Kontaklardan 220
V gerilim, 50 Hz frekans deerlerinde 5 Alik alternatif akm geirilerek deneyler yaplmtr. Yaplan incelemelerde
her kontak malzemesi ifti iin ark erozyonu ve yzeyde ark ile ortaya kan deiiklikler karlatrmal olarak incelenerek B2O3 orannn etkisi deerlendirilmitir.
3. SONULAR
1. Alternatif akm artlarnda (220V, 50 Hz, 5 A) yaplan deneyler sonucu yaklak 20.000 ama-kapamada her
drt eit kontak iftindeki toplam arlk kaybnda nispeten hzl bir art grlm ve bu evrimden sonra arlk
kaybndaki azalma yavalamtr (ekil 8).
ekil 8. Drt farkl malzemeden yaplm kontak iftlerine ait toplam arlk kayplarnn ama-kapama
says ile deiimi
2. Gme % 5 B2O3 katlmasyla retilen kontak iftindeki toplam arlk kayb, saf gm kontaktakine yakn seyrederken, zellikle % 10 B2O3 ieren Ag - B2O3 kontak iftlerinde arlk kaybnda saf gme gre nemli lde
d grlmtr. Kontak malzemesindeki B2O3 oran arttka (yaklak % 10 B2O3 oranna kadar) arlk kaybnda
azalma gzlenmitir (ekil 8 ve ekil 9).
ekil 9. Deiik ama-kapama saylar iin kontak iftlerine ait toplam arlk kayplarnn bor oksit
oranyla deiimi
676

3. Sabit kontaklarda saf gm ile % 5 B2O3 ieren kontak malzemeleri benzer davran sergilerken, % 10 B2O3
ieren kontak malzemelerindeki arlk kayb nemli lde d gstermitir (ekil 10). Hareketli kontaklarda ise,
saf gm ile % 15 B2O3 ieren malzemelerde daha yksek arlk kayb grlmtr (ekil 11).
ekil 10. Drt
farkl malzemeden yaplm sabit kontaklarn arlk kayplarnn ama-kapama says ile
deiimi
ekil 11. Drt farkl malzemeden yaplm hareketli kontaklarn arlk kayplarnn ama-kapama
says ile deiimi
4. zerlerinden akm geen kontak iftlerinin alp-kapanmalar srasnda oluan ark nedeniyle kontak yzeylerinde yapsal deiiklikler olmutur. Genel olarak nispeten fazla arlk kayb gsteren numunelerde arkn etkin olduu
blgenin nispeten daha belirgin ve daha geni olduu gzlenmitir (ekil 12 ve ekil 13).
ekil 12. % 15 B2O3 ieren kontaklarda meydana

gelen ark etkili blgelerin grnm

gelen ark etkili blgelerin dier bir grnm
677

5. Saf gm kontaklarn yzeylerinde oluan ark etkili blge homojen olmayan bir deiim gsterirken, B2O3 ieren
Ag - B2O3 kontak yzeylerinde % 10 B2O3 oranna kadar artan B2O3 oranyla daha homojen bir grnm sergilemitir
(ekil 14 ve ekil 15).

gelen homojen ark etkili blge

gelen homojen ark etkili blgenin dier bir grnm
6. Sabit kontaklarn yzeylerindeki ark etkili blgelerde genellikle ergime sonucu malzeme kntlar ve ark noktalar oluurken, hareketli kontaklarda daha geni alana dalm ukurcuklar ve nispeten kk kntlarn olutuu
grlmtr.
4. KAYNAKLAR
1. Akarsu, F., Dalay, N., Dlen, E., Erdoan, F., Gnsel, E., Kan, B., Savat, G., Sevindik, A. ve Soytrk, E., Nasl
alr, Cilt I, Marshall Cavendish Ltd., Londra ve Geliim Basm Yaym A.., stanbul, 1980.
2. Askeland, D.R., The Science and Engineering of Materials, University of Nostrand Reinhold (International),
Missouri, Rolla, 1988.
3. Onaran, K. ve Altnta, S., Malzemelerin Yap ve zellikleri, Elektronik zellikler, 4. Cilt, Birinci Bask, .T..
Ktphanesi, Say: 1332, Gmsuyu, stanbul, 1986.
4. Ayar, H., Elektrik Kontak Malzemeleri, Bitirme almas, K.T.., Mhendislik Mimarlk Fakltesi, Makine
Mhendislii Blm, Trabzon, 1986.
5. Anonim, Metals Handbook, Properties and Selection: Irons, Steels and High Performance Alloys, A.S.M.,
1993.
6. Sarta, S., Trker, M. ve Durlu, N., Toz Metalurjisi ve Parackl Malzeme lemleri, Ankara, Temmuz 2007.
7. Wingert, P.C. ve Horn, G., The Effects of CdO on the Static Gap Arc Erosion of Silver Based Contacts,
IEEE Transactions on Components, Hybrids and Manufacturing Technology, 16, 2 (1993)
678

AIRLIKA %10 SiC PARACIK TAKVYEL AL MATRSL KOMPOZT

RETMNDE, RETM YNTEMNN KOMPOZT ZELLKLERNE ETKS
Hasan KARABULUT*, Ramazan ITAK**
*
Ankara Altnda Siteler Mesleki Eitim Merkezi, Metal Teknolojisi retmeni, Siteler, 06500, Ankara,
karabulut.hasan@hotmail.com
**
rcitak@gazi.edu.tr
zet
Arlka % 10 SiC parack takviyesi ieren Al matrisli kompozitler turbulada kartrma (TK) ve Mekanik alamlama (MA) yntemi ile retildi. TK ilemi homojen bir karm salamak amacyla 1 saat sreyle yaplm olup,
MA ilemi 10 saat sreyle gerekletirildi. TK ve MA yaplm numunelerin toz boyutu, parack dalm, sertlik,
younluk, gzeneklilik gibi karakteristik zellikleri ve abrasif anma direnleri incelenerek kyaslamalar yapld.
Yaplan deney ve analiz sonularnda MA yaplm numunelerin TK numunelerine gre daha homojen bir parack
dalmna sahip olduu belirlenmitir. TK numunelerinin younluunun daha fazla, dolaysyla daha az gzenek
deerine ve daha yksek abrasif anma direncine sahip olduu; MA uygulanm numunelerin ise, toz boyutunun
daha kk, sertlik deerinin daha yksek olduu belirlenmitir.
Anahtar Kelimeler: Kompozit, mekanik alamlama, SiC, abrasif anma direnci, sertlik.
EFFECT OF PRODUCTION METHODS ON COMPOSTE PROPERTIES FOR

%10 (BY WEIGHT) SiC PARTICLE REINFORCED AL MATRIX COMPOSITES
ABSTRACT
Al matrix composites containing 10 % (by weight) SiC particle reinforcement was produced by turbulent mixing
(TK) and mechanical alloying (MA). Mixing process in order to ensure a homogeneous mixture was carried out in a
three dimensional turbula device for one hour. MA process was performed for 10 hours. Particle size, reinforcement
distribution, hardness, density, porosity and abrasive wear resistances of composites were investigated and compared. It was determined that MA samples had more homogeneous reinforcement distribution than TK samples. TK
samples had high density and less porosity and higher abrasive wear resistance. It has also been determined that
MA samples had smaller particle size and higher hardness.
Keywords: Composite, mechanical alloying, SiC, abrassive wear, hardness.
1. GR
Yeni malzeme gelitirme almalar srekli devam etmekte olup, kompozit malzemeler iin yaplan almalarda
ok hzl bir ekilde ilerlemektedir. Kompozit malzemeler, kimyasal bileimi ve zellikleri farkl olan iki veya daha
fazla malzemenin makro dzeyde birletirilmesiyle elde edilen malzemeler olarak tanmlanmaktadr [1]. Kompoziti
oluturan malzemeler ara yzeylerle birbirlerinden ayrlr ve yap iinde kendi zelliklerini korurlar. Ancak kompozit
malzemenin zellikleri, kendisini oluturan malzemelerin zelliklerinden stndr [2]. Kompozit malzemelerin ou
takviye elemanlar ve bunun etrafn evreleyen matris malzemesinden olumaktadr. Takviye elemanlarnn temel
fonksiyonu gelen yk tamak, matrisin rijitlik ve dayanmn arttrmaktr. Kompozit malzemelerin retiminde uygun
679

artlar oluturulursa hafif alamlarn darbe ve anma dayanm arttrlabilir, yksek scaklklarda alabilecek zellikler kazandrlabilir ve younluklarn drmekte mmkn olabilir [3]. Bu sebeple dk younluklu alminyuma
yaplan seramik takviyesi ile yksek mekanik zelliklere sahip kompozitler retilebilir. Alminyum ve alamlarnn
dayanmlarn artrmak ve dier zelliklerini de iyiletirmek iin sert takviye elemanlaryla (fiber, whisker, parack
gibi) alminyum matrisli kompozitler retilmektedir [4].
Kompozit malzemeler, eitli dkm ya da toz metalurjisi teknikleriyle retilebilir. Bu tekniklerden bir tanesi de bir
kat hal ilem teknii olan mekanik alamlama yntemidir. Mekanik alamlama ilemi ile dkm ynteminde karlalan homojenlik, slatlabilirlik, birbiri ierisinde karmama vb. problemler ortadan kaldrlabilmektedir [5].
Bu almada, Al matrisli ve arlka %10 SiC parack takviyeli kompozitler kartrma ve mekanik alamlama
yntemiyle retilmitir. Mikroyap, tane boyutu, younluk, gzeneklilik ve sertlik gibi zelliklerin yannda abrasif
anma direnlerinin de incelenmesi amalanmtr.
Matris malzemesi olarak kullanlan alminyum tozlar % 99,7 saflkta olup 72 m ortalama toz boyutundadr. Takviye
eleman olarak SiC seramik tozlar ise; 12 m ortalama toz boyutundadr. Kartrma ilemi homojen bir karm elde
etmek amacyla 1 saat sreyle boyutlu kartrma yapabilen turbula cihaznda bilyesiz olarak yapld. Mekanik
alamlama ilemi ise; szegvari modeli dikey bir atritr ierisinde 10/1 bilye/toz orannda 10 mm apnda elik bilye
ve 0,75 g yalayc ile birlikte yapld. MA ilemi 350 rpm hzda, akan argon atmosferinde 10 saat srede uygulanmtr. MA srasnda snmay nlemek iin silindir, akan souk su ile srekli soutuldu.
TK ve MA ileminin toz boyutuna etkisini belirlemek iin toz boyut analizi yaplmtr. Ardndan kompozitlerin mikroyap, younluk, gzeneklilik, sertlik ve abrasif anma direnlerini belirlemek amacyla 12 x 15 mm boyutlarnda
blok numuneler 700 MPa presleme basncnda tek ynl olarak preslendi. Preslenen numuneler 600 C scaklkta
akan argon atmosferinde 1 saat sreyle sinterlendi. Sinterleme ncesi ve sonras younluk lmleri yaplarak
gzenek deerleri belirlenmitir. Sinterlenen numunelerdeki sinterlemeyi ve faz dalmn grebilmek iin, ncelikle
numuneler uygun zmparalama, parlatma ve dalamann ardndan Optik Mikroskop ve Taramal Elektron Mikroskobu ile incelendi. Sertlik lmleri Brinell sertlik lm cihaznda 2,5 mm bilye u ve 31,25 kgf yk uygulanarak
gerekletirildi. Her numune iin 6ar adet lm yapld ve bu deerlerin ortalamas alnd. Anma deneyleri 1200
meshlik SiC abrasif andrc zmparalar ile 7,5 m mesafede kuru ve yasz kayma koullar altnda gerekletirildi.
Anma deney ncesi ve sonrasnda hassas terazi ile arlklar lld ve deney sonras arlk kayplar belirlendi.
Resim 1de anma deneylerinin gerekletirildii deney cihaz grlmektedir.
Resim 1. Anma deney dzenei

[a) SiC zmpara, b) Numune tutucu (mandren), c) Dner disk]
3. DENEYSEL SONULAR
3.1 Toz Boyutu lmleri
ekil 2de grld gibi, MA uygulanm numunelerde toz boyutlar 45 m lara kadar derken, TK ilemi yaplm
numunelerde karmn ortalama toz boyutu 67 m olarak llmtr. Bunun sebebi MA uygulanm numunelerde
tozlarn 10 saat sreyle yksek enerjili deirmen ierisinde deformasyona maruz kalmas ve dolaysyla ortaya
kan peklemenin sonucunda krlma mekanizmasnn etkili olmasdr. Karabulut ve tak benzer artlarda Al Mat-
680

risli ve Al2O3 parack takviyeli kompozit retmiler ve 10 saat MA ileminin sonucunda parack boyutunun 27 m
mertebesine kadar dtn bulmutur [6]. Benzer ekilde Ark ve Trker MA yntemi ile rettikleri Fe-Fe3C kompozitlerde alamlama sresinin artmasyla toz boyutunda azalmalar olduunu tespit etmitir [7]. Her iki almada
da ortaya kan sonular bu almay destekleyici niteliktedir.
ekil 2. Toz boyut analiz sonular

Resim 2de TK ve MA yaplm toz numunelerin SEM fotoraflar verilmitir. Resimlerde de grld gibi MA
yaplm numunelerde tme artlarndan kaynakl deformasyonun etkisi ile oluan tane klmesi ve pullama
belirgindir, ancak turbula cihaznda bilyesiz olarak kartrma yaplm toz numunelerde herhangi bir deformasyon
etkisi grlmemektedir.
Resim 2. TK ve 10 saat MA yaplm tozlarn SEM grnts

3.2 Younluk ve Gzeneklilik Deerleri
ekil 3te blok numunelerin sinterleme ncesi/sonras younluk ve gzeneklilik deerleri verilmitir. Bu sonulara
gre turbulada kartrma yaplm numunelerin daha yksek younlua ve daha az gzeneklilik deerine sahip
olduu grlmektedir. TK ilemi yaplm numunelerin ham younluklar % 96 iken; MA yaplm numunelerin ham
younluklar % 94 olarak belirlenmitir. Sinterleme sonras ise numunelerin younluk deerleri bir miktar artmtr.
Mekanik alamlanm numunelerin TK numunelerine gore younluklarnn dk olmasnn sebebinin MA srasnda yksek deformasyonun etkisiyle tozlarda oluan peklemenin numunelerin presleme esnasnda sktrlabilirliini olumsuz etkilemesinden kaynakland sanlmaktadr.
Karabulut ve taknda ayn artlarda rettikleri Al Matrisli ve Al2O3 ve SiC parack takviyeli kompozitlerde bulduklar benzer sonular bu almay desteklemektedir [6, 8]. Ayrca bu durum MA yaplm numunelerin toz boyutunun
turbulada kartrma yaplm numunelere gre daha dk olmasndan da kaynaklanabilir. nk, kk tozlarn
sktrmaya diren gsterdii ve bundan dolay zellikle nano boyutlu tozlarn sktrlabilirliinin ok zor olduu
belirtilmektedir [9].
681

ekil 3. Turbulada kartrma ve MA yaplm numunelerinin sinterleme ncesi ve sonras younluklar ve

gzeneklilik deeri
retilen blok numunelere ait optik mikroskop fotoraflar Resim 3de verilmitir. MA uygulanm numunelerin TK
numunelerine nispeten daha homojen bir dalm sergiledii grlmektedir. Dier yandan MA ilemi uygulanan
numunelerde TK numunelerine gre gzeneklilik orannn artt belirgindir. Her ne kadar MA ilemleri koruyucu
gaz atmosferi altnda yaplsa da, uzun sreli MA ilemlerinde % 100 denge artlarnn salanmas zordur. Bu sebeple uzun sureli MA ilemlerinde toz yzeylerinde oluabilecek oksitlenmeler presleme ve sinterleme esnasnda
olumsuz etkilere neden olabilir. Doal olarak numunelerin younluklar derken, gzeneklilik deeride bir miktar
artmaktadr.
Resim 3. TK ve 10 saat MA yaplm blok numunelerin optik Mikroskop resimleri

3.3 Sertlik lmleri
Sadece matris malzemesi olarak kullanlan alminyum tozlarndan ayn artlarda retilen blok numunelerin sertlik
sonular 26 HB sertlik deerinde elde edilmiken, doal olarak parack takviyeli kompozitlerin sertlikleri hem
TK ilemi, hem de MA ilemi sonucunda daha yksek kmtr. ekil 4te grld gibi MA yaplm numunelerin brinell sertlik deerleri, turbulada kartrma yaplm numunelerin sertlik deerine oranla neredeyse iki katna
yakndr. Bu artn, MA srasnda oluan tane klmesinden kaynakland dnlmektedir. Ark, MA ile rettii
kompozitlerde sertlik iin en nemli faktrlerden birinin MA sresi olduunu belirtmitir [10].
ekil 4. Sertlik sonular
682

3.4 Anma Direnleri

Tm numunelere anma deneylerinde 10, 20 ve 30 N yk uygulanmtr. Doal olarak yk miktarnn artmasyla
anma miktarlar da artmtr. Saf alminyumda, retilen kompozit malzemelere gre daha kolay deformasyon
olumu, izik oluumu ve srklenme sebebiyle anma daha kolay balamtr (Resim 4). Yumuak malzemelerin
sert malzemelere gre daha abuk deformasyona urayaca ve dolaysyla malzemenin ekil deiimine uramasnn daha kolay olaca belirtilmitir [11]. Anma deneyleri ierisinde beklendii gibi en fazla anma miktar saf
Al malzemede tespit edilmitir. Saf alminyumda abrasif anmada mikro kesmeyle birlikte yksek deformasyon
sonucunda takozlama (srklenme) mekanizmas olumu ve buna bal olarak srekli geni izgiler meydana
gelmitir. Hasrc ve Glde yaptklar almada benzer sonular bulmutur [11].
(a)
(b)
Resim 4. 30 N yk altnda anm numune SEM resimleri
(a) Saf alminyum (b) TK ilemi yaplm kompozit (c) MA ilemi yaplm kompozit
(c)
TK ve MA tekniiyle retilen kompozitler de beklendii gibi anma miktarlar saf Al malzemeye kyasla daha azdr.
Bu durum retilen kompozitlerde sert seramik parack takviyesinin etkisinden kaynaklanmaktadr.
ekil 5. Saf alminyum ve kompozitlerin arlk kayb miktarlar

Genel olarak tm kompozitlerin anma miktarlar incelendiinde (ekil 5), TK ile retilmi olan numunelerin MA
ile retilmi olan numunelere gre daha az andn grlmektedir. Bu durumun TK numunelerinin daha youn
ve bu numunelerde sinterlemenin daha iyi olmasndan kaynakland sanlmaktadr. Benzer ekilde Kurt yapt
almada, Al-Al2O3 takviyeli kompozitleri, 4er saat sreyle turbulada bilyesiz olarak kartrma, MA ve dner deirmende olmak zere farkl yntemle retmitir. retilen blok numunelerde en iyi anma performansnn turbula
cihaznda retilen kompozitlerde olduunu tespit etmitir [12].
1.
SONULAR
MA ilemi ile uygulanm numunelerin toz boyutu nemli oranda klmtr.

Sinterleme sonras tm numunelerin younluk deeri artmtr. TK numunelerinde sinterleme sonras younluk
art daha fazladr, dolaysyla bu numunelerde sinterlemenin daha iyi olduu grlmtr.
TK numunelerinin younluk deerleri MA numunelerine gre daha yksek ve dolaysyla gzenek deerleri de
daha dktr.
MA ile retilmi kompozitler TK ile retilmi kompozitlere gre daha serttir.
MA numunelerinin abrasive anma direnleri TK numunelerine gre daha dktr.
683

TEEKKR
Gazi niversitesi BAP Birimine 07/2010-58 nolu proje kapsamnda yapt katklardan dolay teekkr ederiz.
KAYNAKLAR
1. Kaw, A.K., Mechanics of Composite Materials, Crc Press, Washington, 3: 61-65 (1997).
2. Hull, D. ve Clyne, T.W., An Introduction to Composite Materials, 2nd Edition, Cambridge University Press,
Cambridge, (1996).
3. Sahin, Y., Kompozit Malzemelere Giris, Gazi Kitabevi, Ankara, 65-69 (2000).
4. Jun D., Liu, Y.-H., Yu, S.-R., Li, W.-F. Dry sliding friction and wear properties of Al2O3 and carbon short fibres
reinforced Al-12Si alloy hybrid composites, Wear, 257: 930-940 (2004).
5. Suryanarayana, C., Mechanichal alloying and milling, Progress in Materials Science, 46: 1-184 (2001).
6. Karabulut, H., tak, R., Al matrisli ve Al2O3 parack takviyeli kompozitler iin retim ynteminin kompozit
zelliklerine etkisi 6th International Advanced Technologies Symposium (IATS11), 503-506, Elaz, 2011.
7. Ark, H., Trker, M., Production and characterization of in situ Fe-Fe3C composite produced by mechanical
alloying, Materials & Design, 28: 140-146 (2005).
8. Karabulut, H., tak, R., Al matrisli ve SiC parack takviyeli kompozitlerin farkl mekanik alamlama srelerinde retilmesi ve karakterize edilmesi 6th International Advanced Technologies Symposium (IATS11),
527-530, Elaz, 2011.
9. Sarta, S., Trker, M, Durlu, N,.Toz Metalurjisi ve Parackl Malzeme lemleri, Trk Toz Metalurjisi Yaynlar: 05, Ankara, 2-9, 15-34, 206, 237, 379-387, 404-410, (2007).
10. Ark, H., Production and characterization of in situ Al4C3 reinforced aluminum based composite produced by
mechanical alloying technique, Materials and Design, 25: 1-4, (2004).
11. Hasrc, H., Gl, F., B4C /Al kompozitlerin takviye hacim oranna bal olarak abrasif anma davranlarnn
incelenmesi, SDU International Journal of Technologic Sciences, Vol 2, PP 15-21, 2010.
12. Kurt, H., Alminyum Almina Kompozit Malzeme retiminde Kartrma Tekniinin Kompozitin Anma Davran zerine Etkilerinin Aratrlmas, Yksek Lisans Tezi, Gazi niversitesi Fen Bilimleri Enstits, Ankara,
33-48 (2010).
684

YKSEK ORANDA GZENEK EREN DEMR ESASLI KOMPAKTLARDA

RETM SREC ESNASINDA MEYDANA
GELEN HACMSEL DEMLER
* stanbul niversitesi Metalurji ve Malzeme Mhendislii Blm, Avclar, stanbul.
ZET
Bu almada; toz metalurjisindeki boluk yapc teknii kullanlarak yksek oranlarda gzenek ieren demir esasl
kompaktlarda retim sreci esnasnda meydana gelen hacimsel deiimler incelenmitir. Farkl ekil ve partikl
boyutlarna sahip karbamit, Astaloy Mo tozlaryla kaplandktan sonra 200 MPa basn altnda preslenerek boy/ap
oran yaklak 1,5 olan silindirik ham kompaktlar retilmitir. Ham kompaktlar ierisindeki karbamitin suda zndrlerek uzaklatrlmasyla elde edilen gzenekli yaplar hidrojen atmosferinde 1200 Cde 60 dakika sinterlenmitir.
zndrme sonras ham kompaktlarda hacimsel byme meydana gelmi, artan karbamit miktar ve azalan karbamit boyutuyla hacimsel byme azalmtr. Sinterleme sonras numunelerde; gzenek miktar, ekli ve boyutuna
bal olarak hacimsel ekme gereklemitir.
Anahtar kelimeler: Gzenekli malzemeler, karbamit, sinterleme, hacimsel deiimler.
DIMENSIONAL CHANGES IN HIGHLY POROUS IRON BASED

COMPACTS OCCURRED DURING MANUFACTURING PROCESS
ABSTRACT
In this study; volume changes that occurred during manufacturing process of highly porous iron based compacts
using the space holder technique in powder metallurgy were investigated. Different amount of space holder (carbmide) having different particle sizes and shapes were covered with pre-alloyed Astaloy Mo powder and then compacted at 200 MPa to produced green compacts having length to diameter ratio of about 1.5. Carbamide in the green
compacts was removed by water leaching and then the highly porous green compacts were sintered at 1200 C for
60 minutes under hydrogen atmosphere. Volume expansion in the green compact occurred after water leaching. An
increase in carbamide content and a decrease in carbamide particle size lead to lower volume expansions. Sintering caused volumetric shrinkage in the compacts. The extent of volumetric shrinkage after sintering was dependent
on volume, shape and sizes of the pores.
Keywords: Porous materials, carbamide, sintering, volumetric changes.
1. GR
Yksek oranda gzenek ieren malzemeler; yksek mekanik enerji emebilme kapasitesi ve ok dk zgl arla sahip olduklar iin yapsal ve ilevsel amalarla kullanlmaktadr. Kpks metallerin gsterdii zellikler;
ierdikleri gzeneklerin ekline, dalmna ve gzeneklerin birbirleriyle olan balantsna bal olarak deimekte
ve ok farkl potansiyel kullanm alanlar gstermektedir. Kpks malzemeler ierdikleri gzenek tiplerine gre;
ak, kapal ve kark gzenekli malzemeler olarak ayrlabilir. Gzenek tipi gzenek yapsn belirlediinden ayn
zamanda kpks malzemenin pek ok zelliini de ortaya koymaktadr. Gzenein yaps; kpks malzemenin
s iletkenliini, ses absorbsiyonunu, hava geirgenliini, mukavemetini, rijitliini etkilemektedir. Kapal gzenekli
malzemeler, ak gzenekli olanlara nispeten daha yksek mukavemet, rijitlik ve darbe dayanmna sahiptir. Deformasyon mekanizmasnda gzenek duvar esnemesi ve bzlmesi de nemli bir rol oynadndan bu tip gzenek
685

yapsna sahip malzemelerde gzenek duvarlar yapy rijitletirir. Bu bakmdan kapal gzenekli malzemeler, srekli
titreime maruz kalan makine paralarnda esneklik vermek amacyla kullanlmaktadr. Ak gzenek yaps ise malzemenin rijitliini drmesine karn yksek s tanmn mmkn klan zelliinden dolay yksek g reten
cihazlarda etkili bir soutucu mekanizma olarak kullanm alan bulmaktadr [1-2].
Boluk yapc kullanlarak toz metalurjisi yntemiyle gzenekli malzeme retimi; gzenek zelliklerinin, malzeme
eklinin ve mekanik zelliklerinin kontrolnde dier yntemlere gre salad birok stnlkten dolay son yllarda
kullanlan bir yntem olarak karmza kmaktadr [3-7]. Yaplan almalarda boluk yapc olarak; organik malzemeler,
karbonatlar, metalik tozlar, seramik paracklar, polimerik tozlar, ii bo kresel tozlar veya tuz kullanlmtr. Boluk
yapcnn ana yapdan uzaklatrlmas; boluk yapcnn uygun bir organik zcde veya suda zndrlmesi ve
termal olarak ayrtrma ile yaplabilir. Organik zc ile boluk yapcnn giderilmesi evreye zararl atklar oluturabilir, termal olarak gidermede boluk yapcnn bozunmas sonucu ortaya kan gazn numuneyi paralama riski
vardr bu durum ok dk sinterleme hzlarnda giderilebilir ancak uzun sre gerektirir ve bozunma esnasnda
aa kan gazlar metalle reaksiyona girebilir. Boluk yapcnn suda zndrlerek giderilmesi evreye zarar
olmayan olduka basit ve ucuz bir yntemdir.
Toz metalurjisi ile retilecek bir parann dizaynnda gz nne alnmas gereken en nemli unsur paraya uygulanacak srelerdir. Parann sktrma kalb tasarmndan daha sonra uygulanacak btn sreler ve bu srelerden
kaynaklanan boyutsal deiimler gz nnde bulundurularak kalp dizayn yaplmaldr [8-10]. Bundan dolay yksek
oranda gzenek ieren demir esasl malzemelerin boluk yapc-toz metalurjisi yntemiyle retim srecinde numunelerde meydana gelen boyutsal deiimlerin belirlenmesi nem tamaktadr. Literatrde boluk yapc yntemiyle gzenekli malzeme retiminde; boluk yapc miktar, ekli ve boyutunun hacimsel deiimler zerine etkisinin
aratrld bir almaya rastlanmamtr.
Bu almada, toz metalurjisi yntemiyle Astaloy Mo tozundan yksek oranda gzenek ieren numuneler retilerek
boluk yapc olarak kullanlan karbamitin miktar, ekli ve boyutuna gre; zndrme sonras numunelerde meydana gelen hacimsel deiimler karbamit miktarna gre; sinterleme sonras numunelerde meydana gelen hacimsel
deiimler sinterleme sonras gzenek miktarna gre belirlenmitir.
2. MALZEME VE YNTEM
Bu almada; Hgans firmas tarafndan atomizasyon yntemi ile retilmi ortalama tane boyutu 109 m olan
dzensiz ekilli n alaml Astaloy Mo demir tozu kullanlmtr. Astaloy Mo tozu Fe-%1,5 Mo ve %0,8 Zn-Stearate
PM isimli organik bazl yalayc iermektedir. Ham mukavemeti arttrmak amacyla balayc olarak kullanlan parafin Merck firmasndan temin edilmi olup 46-48 C arasnda erime scaklna sahiptir. Boluk yapc olarak, Merck
firmas tarafndan temin edilen teknik safiyette karbamit (re) kullanlmtr. Karbamitin younluu; 1,34 g/cm , erime
scakl 133 C ve 20 C scaklktaki suda znrl 108 g/mLdir. ekli kresel olan karbamitten eleme yaplarak
+1000-1400 m boyut aralna sahip kresel ekilli; agat havanda tlp ardndan eleme yaplarak da +500-710
m, +710-1000 m ve +1000-1400 m boyut aralklarna sahip dzensiz ekilli karbamit elde edilmitir.
ekil 1de atomizasyon yntemiyle retilmi n alaml Astaloy Mo tozunun Taramal Elektron Mikroskobu (SEM)
grnts, ekil 2-(a), (b) ve (c)de srasyla; +500-710 m, +710-1000 m ve +1000-1400 m boyut aralklarna
sahip dzensiz ekilli; (d)de +1000-1400 m boyut aralna sahip kresel ekilli karbamitlerin stereo mikroskop
grntleri verilmitir.
ekil 1 : Deneysel almada kullanlan Astaloy Mo tozunun SEM grnts
686

ekil 2 : (a) +500-710 m, (b) +710-1000 m ve (c) +1000-1400 m boyut aralklarna sahip dzensiz ekilli;
(d) +1000-1400 m boyut aralna sahip kresel ekilli karbamitlerin morfolojisi
Ham numunelerin mukavemetinin arttrlmas amacyla balayc olarak a.%3 orannda hazrlanan parafin zeltisi, n
alaml demir tozuna hac.%2 orannda katlarak oda scaklnda 30 dakika kartrlmtr. Karma; hac.%50 ile
%80 arasnda deien oranlarda farkl partikl boyut ve ekline sahip karbamit ilave edilip turbula tipi kartrcda
1 saat sre ile kartrma sonucu, karbamit paracklar demir tozlar ile kaplanmlardr. Optimum basn karbamit
eklinin korunmas iin mmkn olduu kadar dk, retimin tamamlanabilmesi iin yeterli olacak kadar byk
olmas amalanarak belirlenmitir. Tm numuneler iin optimum presleme basnc 200 MPa olarak belirlenmitir.
Demir tozlaryla kaplanm karbamitin elik bir kalp ierisinde 200 MPa basn uygulanarak tek ynl preslenmesiyle 12 mm apnda ve yaklak 18 mm yksekliinde silindirik numuneler elde edilmitir. Ham numunelerdeki karbamitin byk blm saf su banyosunda zndrlerek giderilmitir. Numunelerin ierdii karbamit oranna gre
suda zndrme sreleri 3-12 saat arasnda deimitir. Numunelerden zndrlen karbamit miktarlar, Jenco
marka 6350 PH/COND/TEM model Kondktometre cihaz kullanlarak tespit edilmitir. Hacimce %70-80 orannda
karbamit ieren numunelerdeki karbamitin yaklak %91-98i, hac.%50-60 orannda karbamit ieren numunelerdeki karbamitin ise yaklak %73-85i zndrlerek uzaklatrlmtr. Numunelerin ierisinde kalan az miktardaki
karbamit ile balayc olarak kullanlan parafinin termal olarak giderilmesi ve sinterleme ilemi Lenton marka frnda
yaplmtr. Seramik boru ierisine yerletirilen numuneler; ortamdan N2 gaz geirilerek nce 5 C/dak stma hzyla
400 Cye stlm ve bu scaklkta 30 dakika tutulmu daha sonra ortamdan yksek safiyette H2 gaz geirilerek 10
C/dakika stma hzyla 1200 Cde 1 saat sinterlenmitir.
Presleme ncesi; demir tozlarnn, farkl partikl boyut ve ekilli karbamitin ve yzeyi demir tozuyla kaplanm farkl 3
partikl boyut ve ekilli karbamitin grnr younluklarn belirlemek iin 2 cm lk Arnold metre kullanlmtr. Ham numunelerin zndrmeden nce ve zndrmeden sonra younluklar ktle/hacim ilikisinden belirlenmitir. Numunelerdeki karbamitin zndrlerek uzaklatrlmas sonras boyut lmleri, zndrme ncesi boyut lmleriyle
deerlendirilerek; farkl miktar, partikl boyut ve ekline sahip karbamit ieren ham numunelerde meydana gelen
hacim deiimleri karbamit miktarna gre belirlenmitir. Sinterlenmi numunelerin younluklar, ak ve kapal
gzenek oranlar Arimed Yntemine gre belirlenmitir. Ak ve kapal gzenek oranlarn belirlemek iin numuneler
150 Cde kaynayan parafin ierisinde 1,5 saat bekletilerek parafinin gzeneklere emdirilmesi salandktan sonra
numunelerin arlk lmleri gerekletirilmitir. Farkl miktar, partikl boyut ve ekline sahip karbamit kullanlarak
retilen numunelerin sinterleme sonras boyut lmleri, sinterleme ncesi (zndrmeden sonra) boyut lmleriyle deerlendirilerek; numunelerde meydana gelen hacim deiimleri sinterleme sonras numunelerin gzenek
miktarna gre belirlenmitir. lmler 5 numune zerinde yaplarak ortalamalar alnmtr.
3. SONULAR VE DEERLENDRME
Kalp ierisindeki metal tozuyla kaplanm boluk yapcnn grnr younluu sktrlabilirliinde belirleyici rol
oynamaktadr. Demir tozuyla kaplanm farkl boyut ve ekilli karbamitlerin grnr younluklar; demir tozunun ve
karbamitin grnr younluklar ve hacimsel oranlar kullanlarak karm kuralna gre hesaplanan grnr younluklar ve Arnold metre kullanlarak belirlenen grnr younluklar srasyla; (h) ve (b) ile ifade edilerek Tablo 1de
verilmitir.
687

Tablo 1 : Karm kuralyla hesaplanan ve Arnold metre ile belirlenen grnr younluklar
Artan karbamit oranyla grnr younluklar beklendii gibi azalmtr. Arnold metre kullanarak belirlenen grnr
younluk deerleri, karm kuralna gre hesaplanan grnr younluk deerlerinden kk kmtr. Karbamitin
balayc ile kartrlm demir tozlaryla kaplamas iin nemlendirilmesi, nihai karm sonras dk karbamit
oranlarnda artan demir tozu veya yksek karbamit oranlarnda tam kaplanmam karbamitler buna neden olmutur.
Demir tozuyla kaplanm farkl boyut aralklarna sahip dzensiz ekilli karbamitlerin grnr younluu artan karbamit boyutuna bal olarak bir miktar artmtr. Demir tozuyla kaplanm kresel ekilli karbamitin grnr younluu, ayn boyut aralna sahip dzensiz ekilli karbamitin grnr younluundan bir miktar yksek bulunmutur.
Demir tozuyla kaplanm daha byk boyutlu ve kresel ekilli karbamitler ak esnasnda daha az srtnme direnci
gsterdiklerinden grnr younluklar artmtr. Artan grnr younlukla birlikte demir tozuyla kaplanm karbamitlerin kalp ierisine ak davranlar ve preslenebilirlikleri daha iyi olmaktadr.
Ham numunelerin zndrmeden nce ve zndrmeden sonraki younluklar, karbamitin miktar, boyut aral ve ekline gre Tablo 2de verilmitir. Tabloda numunelerin zndrmeden nceki ham younluklar .. ve
zndrmeden sonraki ham younluklar .s. ile ifade edilmitir. zndrme sonras numunelerde bulunan
karbamitin giderilmesi sonucu numunelerin younluklar azalmtr.
Tablo 2 : zndrme ncesi ve sonras numunelerin ham younluklar
ekil 3de; farkl miktar, partikl boyut ve ekline sahip karbamit ilave edilerek retilmi ham numunelerde zndrme sonucu gerekleen hacim deiimleri karbamit miktarna gre verilmitir.
688

ekil 3 : Farkl miktar, partikl

ekli ve boyutuna sahip karbamit
ieren ham numunelerde
zndrme sonucu karbamit
miktarna bal olarak meydana
gelen hacim deiimleri
zndrme sonras tm numunelerde hacimsel byme meydana gelmi ve artan karbamit miktaryla hacim deiimi azalmtr. Metal tozuyla kaplanm karbamitlerin grnr younluklar artan karbamit miktaryla azalmtr.
Grnr younluun azalmasyla preslemede sktrma orann artmas, daha yksek oranda karbamit ilavesiyle
retilen numunelerin biraz daha mukavemetli olmasn saladndan bu numuneler zndrme sonucu daha az
hacimsel byme gstermilerdir. Kresel ekilli karbamit kullanlarak retilen numunelerin hacim deiimleri dzensiz ekilli karbamit kullanlarak retilen numunelere gre daha fazla bulunmutur. +500-710 m, +710-1000 m
ve +1000-1400 m boyut aralklarna sahip dzensiz ekilli ve +1000- 1400 m boyut aralna sahip kresel ekilli
karbamitin hac.%80 orannda ilavesiyle retilen numunelerde zndrme sonras hacimsel bymeler srasyla;
%1,32, 1,45, 1,56 ve 1,89 olarak tespit edilmitir. Demir tozuyla kaplanm kresel ekilli karbamitin grnr younluu yksek olduundan preslemede sktrma orannn dk olmas nedeniyle ham numunelerde hacimsel deiim
daha fazla gereklemitir. Sonular; demir esasl ham numunelerden karbamitin zndrlerek uzaklatrlmas
sonras meydana gelen hacimsel deiimler zerine en nemli etkiyi karbamit miktar ve eklinin yaptn, boyutun
etkisinin ise daha az olduunu gstermektedir. Karbamitin uzaklatrlmas ve 1200 Cde 1 saat sinterleme sonras
farkl oranlarda gzenek ieren numunelerin resimleri ekil 4de grlmektedir.
ekil 4 : (a) %47,5, (b) %56,0,

(c) %60,5 ve d) %70,8 gzenek
ieren numunelerin resimleri
Sinterleme sonras numunele3rin gzenek miktar, boyutu ve ekline bal olarak younluklar 2,25-4,09 g/cm ,
toplam gzenek oranlar %.48,4-71,1 ak gzenek oranlar %.23,8-68,4 ve kapal gzenek oranlar %2,6-27,1 arasnda deimitir. Azalan gzenek miktaryla ak gzenek oran azalrken kapal gzenek oran artmtr. Kresel ekilli
karbamit kullanlarak retilen numunelerde kapal gzenek oran; gzeneklerin birbirinden izole olmasndan dolay
daha yksektir.
ekil 5de farkl miktar, partikl boyut ve ekline sahip karbamit kullanlarak retilen ve 1200 Cde 1 saat sinterlenmi
numunelerde sinterleme sonras gzenek oranna gre gerekleen hacim deiimleri verilmitir.
ekil 5 : Farkl miktar, partikl

ekli ve boyutuna sahip karbamit kullanlarak retilen ve 1200
oCde 1 saat sinterlenmi
numunelerde gzenek miktarna
bal olarak meydana gelen
hacim deiimleri
689

Sinterleme ncesi daha az gzenek ieren numunelerin ham younluklar dierlerine gre fazla olduundan bu
numuneler sinterleme sonucu daha az hacimsel ekme gstermilerdir. Literatrde toz metalurjisi yntemiyle malzeme retiminde; Astaloy Mo tozlarndan retilen ham kompaktlarn 1120 Cde 30 dakika sinterlenmesiyle retilen
6,7 g/cm3 younluundaki kompaktlarda yaklak %0,2 orannda hacimsel ekme tespit edilmitir [11]. Karbamit
ilave edilerek toz metalurjisi yntemi ile yksek oranda gzenekli malzeme retiminde; uygulanan dk presleme
basnc ve retilen ham numunelerden karbamitin uzaklatrlmas sonucu younluklarnn dk olmas sinterleme
sonras daha fazla hacimsel ekmeye neden olmaktadr. Ayn boyut aralna sahip kresel ekilli karbamit kullanlarak
retilen numuneler dzensiz ekilli karbamit kullanlarak retilen numunelere gre daha fazla hacimsel ekme
gstermilerdir. +1000-1400 m boyut aralna sahip dzensiz ve kresel ekilli karbamitin hac.%80 orannda
ilavesiyle retilen numunelerin sinterlenmesi sonucu hacimsel ekmeleri srasyla; %6,88 ve %7,24 olarak tespit
edilmitir. Kresel ekilli karbamit kullanmnda ham numunelerde metal-metal toz temasnn artmasndan dolay sinterleme sonras daha fazla hacimsel ekme gereklemektedir. Farkl boyutlarda dzensiz ekilli karbamit kullanlarak
retilen numunelerde artan karbamit partikl boyutuyla hacimsel ekme artmtr. +500-710 m, +710-1000 m ve
+1000-1400 m boyut aralklarna sahip dzensiz ekilli karbamitlerin hac.%80 orannda ilavesiyle retilen numunelerin sinterlenmesi sonucu hacimsel ekmeleri srasyla; %6,36, %6,57 ve %6,88 olarak tespit edilmitir. Kullanlan
dzensiz ekilli karbamitin boyutu arttka ham numunelerde metal-metal temas noktalar artacandan sinterleme
sonras daha fazla hacimsel ekme meydana gelecektir.
zndrme sonras ham numunelerde karbamit miktar, partikl boyutu ve ekline bal olarak %1,38-3,29 arasnda hacimsel byme; sinterleme sonras numunelerde gzenek miktar, ekli ve boyutuna bal olarak %4,31-7,25
arasnda hacimsel ekme meydana gelmitir. Yksek oranda gzenek ieren Astaloy Mo numunelerin younluklar ve gzenek yapsnn; balangta kullanlan karbamit miktar, ekli ve boyutu ile kontrol edilebilecei saptanmtr.
Teekkr
Bu alma T-1431 proje numarasyla stanbul niversitesi Bilimsel Aratrma Projeleri Birimi tarafndan desteklenmitir.
KAYNAKLAR
1. BANHART, J., Manufacture, Characterisation and Application of Cellular Metals and Metal Foams, Progress in
Materials Science, 46, 559-632, 2001.
2. KREMER, K., LISZKIEWICZ, A., ADKINS, J., Development of Steel Foam Material and Structures, Technology
Roadmap Program 9913 Final Report, The United States Department of Energy and American Iron and
Steel Institute, 2004.
3. KOTAN, G., Production and Characterization of Porous Titanium and Ti-6Al-4V,
Master Thesis, Middle East Technical University, Department of Engineering Science, 2006.
4. CONDE, Y., DESPOIS, J.F., GOODALL, R., MARMOTTANT, A., SALVO, L., MARCHI, C.S., MORTENSEN, A.,
Replication Processing of Highly Porous Materials, Advanced Engineering Materials, 8 (9), 795-803, 2006.
5. BAKAN, H.I., A Novel Water Leaching and Sintering Process for Manufacturing Highly Porous Stainless Steel,
Scripta Materialia, 55, 203-206, 2006.
6. SURACE, R., FILIPPIS, C.D., LUDOVICO, A.D., BOGHETICH, G., Influence of Processing Parameters on Aluminium Foam Produced by Space Holder Technique, Materials and Design, 30, 1878-1885, 2009.
7. TUNCER, N., ARSLAN, G., Designing Compressive Properties of Titanium Foams, Journal of Materials Science, 44, 1477-1484, 2009.
8. GERMAN, R.M., Powder Metallurgy Science, The Pennsylvania State University, MPIF, Princeton, New Jersey,
1-878954-42-3, 1994.
9. KANG, S.L., Sintering, Densification, Grain Growth and Microstructure, Elsevier Butterworth-Heinemann, Linacre House, Jordan Hill, Oxford, 0-750663-855, 2005.
10. ORBAN, R.L., New Research Directions in Powder Metallurgy, Romania Report in Physics, 56(3), 505-516,
2004.
11. HGANS HANDBOOK-1, Material and Powder Properties, Sweden, 2004.
690

PSKRTMEL EKLLENDRME LEMNN GZENEKLLE

ETKLER
Shaker M. ASWAD ve Yusuf USTA*
Makina Mhendislii Blm, Mhendislik Fakltesi, Gazi niversitesi, 06570, Maltepe-Ankara,
*uyusuf@gazi.edu.tr
ZET
Bu almada, tasarmlar ve imalatlar yaplm olan yakndan elemeli nozullar ve gaz atomizasyon
nitesinde, alminyum tozu kullanarak pskrtme ekillendirme (P) ile silindir zerinde bir kaplama
tabakas oluturulmutur. Mekanik zellikleri dorudan etkilemesi nedeniyle, ekillendirme parametrelerinin gzeneklilie etkileri aratrlmtr. almann gerekletirilmesi iin kendi ekseni etrafnda dnen
bir silindir atomizasyon dorultusuna dik olarak konumlandrlmtr. Deneyler srasnda atomize edilen
tozlarn henz sv iken, sz konusu dnen silindire tutunmas salanmtr. Deney parametreleri olarak
pskrtme mesafesi, atomizasyon basnc ve yakndan elemeli nozulun u ksmnn knt mesafesi
seilmitir. Her bir parametre iin ayr deer (pskrtme mesafesi: 135, 165, 200 mm; atomizasyon
basnc: 5, 10, 15 bar ve knt mesafesi: 4, 6, 8 mm) eitli denemeler sonucunda belirlenmi ve her
bir art kez tekrarlanarak kaplamalar gerekletirilmitir. Yaplan deneylerin sonunda elde edilen
kaplamalarn kenar ve orta ksmlarndan numuneler alnarak gzeneklilik, taneler aras balant, tane
bykl ve tane ekli optik mikroskop altnda incelenmitir.
Anahtar Kelimeler: Pskrtme ekillendirme, yzey kaplama, gaz atomizasyonu, alminyum boru
EFFECT OF PARAMETERS OF SPRAY FORMING ON POROSITY

ABSTRACT
In this study, a coating layer has been formed on a cylinder with spray forming technique by using aluminum powders which has atomized by close coupled nozzles which have been designed and produced
before. Since porosity has a major effect on the mechanical properties of spray formed parts, effect of
the parameters on the porosity have been investigated in order to have higher mechanical properties.
n the experimental step, a spinning cylindrical tube has been located straight forward to the atomization direction. During the experiments, the atomized aluminum powder has been sprayed with the help
of nozzles when they were yet in the liquid form. The cylindrical tube rotates at different speed and the
coating has been applied from 3 different distances as being 135, 165 and 200 mm. Therefore, a coating
layer has been deposited on the surface of cylinder. n the study, the protrusion of 4, 6 and 8 mm at nozzle tip and 5, 10 and 15 bar pressure have been used besides of the spray distance. Each experimental
condition has been repeated 3 times. Samples have been taken from the center and side of the each
coated parts in order to examine their porosity, bonding with powders and substrate, powder sizes and
powder shapes under an optical microscope.
Keywords: Spray forming, surface coating, gas atomization, aluminum pipe
691

1. GR
Toz metalurjisi endstriyel olarak kullanlan imal usullerinden olmakla birlikte en farkl imalat yoludur.
Toz metalurjisi, metalrjinin, metalik toz veya bu tozlarn ekillendirilip sinterlenmesiyle yaplan rnlerin
imalat ile ilgili bir blmdr [1].
Toz metalurjisinin (T/M) amac metal ve metal alamlarnn tozlarn ergitmeden, basn ve scaklk
yardmyla dayankl malzemeler haline sokmaktr. Dier metal ileme yntemlerine gre daha farkl bir
uygulama olan T/Mnin stnlkleri; paralarn yksek kalitede, karmak yapda, kk toleranslarla ve
daha ucuz olarak retilebilmesidir [2].
T/M kk, karmak ve boyutsal hassasiyeti yksek paralarn seri imalatna son derece uygundur.
Belirli derecede gzenek (porozite) ve geirgenlik elde edilir. T/M ile retilen paralarn byk bir ksmnda elde edilen boyutsal hassasiyet ve yzey kalitesi talal ilem gibi ekstra operasyonlara olan gereksinimleri ortadan kaldrmas ve malzeme kaybnn ok az olmas T/M ynteminin ekonomik bir retim
yntemi olduunun gstergesidir [3].
Tane boyutu ve gzenek miktar gibi zellikler malzemelerin mekanik zelliklerini nemli lde etkiler.
Mekanik zelliklerin yksek olmasnn istendii durumlarda, tane yapsnn kk olmas ve gzeneklerin en az seviyede olmas gerekmektedir [4].
Metal pskrtmede esas prensip, zel olarak hazrlanm metalik yzeylere, ergitilmi sv metalin basnl gazlarn kinetik hz (itmesi) ile pskrtlmesidir. Bunlarn gnmz teknolojisinde kullanlan deiik usulleri olduu gibi daha yeni usuller de denenmekte ve kullanlmaktadr [5].
P ilemi, para retmek iin, atomizasyon ve birletirme/pekitirme olaylarnn srayla gereklemesi
prensibine dayanr. lemin ana ekiciliklerinden biri yksek malzeme biriktirme orandr (0,2-2 kg/s)
[6].
Ergimi metali hava, azot, argon veya helyum gazlar kullanarak paralamak suretiyle toz elde etme
ilemine gaz atomizasyonu denir. Sv metal akkan nozuldan kan yksek hzl gazn genlemesi
suretiyle paralanarak kk tanelere ayrlr. Gaz atomizasyonu; kresel yapl yksek younlukta, iyi
akclkta ve yksek kalitede olan tozlarn retilmesinde yaygn bir ilemdir. Ayn zamanda gaz atomizasyonu ile yksek saflkta az oksijen ieren metal tozu retimi mmkndr. Byle tozlarn, pskrtme
kaplama, pskrtme balama, kimya endstrisi, tp teknolojisi gibi geni bir kulanm alan vardr. Gaz
atomizasyonu, sper alamlar ile yksek alaml metallerde de ok baarl sonular vermektedir.
Bu yntemde gaz cinsi, gaz basnc, gaz ve sv metal ak debileri ile nozul geometrisi gibi retim parametreleri tozlarn fiziksel ve kimyasal zelliklerini etkilemektedir [7]. Yaygn bir toz retim teknii, metal
tozlarnn yaklak olarak %80i bu yntemle retilmektedir [8].
Pskrtme ekillendirme ynteminin iki nemli avantaj vardr. Bunlardan birincisi eriyikten direk olarak
tek bir operasyonla net ekillendirilmi rn elde etme imkandr. P ynteminin ikinci avantaj metalurjik
ve mekanik zelliklerde nemli lde iyilemenin salanmasdr [9].Biriktirilen damlacklarn yaps malzemedeki en belirgin zelliktir. nk son rnn mekanik zellikleri tamamen bu yapya baldr[10].
Bu paralar diske ulamadan katlam ve toz haline gelmilerdir. Pskrtlen sv younluu az ise bu
tabakalar arasnda kalnt gzenekler oluur. Genellikle gzenek miktar %3 ile %15 arasnda deiir.
Bununla beraber vurgulanmas gereken dier bir nokta ise, bu ekilde retilen paralarn mukavemetinin sinterlenmemi T/M rnlerine gre ok daha yksek olmasdr. Parann yaps disk dzleminde genellikle izotropik, normal ynde ise anizotropiktir. Snrl miktarda yaplan scak ekillendirme veya souk
ekillendirme ileminden sonra bu gibi yaplar genellikle izotropisini korurlar. Bu durum ise, genellikle
faydaldr (derin ekme srasnda kulakk verme, baak verme olayn azaltr) [11].
Bu almada, tasarmlar ve imalatlar daha nceden yaplm olan yakndan elemeli nozullar kullanlarak gaz atomizasyon nitesinde, alminyum tozu kullanlarak silindir zerinde homojen bir kaplama
tabakas oluturulmutur ve gzenekliliin mekanik zellikleri dorudan etkilemesi nedeniyle parametrelerin buna etkileri aratrlmtr.
692

2. DENEYSEL YNTEM
2.1. Atomizasyon almalar
Gaz atomizasyonu almalarnda, tasarm ve imalat yaplm olan yakndan elemeli laval tipi nozul
kullanlmtr. knt aparat olarak farkl uzunluklara sahip adet para, tozu retilecek metal olarak
alminyum, atomizasyon gaz olarak ise hava kullanlmtr.
Alminyum ergime scakl 660Cdir. Yaplan atomizasyon almalarnda ergimi alminyum 725
Cye kadar stlmtr. Ergimi alminyum, elik potann altndan atomizasyon gazyla buluma noktasna doru seramik tpn iinden akarken sv metalin scaklnn deimemesi iin ak memesi
ierisindeki seramik tpn etrafna, iki ucu voltaj deitiriciye bal olan diren teli sarlmtr. Metal ergitmeye baland andan itibaren voltaj deitirici 25 Va ykseltilmitir ve atomizasyon ilemi boyunca
bu deerde sabit tutulmutur.
6x4x145 mm boyundaki seramik tpn etrafna 0,7 mm apnda 1200 Wlk diren teli sarlm, seramik
tp ak memesinin iine yerletirilmitir. Seramik tpn dier ucuna knt aparat yerletirilmi ve
ak memesi ile knt aparat birbirine balanmtr. Seramik tpn iki ucundaki diren telleri 700Cye
kadar dayankl yanmaz kablo ile kaplanarak ak memesi zerindeki delikten dar karlm ve telin
iki ucu voltaj deitiriciye balanmtr. Ergitilecek olan alminyum pota ierisine atlmtr. Yaplan almalarda yaklak olarak her deney iin 250 g alminyum kullanlmtr. Alminyum scakl 725Cye
ulatnda ama-kapama mekanizmas zerindeki ubuun kaldrlarak, sv metalin atomizasyon ilemi gerekletirilmitir.
alma esnasnda Pyi etkileyen parametrelerden nozul ucundaki knt mesafesi, gaz basnc ve
pskrtme mesafesinin (pozisyon) etkilerini grmek amacyla baz n testeler uygulanarak parametrelerin balang deerleri belirlenmi ve sonularn etkilerini boyutlu grafiklerde yzey cevaplar eklinde grebilmek iin bir deney program yaplmtr. Bunun iin MINITABTM yazlmndan yararlanlmtr.
Her bir parametre iin deiik deer ve her bir artta tekrar esas alnarak Box-Behnken tipi deney
program oluturulmu, bylece normalde 81 adet olmas gereken deney says baz u deerlerin tekrarlarnn azaltlmas suretiyle 42 olarak bulunmutur. Bu deney program esas alnarak kaplamalar
yaplmtr.
2.2. Pskrtme ekillendirme Deneyleri
Atomizasyon ilemiyle elde edilen damlacklarn st ste ylarak biriktirebilmesi iin, gaz atomizasyon
nitesinde, nozul altna denk gelecek ve nozul ile mesafesi ayarlanabilecek bir mil tasarm ve imalat
yaplmtr (ekil 1). Bu milin belli bir hzla dnmesini salayabilmek iin 0,37 kW ve 200 dev/dk nominal
hza sahip tahrik motoru (redktr) ve AC motor srcs kullanlmtr (ekil 2). 50x40x250 mm boyutlarnda alminyum boru milin zerine yerletirilmitir (ekil 3).
ekil 1. Deney dzeneinin ematik grnts
693

ekil 2. Deney dzenei
ekil 3. Nozul altna yerletirilen mil ve boru montaj

Bundan sonraki aamada alminyum boru yzeyine nozullar vastasyla deney programna uygun srayla pskrtme ilemi uygulanp alminyum borunun yzeyi kaplanmtr (ekil 4).
(a) 5 bar, 4 mm knt uzunluu ve

135 mm pskrtme mesafesi
(b) 10 bar, 6 mm knt uzunluu ve

165 mm pskrtme mesafesi
(c) 15 bar, 6 mm knt uzunluu ve 200 mm pskrtme mesafesi

ekil 4. Kaplanm numunelerden rnek resimler
694

3. DENEYSEL BULGULAR VE TARTIMA

3.1. Testler in n Hazrlklar
Yaplan deneyler sonucu elde edilen kaplamalarn, nozulun tam altna gelen orta ksmlarndan ve kenar
ksmlardan birer numune alarak bakalite gmme ilemi yaplm ve parlatma ilemi yaplmtr. Elde
edilen parlatlm numunelerin OLYMPUS GX71 optik mikroskopta yzey morfolojileri incelenmi ve her
yzeye farkl yerlerden 5 adet fotoraf ekilmitir. Bu fotoraflar Image-J programnda (ekil 5) analiz
edilerek % cinsinden gzeneklilik miktarlar hesaplanmtr. Bu ilem iin nce fotoraflar ikili (binary)
koda dntrlm ardndan da siyah ksmlarn beyaz ksmlar oran bulunmutur. Elde edilen saysal deerler Minitab yazlmnda kullanlarak 3 boyutlu yzey cevaplar elde edilmi ve bu grafikler
zerine yorumlar yaplmtr. Numunelere ait mikroskoptan alnan rnek yzey grntleri ekil 6da
grlmektedir.
ekil 5. Image-J yazlmnda ikili koda dnm ve bulunan % gzeneklilik
(a) 5 bar, 8mm knt uzunluu,

kenar ksm, 135 mm pskrtme mesafesi
(b) 10 bar, 6mm knt uzunluu,

orta ksm, 165 mm pskrtme mesafesi
15 bar, 6mm knt uzunluu, orta ksm, 200 mm pskrtme mesafesi

ekil 6. Kaplama ile elde edilmi numunelerin rnek mikroskop grntleri (x400)
695

3.2. Gzeneklilik Testi

Kaplamalarn orta ksmlarndan alnan rnekler incelendiinde, 135 mm mesafeden yaplan pskrtme
deneylerinde beklendii gibi gzenek miktarnn orta blgede (%8) kenar ksmlardan daha az olduu
gzlenmitir (%11) (ekil 7). Pskrme mesafesinin artmasyla birlikte katlamann daha fazla olaca
bylece tanelerin kaplanan yzeye ylmas srasnda ekil deitirme kabiliyetinin azalmas nedeniyle
daha fazla gzeneklilik beklenmekte olup ekil 7 incelediinde artan pskrtme mesafesiyle birlikte
gzenekliliin de art gsterdii grlmektedir. Dier taraftan ekil incelendiinde, tane boyutunu etkilemesi dnlen nozul ucundaki knt mesafesinin deitirilmesinin gzeneklilik zerinde dikkate deer
bir etkisinin olmad grlmektedir. ekil 7den kartlan bir dier sonu ise btn artlar iin geerli
olmak zere gzenekliliin kenar blgelerde biraz daha yksek olduudur.
ekil 7. Kaplamalardaki gzeneklilie pskrtme mesafesi ve kntnn etkileri

Yaplan deneylerde atomizasyon basncnn etkileri incelendiinde, gerek kenar ve gerekse orta ksmlarndan artan basncn gzeneklilii etkili bir ekilde ve neredeyse lineer olarak azaltt grlmektedir
(ekil 8). Bu durum artan basnla birlikte toz boyutunun klmesi ve silindir zerine giderken daha
yksek hza sahip olmalar, bylece tozlarn daha yksek hzlarda arpmalar eklinde aklanabilir.
Yine beklendii gibi, basncn artmasnn orta ve kenar blgedeki gzenekliliklerde etkisinin olmad,
yani kenar blgelerde atomizasyon basnc artrlm olsa bile orta ksmlara gre daima daha yksek
gzenekliliin olutuu gzlemlenmitir.
ekil 8. Atomizasyon basnc ve knt uzunluunun gzeneklilie etkileri

3.3. Taneler Aras Balant, Tane Bykl ve Tane ekli Testleri
Tane eklinin, boyutunun ve mikro yapsnn incelenmesi iin numunelere dalama yaplmtr. Dalama
ilemi KELLER zeltisi kullanarak yaplmtr (2.5ml HNO3+1.5ml HCL+1ml HF +95ml saf su).
Dalama ilemi yaplmadan nce tane ekli ve bykl grnmemektedir (ekil 9).
696

ekil 9. Dalama ilemi yaplmadan nceki optik mikroskobu altnda yzey grnts (x400).
Dalama ilemi hem kle alminyuma ve kaplama numunelerine uygulanmtr. Yaplan dalama ilemi sonrasnda elde edilen grntler ekil 10da kle alminyum ve ekil 11de ise pskrtme sonras
elde edilen kaplamaya ait olacak ekilde verilmitir. Grlecei zere, atomizasyon ilemi P ile elde
edilen parann mikroyapsn nemli lde kltm, yass ve iri mikroyapy ortadan kaldrp, gittike kreselleen ve en nemlisi kk ve homojen bir mikroyapsn ortaya karmtr. Atomizasyon
basncnn 5 bar olduu numune incelendiinde, tane boyutunun olduka byk ve karmak geometrili
(kimi tanelerin ubuumsu kimisinin yamuk geometrili) olduu grlmektedir. Basn arttrlp 10 bara
ykseltildiinde tanelerin kld ayn zamanda da kreselletii gzlemlenmitir. Basn 15 bara
ykseltildiinde ise tane boyutunun beklendii gibi daha da kld ve neredeyse tamamnn kresel
geometriye brnd grlmektedir.
Resim 10. Dalama ilemi yaplan alminyum ktk numunesinin tane ekli ve bykl (x400)
ekil 11. Orta ksm alnm bir numunede tane ekli ve bykl (x400)
697

Her ne kadar tanelerin yar kat bir ekilde arpt ve taneler arasndaki snrlarn ok net olarak
grlmesi beklenmese de, elde edilen dalanm numunelerin mikroskop grntlerinden tozlarn tane
boyutlar llmeye allmtr. Tane boyutunu lmek iin mikroskopta daha nce numune fotoraflar iin kullanlan ayn piksel ayarlarnda gerek kalnl 0,100 mikron olan sac malzemenin fotoraf
ekilmi, buna gre tane boyutlarnn gerek lsn bulmak iin karlatrma yaplmtr. En az 7
adet rnein tane boyutu ortalamas alnmtr. Bunun sonucunda, 5 barda yaplan kaplamalarn tane
boyutlarnn ortalamas = 22,3 m iken bu byklk 10 bar iin 10,5 m ve 15 bar iin de 4,8 m olarak
llmtr (ekil 12).
Resim 12. Image-J program ile tane boyutu lme

4. SONULAR
Bu almada, nceden yaplm yakndan elemeli laval tipi nozul kullanlarak, gaz atomizasyonu yntemiyle hava atomize alminyum tozu retilmesi ile birlikte eitli mesafelerde dnen bir silindirin yzeyinde pskrtme ekillendirme ile alminyum kaplamas yaplmtr. almadan elde edilen sonular
aada verilmitir:
1. Kaplamalarn orta ksmlarndaki gzenekliliklerin, kenar ksmlardan daha az olduu gzlenmitir.
2. Pskrtme mesafesi arttka gzenek miktar artt tespit edilmitir. En az gzenek miktar 135mm
pskrtme mesafesinde elde edilmitir. Dolaysyla, yksek younluk iin pskrtme mesafesinin
mmkn olduunca ksa tutulmas gerekmektedir.
3. Artan atomizasyon basncyla gzenek miktarnn da dzenli olarak azald grlmtr.
4. Mikroyaplar incelendii zaman, beklendii gibi normal bir dkme gre olduka ince ve homojen bir
yap elde edilmitir. Daha nceki almalardan anlalaca gibi, ince taneli mikroyapnn mekanik
zellikleri arttraca beklenmektedir. Bu alma sonucunda elde edilen avantajlardan biri, pskrtme ekillendirme yntemi ile tozlarn ylmas yapldndan, ok ince bir tane yaps, dolaysyla
mekanik zelliklerde belirgin art olarak zetlenebilir.
698

TEEKKR
Bu alma Gazi niversitesi Bilimsel Aratrma Projeleri tarafndan 06/2010-58 kodlu proje olarak desteklenmitir. Teekkr bir bor biliriz.
KAYNAKLAR
1. Bozkurt, ., nal, R., Gaz atomizasyon yntemi ile metal tozu retiminde gaz ak modelleri, I.
Ulusal Metalurji Ve Malzeme Gnleri Bildiri Kitab, Osmangazi niversitesi, Eskiehir, 099, 2004.
2. German, R., M., Powder Metallurgy Science 2nd edition, Metal Powder Industries Federation,
USA, 16-20, 76-90, 1984.
3. nternet:http://mf.dumlupinar.edu.tr/~runal/toz/powdermet.html
4. Yldz, E., S., Gaz atomizasyonu ile metal tozu retiminde, nozul geometrisinin toz boyutuna etkisinin aratrlmas, Yksek Lisans Tezi, Dumlupnar niversitesi Fen Bilimleri Enstits, Ktahya,
2007.
5. nternet:http://mf.dpu.edu.tr/~runal/toz/sprayforming.pdf
6. Bozda, V., Yakndan elemeli laval nozul kullanlarak yaplan pskrtme ekillendirmenin mekanik
zelliklere etkisinin aratrlmas, Yksek Lisans Tezi, Gazi niversitesi Fen Bilimleri Enstits,
Ankara, 2008.
7. Uslan, ., Kkarslan, S., Kalay tozu retimine gaz atomizasyonu parametrelerinin etkisinin incelenmesi, Gazi niversitesi Mhendislik Mimarlk Fakltesi Dergisi, 25(1): 1-8 2010.
8. Uslan, ., Toz Metalurji retim Teknikleri, Gazi niversitesi, Mh. Fak. Yksek Lisans Ders
Notlar, 2009.
9. Odaba, A., Altmolu, S., A., Eruslu, N., Toz metalurjisine alternatif: Osprey prosesi, I. Ulusal
Metalurji ve Malzeme Gnleri Bildiri Kitab, Osmangazi niversitesi, Eskiehir, 099, 2004.
10. Cai., W., D., Smugeresky, J., Lavernia, E., J., Low-Pressure Spray Forming of 2024 Aluminum
Alloy, Material Science and Engineering A, 241 (1-2): 60-71 1998.
11. Ekici, A., Ekstrzyonla tam younlatrlm pskrtme ekillendirme alminyumun mekanik zelliklerinin deneysel olarak aratrlmas, Yksek Lisans Tezi, Gazi niversitesi Fen Bilimleri Enstits, Ankara, 2005.
699

MECHANICAL
ALLOYING
www.turkishpm.org
700

The effect of gradual process control agent technique

on the morphology of Al powders fabricated by high
energy ball milling
Aykut Canakci1, Temel Varol1
Abstract
In this work, a new method was developed in relation to process control agent. This new method was called as
gradual PCA technique. The morphology and the microstructure of the milled powder were evaluated using SEM
and XRD techniques, respectively. Also the relationship among the stages of milling was examined. For determining
relationship between particle hardness and amount of PCA was measured the microhardness of the particle. In addition, the particle size change with milling time and the amount of PCA was investigated. It was observed that the
effectiveness of milling increase by the gradual PCA technique. In other words, this method increases the efficiency
of milling balls at the beginning of the process. Hence, it is observed that the amount of PCA up to 2h of milling time
has a significant effect on particle microhardness and particle size. As a result, a new technique which increases
the efficiency of milling process were carried out using a planetary ball mill.
Keywords: Process control agent (PCA), Gradual PCA technique, Mechanical alloying (MA), High energy milling
1. Introduction
Mechanical alloying or high energy milling (HEM) is a solid-state powder processing involving repeated welding,
fracturing, and rewelding of powder particles in a high-energy ball mill and this process has the advantages of
the synthesis of nanostructure materials with high purity at large quantities at room temperature [1-4]. Besides
mechanical alloying or high-energy ball milling can produce a fine and homogeneous distribution of the hardening
particles [5-10]. The high energy involved in the MA process fragments and cold rewelds powder particles that form
the initial mix. The microstructure of final powders is usually finer than of powders obtained by atomization and has
grain size levels similar to those obtained using rapid solidification techniques [11].
Process variables in MA technique or HEM process such as milling time, milling speed, ball-to-powder weight ratio
and process control agent have effects on the final structure and morphology of the powders [12].
In high energy milling process, process control agents (PCAS) play a significant role in controlling the particle size
and degree of cold welding during ball milling. A process agent is a surface additive used in the milling process in
order to control the balance between the fracturing and cold welding of particles. The application of PCA to MAed
powder enables to reduce cold welding and promote fracturing [13-16]. PCAs adsorb on the surface of the powder
particles and minimize cold welding among powder particles, thereby inhibiting agglomeration. A wide range of
PCAs has been used in practice at a level of about 1-5wt% of the total powder charge. The most important PCAs
include stearic asit, hexane, methanol and ethanol [17].
PCA must be used in milling process for most material systems because of the balance between cold welding and
fracturing doesnt occur naturally. Many researches [18-20] have used PCA to prevent excessive cold welding of
particles during milling but so far, any researchers has not used gradual PCA technique. All of PCA is usually emptied to vial at the beginning of the process. However There are important differences between the two processes
in of results.
701

The present work aims to investigate of the gradual PCA technique on the characteristics of mechanical alloyed
powders.
2. Experimental procedure
Gas atomized Al powders with average particle size of 377m (Gndodu Exotherm Company, Turkey) were used
as raw materials. Fig 1 shows the morphology of the as received Al powders. The chemical composition of the
as-atomized Al alloy (in wt. %) is 1.230Fe, 1.000Si, 1.000Pb, 0.710Cu, 0.530Zn, 0.116Mn, 0.071Ti, 0.050Mg and
Al (balance).
Fig. 1. Morphology of the as received Al powder.

The initial powders have ligamental shape and which were milled by a high-energy ball milling up to 7h. The milling
process was carried out in a planetary ball-mill (Fritshc Gmbh, model Pulverisette 7 premium line) at room temperature using tungsten carbide bowl and high argon atmosphere. Tungsten carbide ball with a diameter of 10mm
were used to milling process. The ball-to-powder weight ratio (BPR) and rotational speed were 10:1 and 400rpm,
respectively. Methanol (Merck) was used as PCA. In order to investigate the effect of gradual PCA technique were
used wt.% beginning of PCA 0, 0.25, 0.5, 0.75, 1 and 2, respectively. This process is given in Table 1. In order to
avoid the formation of some intermetallic fractions and the heating by milling, process was stopped every 30 minutes than resumed when the temperature of the bowl decreased to the room temperature.
Table 1. Gradual PCA application process.
Milling Time (h)
Process
Code
Total of PCA
(wt.%)
P1
P2
0.25
0.25
0.25
0.25
0.25
0.25
0.25
0.25
P3
0.5
0.214
0.214
0.214
0.214
0.214
0.214
0.214
P4
0.75
0.179
0.179
0.179
0.179
0.179
0.179
0.179
P5
0.143
0.143
0.143
0.143
0.143
0.143
0.143
P6
The size distribution of as-received and milled powders was quantified by a laser particle size analyzer (Malvern,
model Mastersizer Hydro 2000). The phase analysis of milled products was evaluated by X-ray diffraction (XRD)
(Rigaku Corporation, Japan) using CuK radiation (1,54059 Ao) operating at 30mA and 40 kV. The XRD patterns
were recorded in the 2 range of 20-100 o (step size 0.02o and time per step 1s). Crystallite size in the milled powders were calculated from the XRD line broadening using the Scherrer equation. For this purpose, some Al powders
were annealed to minimize the strain field in lattice of the powder particles. After annealing, x-ray diffraction patterns
of annealed powders and the full width at half maximum intensity of the peak were measured to eliminate instrumental broadening effect. After that the full width at half maximum intensity of the peak was recorded from x-ray
diffraction patterns of milled powders. Scherrer equation can be written as follow:
702

(1)
(2)
where, B is the modified peak full width, is the Bragg angle, is the wavelength of the x-radiation used, d is the
crystallite size, Bm is the peak full width at half the maximum intensity of x-ray diffraction patterns of milled powders,
and Ba is the peak full width at half the maximum intensity of x-ray diffraction patterns of annealed powders.
The morphology of powders particles was investigated by scanning electron microscopy using Zeiss LS10. Morever
the microhardness of Al powders have been measured using a vickers microhardness tester (Struers microhardness tester) at an load of 98.7mN for 10s.
3.1. Effect of gradual PCA technique on milling process
Milling process is given in Table 2. Process is summarized in the Table 2 for better understanding of the stages of
milling. Table 2 shows the effect of the gradual PCA process on the mechanical alloyed Al powders.
Table 2. The shapes of milling during the mechanical alloying.
Milling Time (h)
Process
0.5
P1
Fracture and cold

welding
Cold welding
Cold welding
Cold welding
Cold welding
P2
Fracture and cold

welding
Fracture and
flattened shape
Fracture
Fracture
Fracture
continues
P3
Little fracture
A little fracture and

a little flattened
shape
Fracture and
flattened shape
Fracture
Fracture
continues
P4
A little fracture
A little fracture and

a little flattened
shape
Fracture and
flattened shape
Fracture
Fracture
continues
P5
No fracture
Little fracture and

little flattened
shape
Little fracture and

little flattened
shape
Fracture
Fracture
continues
P6
No fracture
Little fracture and

little flattened
shape
Little fracture and

little flattened
shape
Fracture
Fracture
continues
Fig. 2 shows the used milling medium component (bowl and balls) and Al powders before and after milling. Fracture
and cold welding occured between particles up to 0.5h of milling.
Cold welding process is effective up to from 0.5 h to 7h and particle size is increasing continuously. The average
particle size is 1600 m at the end of 7h. It can be observed that cold welding lead to be little cold welded to bowl
surfaces after milling time of 7h (Fig. 2b). One of the remarkable events of this process, sticking of Al powders on
the surface of the bowl is very little.
However, Fig. 2c gives another example of Al powders being serious cold welded to a milling ball. As it can be seen
in Fig 2b and 2c, the sticking of Al powders on the surface of bowl and balls increases with increasing milling time
so impact energy of balls decreases. As a result, the milling of ductile metal powders is not possible without PCA.
This result is a negative result for milling process but this process may be considered as a new surface coating
method [21,22].
703

(a)
(b)
(c)
Fig. 2. Used milling medium components (bowl and balls) and Al powders before and after milling for P1 . (a)
Bowl and balls before milling, (b) Bowl after milling (7h), (c) Al powders and ball surfaces after milling (7h).
Compared to applications by looking at process images of the P1 and P2, the addition a small amount of PCA can
easily see the effect on milling process. With the addition of 0.25 wt. %PCA, powders were fractured and flatten
shape after 0.5h of milling. This result is an evidence showing that a high level of efficiency of the P2 process. As
shown in the process images (Fig. 3a), At the end of milling, balls and bowl surfaces for P2, P3, P4, P5, and P6
processes have light freckles (Fig. 3).

Bowl after milling
Al powders and ball surfaces after milling
(a)
(b)
704

(c)
(d)
(e)
Fig. 3. Used milling medium components (bowl and balls) and Al powders after milling for gradual PCA processes:
(a) P2, (b) P3, (c) P4, (d) P5, and (e) P6.
3.2. Effect of gradual PCA technique on the powder morphology
The particle morphology of milled powders for gradual PCA processes are showed in Fig. 4. It can be observed
that different powder morphologies were obtained for different amounts of PCA and different milling times. Initial Al
powders particles have ligamental shape. When particle morphologies was examined at the end of 0.5h of milling it
was observed; ligamental morphology was completely disappeared and an abnormal growth of particle size due to
the cold welding in the P1 process. Moreover, powders morphology have spherical and flatten shape and particle
size is constantly growing for all milling times. Eventually, the cold welding process becomes almost dominant on
the powder which was milled without PCA. Ligamental powders were fractured and which change into flatten shape
in P2 process during 0.5h of milling process (Fig. 4a).
After that 0.5h, fracture process is active process. There is no significant change in particle morphology up to 2h
of milling, but the particle size slightly decreased. After this stage up to 7h, the tendency to fracture dominates
over cold welding. Particle morphology exhibited a morphology which has similar spherical morphology after 2 h of
milling. The amount of PCA is above the critical value for the P3 process so fracture process efficiency is little up
to 0.5h (Fig. 4b). After this stage up to 7h, the tendency to fracture dominates over cold welding and particle size
decreases with increasing milling time.
A similar behaviour was observed with previous studies [23-26] in all the cases. Moreover, the amount of reduction
in particle size decreases with increasing the amount of PCA. Flatten particle morphology can not be reached at the
end of 1h milling in P4 process (Fig. 4c). As can be seen from SEM images (Fig. 4c and Fig. 4d), the effectiveness
of fracture decreases with increasing the amount of PCA. P4, P5, and P6 processes are similar to the processes in
terms of change of particle morphology but changes in particle size are slightly different.
705

Fig. 4. Morphologies of Al powders at after different milling times for gradual PCA processes: (a) P2, (b) P3, (c)
P5, and (d) P6.
3.3. Effect of gradual PCA technique on the particle size
During high energy milling, plastic deformation, cold welding and fracture are predominant mechanisms, in which
the deformation leads to a change in particle shape, cold welding leads to an increase in particle size and fracture
leads to decrease in particle size. Fig. 5 shows the particle size distribution of Al powders for P2 process after the
milling times of 0.5, 1, 2, 5, 7h, respectively. Table 3 presents average particle size values after 0h, 0.5h, 1h, 2h, 5h,
7h of milling times for all processes. As can be seen from Table 3, except for P1 process, particle size decreases
with increasing milling time for all processes. However, the particle size of P2 decreases to be the highest in gradual
706

processes. This result is another evidence showing that a high level of efficiency milling of the P2 process. Unlike
most of the work related to mechanical alloying [10,27-33], in this study, this particle size decreases continuously
because of initial powders have ligamental shape. Powders are deformed due to high energy collisions of balls and
they are fractured from fine regions. Flatten shape occurs after this fracturing process so particle size decreases
unlike increasing at early stage of milling. With increasing milling time, work hardening of powders causes brittle of
powders and fracturing process becomes effective process.
Table 3. Particle size of Al powders at after differents milling times for gradual PCA processes.
Process
Milling time (h)

0
0.5
P1
377
500
790
950
1200
1600
P2
377
269
200
120
40
18
377
337
242
150
58
34
P3
P4
Particle
size
(m)
377
344
327
186
63
40
P5
377
360
340
269
68
43
P6
377
367
361
332
71
45
Fig. 5. The change of particle size of Al powders with milling time and gradual PCA process.
The most effective gradual proces was found to be P2 process. The average particle size in this process was decreased from 377m to 18m, as seen in Table 3. Ball-impact energy of balls decreases because of increasing the
beginning amount of PCA so work hardening of particles decreases and there was no significant change in particle
size. Significant reduction of particle size in P3, P4, P5, P6 processes occur during milling from 2h to 7h. It should
be noted that almost no change in particle size up to 2h of milling in P6 process because of the beginning amount
of PCA is higher than the beginning amount of critical PCA.
4. X-ray Diffraction analysis of milled powders
Crystallite size determination is one of the most important applications in powder diffractometry for materials characterization. XRD pattern of milled powders for P2 process are illustrated in Fig. 6. Al powders underwent deformation and cold welding caused by continuous collision and split between balls and powders. As can be seen in Fig.
6, ball milling makes diffraction peaks become wide and the peaks intensities decrease.
707

Fig. 6. The change of XRD patterns of milled Al powders at different milling times for P2 process.
The effect of milling time on the crystallite size for Al powders are shown in Fig. 7. A rapid decrease in crystallite size
of Al powders from 0h to 0.5h of milling time but after 0.5h of milling only a slight further decrease in crystallite size
occurs as confirmed by other studies [15,16,34]. This result indicates that P2 process is highly effective in reducing
crystallite size by increasing milling time.
Fig. 7. Variation in crystallite size for as a function of milling time.

5. Effect of gradual PCA technique on the particle microhardness
The change of microhardness of milled powders as a function of milling time and gradual PCA is given in Table 4.
Generally, increasing milling time increases the deformation and work hardening of powders. As can be seen in
Table 4 and Fig. 8, there is a continuous increase in microhardness of all process with increasing milling time and
there is a continuous decreases in microhardness with increasing the beginning amount of PCA up to 2h of milling.
The initial amount of PCA begins to approach for all processes after 2h of milling so the microhardness values are
almost the same for 5h and 7h.
708

Table 4. Milled powder of microhardness at different milling time for gradual PCA processes.
Milling time (h)
Process
0.5
P1
33
101
117
124
125
125
P2
33
89
106
123
126
128
P3
P4
P5
P6
Microhardness
(Hv)
33
68
88
115
123
124
33
67
87
113
121
122
33
66
75
93
120
121
33
65
74
88
110
120
Fig. 8 shows variation of microhardness of powders versus milling time for P2, P4 and P6 processes. As can be
seen increasing milling time causes a raise in microhardness of particles. The main factor effecting the microhardness of powders is work hardening of powders. At the beginnig of milling the rate of increasing of microhardness is
so much but this rate decreases as milling time increases gradually.
Fig. 8. The change of microhardness at different milling time for gradual PCA processes.
6. Conclusions
The effect of gradual process control agent on high energy milling process was examined. Stages of the process,
powder morphology and particle size for All process were investigated. The results showed that the P2 process is
the most efficient process so crystallite size of P2 process was investigated. Morever, change of microhardness of
powders as a function of milling time for all process were examined.
The results are remarked as below:
1. Gradual process control agent technique reduces the size of Al powders rapidly because of increasing the fficiency of milling balls at the beginning of high energy milling process. Consequently, the researchers working on
high energy milling or mechanical alloying, avoiding the use of PCA more than critical amount of PCA may increase
the efficiency of milling process.
2. The optimal amount of PCA for Al powders (10:1 ball-powder weight ratio) is 2 % by weight.
3.Particle microhardness decreases with increasing amount of PCA during 2h of milling.
4. Particle microhardness increases wiht increasing milling time.
5. It was seen, milling process which is applicated without PCA can be used as a novel surface coating technique.
709

Acknowledgement
providing Al powders.
References
1. I. Estrada-Guela, C. Carreno-Gallardo, D.C. Mendoza-Ruiz, M. Miki-Yoshida, E. Rocha-Rangel, R. MartinezSanchez, Journal of Alloys and Compounds 483 (2009) 173177
2. S.Gomari, S.Sharafi, Journal of Alloys and Compounds 490 (2010) 2630
3. Li Lu, Y.F. Zhang, Journal of Alloys and Compounds 290 (1999) 279-283
4. B.D. Long, H. Zuhailawati, M. Umemoto, Y. Todaka, R. Othman, Journal of Alloys and Compounds 503 (2010)
228-232
5. B. Prabhu, C. Suryanarayana, L. An, R.Vaidyanathan, Mater Sci Eng A 425 (2006) 425:192.
6. MS. El-Eskandarany, Journal of Alloys and Compounds 279 (1998) 26327.
7. H. Arik Materials & Design 25 (2004) 31:40.
8. Naiquin Zhao, Philip Nash, Xianjin Yang, Journal of Materials Processing Technology 170 (2005) 586-592.
9. Yusuf Ozcatalbas, Composites Science and Technology 63 (2003) 53-61.
10. SS. Razavi Tousi, R. Yazdani Rad, E. Salahi, I. Mobasherpour, M. Razavi Powder Tech 192 (2009) 346351.
11. E.M. Ruiz-Navas, J.B. Fogagnolo, F. Velasco, J.M. Ruis-Prieto, L. Froyen, Composite: Part A 37(2006) 21142120.
12. Kh. Gheisari, S. Javadpour, J.T. Oh, M.Ghaffari Journal of Alloys and Compounds 472 (2009) 416-420.
13. Keke Gan, Mingyuan Gu, Journal of Materilas Processing Technolgy 199 (2008) 173-177.
14. M. A. Shaikh, M. Iqbal, J. I. Akhter, M. Ahmad, Q. Zaman, M. Akhtar, M.J. Moughal, Z. Ahmed, M. Farooque,
Materials Letters 57 (2003) 3681-3685.
15. L. Shaw, M. Zawrah J. Vllegas, H. Luo, D. Mracle, Metallurgical and Materials Transactions A 34A (2003)
159-170.
16. M. Pilar, J.J. Sunol, J. Bonastre, L. Escoda, Journal of Non-Crystallne Solids 353 (2007) 848-850.
17. C. Suryanarayana, Mechanical Alloying and Milling, New York, 2004.
18. Lu, Li., Zhang, Y.F., Influence of process control agent on interdiffusion between Al and Mg during mechanical
alloying, Journal of Alloys and Compound, vol. 290, 1999, pp. 279-283.
19. Pilar, M., Suol, J.J., Bonastre, J., Escoda, L., Influence of process control agents in the development of a
metastable FeZr based alloy, Journal of Non-Crystalline Solids, vol. 353, 2007, pp. 848-850.
20. Long, B.D., Zuhailawati, H., Umemoto, M., Todaka, Y., Othman, R., Effect of ethanol on the formation and properties of a CuNbC composite, Journal of Alloys and Compound, vol. 503, 2010, pp.228-232.
21. Iman Farahbakhsh, Alireza Zakeri, Palavesamuthu Manikandan, Kazuyuki Hokamoto, Applied Surface Science
257 (2011) 28302837.
22. S. Romankov, W. Sha, S.D. Kaloshkin, K. Kaevitser, Surface & Coatings Technology 201 (2006) 32353245.
23. M. Azimi, G.H. Akbari, Journal of Alloy and Compounds 509 (2011) 27-32.
24. Hafeez Ahamed, V. Senthilkumar, Journal of Alloy and Compounds 505 (2010) 772-782.
25. S.M. Zebarjad, S.A. Sajjadi, Materials and Design 27 (2006) 684-688.
26. JB. Fogognolo, F. Velasco, MH. Robert, JM. Torralba, Mater Sci Eng A 342 (2003) 131143.
27. J. A. Rodrigues, J. M. Gallardo, E. J. Herrera, Journal of Materials Science 32 (1997) 3535-3539.
28. H. Abdoli, H. Asgharzadeh, E. Salahi, Journal of Alloys and Compounds 473 (2009) 116-122.
29. J.J. Fuentes, J.A. Rodriques, E.J. Herrera, Materials Characterization 61 (2010) 386-395.
30. Yan J-w, Lu Y, Peng A-f, Lu Q-g, Trans. Nonferrous Met. Soc. China 19 (2009) 711-717.
31. G. Pozo Lopez, S.P. Silvetti, Physica B 354 (2004) 141-144.
32. J.B. Fogagnolo, D. Amador, E.M. Ruiz-Navas, J.M. Torralba, Materials Science and Engineering A 433 (2006)
45-49.
33. Xuren Liu, Yongbing Liu, Xu Ran, Jian An, Zhanyi Cao, Materials Characterization 58 (2007) 504-508.
34. H. Zuhailawati, Y. Mahani, Journals of Alloys and Compounds 476 (2009) 142-146.
710

MEKANK ALAIMLAMA LEMNDE UYGULANAN DK ENERJL

KESME GERLMLER YARDIMIYLA KARBON NANO UBUKLARIN
RETM
mer GLER, Ertan EVN
Frat niversitesi Metalurji ve Malzeme Mhendislii Blm, Elaz oguler@firat.edu.tr
zet
Bu almada, mekanik alamlama ilemi esnasnda grafit tozlarna dk enerjili kayma gerilimleri uygulanmtr.
Alamlama ilemi 250 saatte tamamlanm ve ardndan elde edilen tozlar argon atmosferi altnda 1600 Cde 4
saat sre ile tavlanmtr. Alamlanan numuneler, X-n difraksiyon analizi (XRD), Alan etkili taramal elektron mikroskobu (FE-SEM) kullanlarak incelenmitir. ncelemeler sonucunda karbon nano ubuk yaplar tespit edilmitir.
Anahtar Kelimeler: Karbon Nano ubuk, Mekanik Alamlama
THE PRODUCTION OF CARBON NANOROD THE HELP OF LOW ENERGY

SHEAR STRESSES APPLIED AT THE MECHANICAL ALLOYING PROCESS
Abstract
In this study, low energy shear stresses were applied to graphite powders during mechanical alloying process. Mechanical alloying process was performed for 250 hours and subsequently, milled powders were annealed at 1600
C under argon atmosphere during 4 hours. Samples were investigated by using X-ray diffraction analysis (XRD),
field emission scanning electron microcopy (FE-SEM). Carbon nano-rods were determined by investigations.
Keyword: Carbon Nano-Rod, Mechanical Alloying
1. GR
Grafit, hegzagonal kristal yapnn yksek anizotropisinden dolay pek ok farkl zellikler sergileyen ve bu sebeple
zerinde youn almalar yrtlen bir malzemedir. Grafit nano-partikller ve nano-tabakalar, arj edilebilir lityum
bataryalarda elektrot olarak, yksek scaklk uygulamalar iin conta olarak, nano-kompozit malzemelerde takviye
eleman olarak kullanlmas gibi pekok teknolojik uygulamada kullanm asndan byk potansiyele sahiptirler
[1]. Bu malzemeler kimyasal veya mekanik olarak retilebilirler. Mekanik deformasyon ile karbon nano yaplarn
elde edilmesi uzun yllardr allan bir konudur [2-3]. Yaplan almalar sonucunda, plastik deformasyonun grafitte yapsal deiimlere sebep olduu ve farkl trden hatalar ortaya kt grlmtr. Mekanik deformasyon
iin en ok kullanlan deneysel metot, bir deirmen ierisinde grafitin tlmesi ilemidir. Mekanik alamlama
ilemi sresince partikl boyutunda klme ve mikro yapsal deiim meydana gelir. Bu durum, bilyeler tarafndan
uygulanan gerilme trne gre deiir. Uygulanan gerilme tr darbe veya kayma eklinde olabilir. Grafite kayma
trnden gerilmeler uygulanmas durumunda nispeten kristal yapsn muhafaza etmi yksek anizotropik partikller meydana gelirken [1], darbe trnden gerilmeler uygulanmas durumunda amorf veya nano poroz karbon yaplar
meydana gelir [4].
711

Bu almada grafit tozlar mekanik alamlama (MA) ilemine tabi tutulmu ve mekanik alamlama (MA) srasnda
kayma trnden gerilmeler uygulanmtr. Mekanik alamlama ileminden hemen sonra tozlara yksek scaklkta
sl ilem uygulanarak tozlarda meydana gelen deiimler incelenmitir.
2. DENEY ALIMALARI
Grafit tozlar (Merck kGAA, 99.5%, <50 m) Planeter tipteki Fritsch Pulverisette P7 cihaz ile 19 mm apnda tek
bilye kullanlarak (Bilye/toz oran 8/1) 50 saatten balayarak 250 saate kadar MA ilemine tabi tutulmutur. MA ilemi 15 dakika MA ve 30 dakika souma iin bekleme eklinde yaplmtr. MA deneyleri ncesinde kaplar ve bilyeler
alkolle temizlenmitir. alma devri olarak 400 devir/dak seilmitir. 250 saat MA yaplm tozlara 1600 oC de 4
saat sl ilem uygulanmtr. Numuneler koruyucu ortam ierisinde argon atmosferi altnda hazrlanm, sl ilemler ise 0,1L/dak debideki akkan argon yatak altnda yaplmtr. MA ilemi sonras tozlar CuK (1,5406 ) mas
altnda XRD incelemelerine tabi tutulmutur. Isl ilem sonrasnda toz numuneler zerinde Fei Nova Nanosem 600
markal cihazla FE-SEM incelemeleri yaplmtr.
3. SONULAR
ekil 1. de 400 devirde tek bilye ile 50, 100, 150, 200 ve 250 saat MA yaplm tozlarn XRD deiimi verilmitir.
ekil 1: 50, 100, 150, 200 ve 250 saat MA yaplan tozlarn XRD deiimi.
26o civarnda grlen karbonun (002) pikinin 250 saat MA sonunda iddetinde azalma meydana gelmitir
ve artan MA sresiyle birlikte tozlarda bir miktar amorf yap ortaya kmtr. 50 saat MA ile 250 saat MA sonunda
elde edilen piklerin iddetleri oran () 2,6dr. Yaplan TEM incelemeleri sonucu ve Debye-Scherrer forml (1)
kullanlarak yaplan hesaplamalar sonucu 50 saat MA sonras ortalama toz boyutunun 230 nm olduu ve artan MA
sresiyle birlikte toz parack boyutunun azald ve 250 saat MA sonunda ise 160 nm ye kadar dt tespit
edilmitir.
(1)
712

Ps parack boyutu, dalga boyu, FWHM full width at half-maximum, 1 ise krnm asdr.
50 saatten balayarak 250 saate kadar olan MA srecinde kap ve bilyelerden anarak kopan Fe nin sementite
(FexC) dnt tespit edilmitir. MA srasnda tozlara uygulanan deformasyon enerjisi FexC nin (x=2 ve 3) dk
scaklkta olumasna sebep olmaktadr. MA ileminin balangcndan 24 saat sonra, tme kaplarnn scakl bir
sl ift ile llm ve 32 oC olduu grlmtr.
Literatrde molar oranlarda kartrlan Fe ve C tozlarnn MA ilemi ile 5 saat sonunda Fe3C ye dntkleri (in-situ
dnm) hususunda bilgiler bulunmaktadr [5]. FexC tozlarnn parack boyutunun ise (1) denklemi kullanlarak
240 nm den balayp 170 nm ye kadar indii hesaplanmtr.
Grafite kayma trnde gerilmelerin uyguland almalar incelendiinde bu almalarn tamamnda kayma gerilmesinin darbe tipi gerilmelere gre daha az kristal kusuru oluturduu belirtilmektedir [1,6,7].
Kayma gerilmeleri ksa bir sre iin uygulandnda yapda pek bir deiim gzlenmemi ve tlmemi grafitin
yapsna yakn yaplar tespit edilmitir. Artan MA sresiyle beraber grafit tabakalarnda pul pul dklmelerin olduu
ve kristal yaplarn koruyan nano tabakalarn olutuu rapor edilmitir [1].
Yaplan FE-SEM incelemeleri sonucu, 250 saat MA ilemine tabi tutulmu 1600 oC de 4 saat tavlanm numunelerde kalnl 15 nm in altnda olan hegzagonal yapl kaln tabakalara rastlanmtr (ekil.2de ok ile gsterilmitir).
Bu kaln tabakalarn, yukardaki ksmda da belirtildii gibi, grafit tabakalarnn mekanik alamlama ilemi sresince
boyutu klm ve pul pul dklmesi sonucu olumu ince grafit tabakalarnn tavlama ilemi sayesinde st ste
gelerek olutuu dnlmektedir.
ekil 2. 250 saat MA sonras 1600 oC de 4 saat sl ilem uygulanm numunede oluan grafit nano tabakalarn
FE-SEM grnts.
Isl ilem scaklnn veya sresinin yetersiz olmasndan dolay bu tabakalarn tam olarak byyemedii dnlmektedir. Bu yaplarn tam anlamyla bymesi durumunda nano ubuk yaplara dnmesi mmkndr.
250 saat MA ilemine tabi tutulmu 1600 oC de 4 saat tavlanm numunenin baz blgelerinde karbon nano ubuk
(karbon nanorod) yaplar grlmtr. Bu nano ubuk yaplar ekil 3.a ve b de gsterilmitir. ekil 3.a da grld gibi yapda kalnl 50 nm civarnda olan grafit nano tabakalar bulunmasna karn, tabakalarn st ste gelerek
byd, u ksm gittike sivrileen ve boyu yaklak 10 m civarnda olan karbon nano ubuk yap grlmekte-
713

dir. ekil 3.b de ise yaklak 100 nm kalnlnda ve 400 nm geniliinde nano ubuk yap grlmektedir. Bu yap
sl ilem srasnda yeterli derecede byyememitir. ekil 3.bdeki bu yap ekil 2 de belirtilen karbon tabakalara
benzemektedir. Aradaki fark, ekil 3.bdeki yap scakln etkisiyle daha fazla oranda bym dolaysyla kalnl
daha fazla olan karbon nano ubuk yapdr. ekil 2. deki yaplar ise, yeteri kadar byyememi ve bu sebeple
ubuk formu kazanamam nispeten kaln karbon nano tabakalardr. ekil 3.b. deki yap iki paradan olumutur.
Paralardan biri daha kaln olan ve yzeyini grdmz ksmdr. Dier para ise, yzeyi resimde grlemeyen
ve kalnl nispeten daha az olan ksmdr. Kalnl daha az olan para ksmen hegzagonalliini yitirmitir (okla
gsterilmitir). Hegzagonal yzeydeki bu hasar muhtemelen mekanik alamlama ilemi srasnda bilye darbeleri
sebebiyle meydana gelmitir.
714

ekil 3: a) ve b) 250 saat MA sonras 1600 oC de 4 saat sl ilem uygulanm numunenin FE-SEM grnts,
c) karbon nano ubuklarn bymesinin ematik olarak gsterilmesi [8]
Grafitin tlmesi sonucu karbon nano ubuklarn oluma sebebinin tme trnden kaynakland sanlmaktadr. MA ilemi srasnda bilyelerin tozlara kayma trnde gerilmeler uygulamas grafit tabakalar arasndaki zayf
balarn krlmasna sebep olmutur ve uygulanan gerilmeler grafit tabakasna, baka bir deyile bazal dzleme
zarar vermemi, hegzagonal yaplarn muhafaza etmelerine imkan tanmtr.
MA ilemi sonunda uygulanan tavlama ilemi ise hegzagonal yapdaki grafen tabakalarnn st ste gelerek [0001]
ynnde bymesine sebep olmutur ve bylece nano ubuk yaplar ortaya kmtr [8]. Nano ubuklarn oluumu
ematik olarak ekil 3.c. de gsterilmitir. Baz blgelerde ise byme gereklememi ve tabakalar bymeden
olduu gibi kalmtr.
Karbon nano ubuk yaplarn MA srasnda tozlara darbe trnden gerilmeler uygulandnda olumad rapor
edilmektedir [7]. Uygulanan gerilme trne gre grafitin kristal yapsnda meydana gelen deiimler ekil.4 de ematik olarak verilmitir. Grld gibi, darbe trnden gerilmeler uygulanmas durumunda sadece grafit tabakalar
arasndaki ba deil ayn zamanda tabaka ierisindeki gl C-C balar da krlarak yap tamamen amorf hale
gelmektedir. Fakat kayma trnden gerilmeler uyguland zaman bilyelerin toza uyguladklar gerilme miktar nispeten dn olmasndan dolay sadece tabakalar arasndaki balarda krlmalar meydana gelirken, tabaka iindeki
balar krlmadan kalmaktadr. Bu almada kayma trnden gerilmeler uygulandndan tr MA ilemi sonunda
pek ok grafit tabakas kristal yaps bozulmam halde kalmtr. MA ilemi sonunda elde edilen toza uygulanan sl
ilem bu tabakalarda bir etkiye sebebiyet vermemitir. Sadece tabakalarn st ste gelerek dizilmesine baka bir
deyile nano ubuk tipi yaplarn olumasna sebep olmutur.
ekil 4: MA ilemi srasnda grafit tozlarna uygulanan gerilme trne gre tozun kristal yapsnda meydana gelen
deiimlerin ematik grnts [6]
715

ekil 3.a da karbon nano ubuklar, kristal yapsn muhafaza etmi grafitik tabakalarn yannda nano topak haldeki
amorf karbon da bulunmaktadr. Planeter bir deirmende belli bir hzda tek bir bilye ile yaplan MA ilemi srasnda
bilyenin toza uygulad gerilmeler kayma gerilmeleri eklindedir ve kapta ok bilye olmad iin tozlara uygulanan
darbe trndeki gerilmeler minimum dzeydedir. Fakat tek bilye ile yaplan deneylerde tozlarn kesinlikle darbe
gerilmelerine maruz kalmayacaklarn sylemek mmkn deildir. Tek bilye ile yaplan MA ileminde ortaya kan
darbe gerilmeleri, bilye ile kabn arasndaki arpmalardan tr meydana gelmektedir. Bu dk enerjili arpmalar darbe gerilmeleri yaratmakta ve MA sresinin artmasyla bir ksm tozlarn amorflamasna, bir ksm tozlarda
ise grafitik tabakalarn bklmesine sebep olmaktadr.
4. GENEL SONULAR
Grafite uygulanan kayma trnden gerilmeler kristal yap bozulmakszn nano boyutlu grafit tabakalarnn olumasn salamaktadr. MA sresi 250 saat olmasna karn (002) piki tamamen kaybolmamtr. Tozun baz blgelerinde
ksmen amorflama mevcuttur ve bu amorf yaplar sl ilem sonunda yeniden kristalleememilerdir. Yaplan sl
ilem sonunda nano boyutlu grafit tabakalar st ste gelerek karbon nano ubuklar oluturmutur.
5. KAYNAKLAR
1. Antisari M.V., Montone A., Jovic N., Piscopiello E., Alvani C., Pilloni L., Low Energy pure shear milling: A
method fort he preparation of graphite nano-sheets, Scripta Materialia vol.55, pp.1047-1050, 2006
2. Huang J.Y., Yusuda H., Mori H., Highly Curved Carbon Nanostructures Proced by ball-milling, Chem. Phys.
Lett. Vol.303, pp. 130, 1999
3. Chen Y, Conway M.J., Fitz Gerald J.D., Carbon nanotubes formed in graphite after mechanical grinding and
thermal annealing, Applied Physics A, vol. 76, pp. 633-636, 2003
4. Chen Y. Solid-state formation of carbon nanotubes. In: L. Dai, editor. Carbon Nanotechnology, UK;Elsevier;
53-8, 2006
5. Gosh, B., Pradhan, S.K., Microstructure characterization of nanocrystalline Fe3C synthesized by high energy
ball milling, J. Of Alloys and Compounds, 477, pp 127-132, 2009
6. Disma F.S., Tarascon J.M, Clinard C., Rouzaud J.N., Transmission Elektron microscopy studies on carbon
materials prepared by mechanical milling, Carbon vol.37, pp.1941-1959, 1999
7. Gler ., Mekano-Termal Yntem le Karbon Nano Tp retimi Ve Karakterizasyonu, Doktora Tezi, Frat
niversitesi F.B.E., 2011
8. J.S. Lee, K. Park, M.I. Kang, I.W. Park, S.W. Kim, W.K. Cho, H.S. Han, S. Kim, ZnO nanomaterials synthesized
from thermal evaporation of ball-milled ZnO powders, J. Crystal Growth, 254, 428, 2003
716

FARKLI SRELERDE MEKANK ALAIMLANAN NKEL ESASLI

SPERALAIM TOZUN KARAKTERZASYONU
nn . Mh. Fak. Makine Mh. Blm, Malatya, mehmet.erdem@inonu.edu.tr
*Gazi ., Tekn. Fak., Metalrji ve Malz. Mh. Blm, Ankara, mturker@gazi.edu.tr
ZET
Bu almada, Ni esasl speralam toz karm (%75 Ni, %20 Cr, %4 Al2O3, %0.6 Ti, %0.4 Y2O3), seramik bir kazanda farkl srelerde (-24 saat) ve 450 rpm sabit hzda mekanik olarak alamland. Farkl mekanik alamlama
srelerinin speralam toz boyutuna, ekline ve mikro sertliine etkisi tespit edildi. Mekanik alamlanan tozlarn
karakterizasyonu iin toz boyut analizi, mikro sertlik lm ve elektron mikroskop (SEM) almas yapld. Bu analizlerde; artan mekanik alamlama sresi ile speralam toz boyutunun mikron alt boyutlara kadar kld, souk kaynak sonucu lamelli yapnn olutuu ve lameller aras mesafenin zamanla darald ve toz mikro sertliinin
art tespit edildi. Ayrca, 4-8-12-16-24 saat mekanik alamlanan speralam tozlarn X-RD (X-Ray Diffraction)
analizleri yapld ve herhangi bir metaller aras bileiin olumad belirlendi.
Anahtar Kelimeler: Ni esasl speralam, Mekanik alamlama sresi, Mikroyap karakterizasyonu
CHARACTERIZATON OF Ni BASED SUPERALLOY POWDER MECHANICAL

ALLOYED FOR VARIOUS DURATIONS
ABSTRACT
In this study the Ni based superalloy powder mixture (75% Ni, 20 % Cr, 4% Al2O3, 0.6% Ti) were alloyed in a ceramic container under different durations (-24 hours) and 450 rpm constant speed. It has been determined the
effect of different mechanic alloying durations for superalloying powder dimensions, forms and micro hardness. The
powder dimension analyze, micro hardness measurement end SEM has been carried out for characterization of
the mechanically alloyed powder. In this analyses; it has been determined that the superalloy powder dimension
were diminished to sub-micron dimensions, lamellae structure got finer and the distance between the lamellaes
got closer and the micro hardness of powder were increased with increasing the milling time. Moreover the X-RD
(X-Ray Diffraction) analyses of mechanical superalloyed powder for 4-8-12-16-24 hours were carried out and there
has been determined that a inter-metallic compound was not formed.
Keywords: Ni based superalloy, mechanical alloying duration, microstructural characterization
1. GR
Mekanik alamlama (MA) son derece homojen ve ince mikro yaplar elde etmek amacyla kuru, ya, yksek enerjili,
bilyeli ve/veya ubuklu tme teknii olarak tanmlanmtr [1-3].
MA mekanizmas ayr aamadan meydana geldii kabul edilmektedir. Birinci aamada, tme srecindeki
bilye-bilye, bilye-cidar ve kartrclar-cidar arpmasyla arada kalan tozlara bir miktar darbe enerjisi yklenir. Bu
darbe enerjisi yumuak tozlarda ekil deiimine, sert tozlarda ise krlmaya neden olur. Deformasyon ve krlmayla
717

oluan yeni yzeyler ilemin devam etmesiyle birbirleriyle kaynaklanr. Bylece, alamlamann ilk aamasnda toz
parack boyutu artar. Bu aamada parack boyutu byyerek balang parack boyutunun 3 katna kadar ulaabilir [4]. kinci aamada, artan MA sresi ve deformasyon ile tozlarda ki deformasyon peklemesi ve sertlik artar
[5]. Bu sertlik etkisiyle toz paracklarnda krlma balar ve bu aamada krlma souk kaynaktan daha etkindir.
nc aamada ise her bir toz parac ierisinde bulunan alam tabakalar arasndaki boluklar azalrken, ayn
zamanda bu alam tabakalarnn says artar. Parack iindeki katmanlar aras mesafe azalrken, katman says
da artar. Belli bir sre tmenin ardndan, ortalama parack boyutunu artran kaynaklanma ve ortalama toz partikl boyutunu azaltan krlma, miktarlar arasnda bir denge yakalandnda kararl hal dengesine ulalr.
Salkl bir mekanik alamlama ileminin gerekletirilebilmesi iin ilem zerinde olduka fazla etkileri olan deirmen tipi, tme kazan, tme hz, zaman, tme malzemesi (bilye), bilye-toz arlk oran, kazan doldurma
miktar, tme atmosferi, scakl, ilem kontrol kimyasal gibi parametrenin doru bir ekilde seilmi olmas
gerekir. Bunlar tlecek tozun miktarn, boyutunu, kirlenme orann, tme enerjisini ve toz kaybn etkileyen
en nemli parametrelerdir.
MA da, tcden elde edilen enerjinin verimli kullanlmas ve tozun kimyasal yapsnn deimesine kazan tipi
etki eder. MA ilemi srasnda tc bilyelerin tme tanknn i cidarna uyguladklar darbeler nedeniyle kap
malzemesinin bir ksm yzeyden koparak toza karabilir. Bu durum tozun kimyasal yapsnn deimesine veya
paracklarn kalkt blgelere tlen tozun yapmasna neden olur. Buda, toz kaybna ve toz kirliliine neden
olur. Bu konu ile ilgili yaplan bir almada [6], bakr kap iinde Cu-In-Ga-Se toz karm tlm ve toz iindeki
bakr miktarnn balang toz karmna gre daha yksek olduu tespit edilmitir. tme kabndan kopan bakr
paralarnn toza karmas neden olarak belirtilmitir. Byle durumlarda tozun kimyasal bileiminin deimemesi
iin uygun tme kab seilerek gerekli nlemler alnmaldr. tc maddenin younluu, toz zerine yeterli
darbe enerjisi oluturabilecek byklkte olmaldr. rnein elik bilye yerine WC bilyeler kullanlarak yaplan bir
almada daha yksek darbe enerjisi elde edilmitir [7]. Ayn zamanda tc madde boyutu da tme verimini
dorudan etkiler. Genelde byk boyutlu bilyeler toz paracklar zerine daha fazla darbe enerjisi transfer ederler.
Ancak gereinden byk bilyeler toz boyutunun klmesini engelleyebilirler. tc madde boyutunun tozun
final yaps zerinde etkili olduu tespit edilmitir. Bu konuyla ilgili yaplm bir almada, titanyum alminyum toz
karm 5 ve 8 mm apnda ki bilyeler kullanlarak tldnde amorf fazn olutuu 12 mm apndaki bilyeler
kullanldnda ise amorf fazn olumad gzlemlenmitir [8]. Pd-Si sisteminde de benzer ekilde amorf fazn
olumas iin kk boyutlu bilyelerin tercih edildii bildirilmitir ve kk bilyelerin gl srtnme hareketi rettii
ve bununda amorf faz oluumunu hzlandrd belirtilmitir [9].
Toz paracklarn kararl hal dengesine ulamasnda en nemli parametrelerden biride MA sresidir. Normal artlarda sre, toz paracklar arasndaki krlma ve souk kaynaklama kararl hale gelecek kadar seilmelidir [10].
zellikle titanyum ve zirkonyum gibi reaktif elementlerin bulunduu tozlar eer gereinden fazla tlrlerse,
kirlenmeleri ve istenmeyen fazlarn olumas kanlmaz olur [11]. Bu nedenle tozlar sadece gerekli olan sre kadar
tlmelidir. Toz paracklarnn kararl hale gelmesi iin, yksek enerjiyle ksa sreli ve dk enerjiyle de uzun
sreli tme yapmak genel olarak kabul edilen bir kuraldr. Yani, yksek bilye-toz orannda az sre, dk bilye-toz
orannda ise daha fazla sre kullanlmaldr. MA iin gerekli sre tme hzna, tc tipine, tme younluuna, tme scaklna ve bilye-toz arlk oranna bal olarak deiiklik gsterir. Bu parametreler, her bir toz
kombinasyonu iin ayr ayr belirlenmelidir [12].
Bu almada, nikel esasl sper alam toz karmna MA sresinin etkisi aratrlmtr. Bu amala farkl srelerde
mekanik alamlanan tozlar toz boyut analizi, mikro sertlik lm, taramal elektron mikroskop (SEM) almas ve
XRD analizleri ile karakterize edilmitir.
2. MALZEME VE METOD
Deneylerde kullanlan toz komposizyonu Tablo 1de, SEM ve EDAX analizleri de Resim 1-5de verilmitir. Deneylerde kullanlan Ni tozunun ortalama toz boyutu 10,38 m, Cr tozunun 87,90 m, Al2O3 tozunun 3 m, Y2O3 tozunun
3 m ve Ti tozunun ise 2-50 m gibi geni bir aralkta deitii grlmektedir. MA ilemi esnasnda yalayc olarak
%2 toz Zn-stearat kullanlmtr. Ancak, 16 ve 24 saat MA esnasnda tozlarn, kartrc kollara, bilyelere ve kazan
i yzeyine svanmas nedeni ile atritrn zorland grlm ve Zn-stearat miktar %3e kartlmtr.
Mekanik alamlama ilemi Unionprocess firmas tarafndan imal edilen 2 litrelik tme tankna sahip dnme hz
dijital olarak ayarlanabilen SZEGVARI modelli bir atritrde 450 dev/dak hzda ve 10/1 bilye-toz arlk oran kullanlarak yaplmtr. Deneylerde 50 gram toz karm 10 mm apnda elik bilyeler kullanlarak tlmtr. Mekanik
alamlama esnasnda koruyucu atmosfer olarak yksek saflktaki (%99,999 orannda) argon gaz kullanlmtr.
Argon gaz iindeki nemi kurutmak ve bulunmas muhtemel oksijeni yapdan uzaklatrmak iin gaz, boru ierisine
doldurulmu 650oCdeki bakr talalarnn ierisinden geirilmitir.
718

Optimum mekanik alamlama sresini tespit etmek amacyla seramik kazanda sekiz farkl sre (, 1, 2, 4, 8,
12, 16, ve 24 saat) kullanld. Deneyler esnasnda alamlama tank srekli olarak su sirklasyonu ile soutuldu.
Deiik srelerde yaplan mekanik alamlama deneyleri sonras elde edilen tozlar rnga ile vakumlanan kk
plastik kutulara konularak muhafaza edildi. Farkl srelerde mekanik olarak alamlanan tozlarn karekterizasyonu
iin toz boyut analizi Malvern Mastersizer E ver 1.2 b cihaznda, mikro sertlik lmleri 10 g yk altnda SHIMADZU
HMV-2 cihaznda, SEM ve EDX analizleri J0EOL JSM-6060 LV markal elektron mikroskobunda ve XRD analizleri
de Bruker D 8 Advance markal cihazda oda scaklnda yaplmtr. Mikro yap almalarnda Marbel dalaycs
kullanlmtr.
Tablo 1. MA deneylerinde kullanlan toz kompozisyonu (% arlk).
Element
Ni
Cr
Al2O3
Ti
Y2O3
% Arlk
kalan
20
0.6
0.4
Resim 1. Nikel tozu ve tozun EDAX analizi
Resim 2. Krom tozu ve tozun EDAX analizi
Resim 3. Al2O3 tozu ve tozun EDAX analizi
719

Resim 4. Y2O3 tozu ve tozun EDAX analizi
Resim 5. Titanyum tozu ve tozun EDAX analizi

3.1. SEM Sonular
saat mekanik alamlama sonunda elde edilen tozlara ait SEM grnts Resim 6-ada verilmitir. Mekanik
alamlamann bu aamasnda, sert tozlarda krlma, yumuak tozlarda ise deformasyon nedeni ile azda olsa katmans yap oluumunun balad grlmektedir. ekil 6-bde 1 Saat MA sonunda elde edilen tozlarn mikro yaplar
verilmitir. Bu aamada sert toz tanelerinin krlma ile inceldii ve yumuak toz tanelerinin ise souk kaynak ve
deformasyonla uzad grlmektedir. ekil 6-cde 2 saat sreyle MA ilemine tabi tutulan tozlarda, heterojen bir
boyut dalm dikkat ekmektedir.
Tozlarn, e eksenli tane yaplarnn souk kaynaklanma nedeniyle zaman zaman bozularak tozlarn boy/en orannn artt grlmektedir. Resim 6-dde 4 saat mekanik alamlanm toz paracklar deformasyonun etkisi ile
inceldii ve boy/en oranlarnn artt grlmektedir. Ayrca kaynaklama sonucu oluan katmanl (lamelli) yaplarn
artt grlmektedir. ekil 6-ede 8 Saat mekanik alamlanm tozlarn SEM grntsnde tamamen lamelli yapnn hakim olduu ve lameller aras mesafenin 1 m dan fazla olduu ak bir ekilde grlmektedir.
Alamlanm toz tanelerinin her biri, balang kompozisyon oranlarna sahip olup, tm balang bileenlerini
ierdii sylenebilir. Resim 6-fde 12 saat MA ilemi sonras tozlarn SEM grnts verilmitir. Resimde, tozlarn
kresel ve e eksenli tane yapsnda olduklar grlmtr. Lamel boy/en oran yaklak 10/1, lameller aras mesafenin ise yaklak 1 m civarnda olduu tespit edilmitir. 16 saat MA sonrasnda tozlar homojen grnml ve
tane boy/en oranlar yaklak 1/1 civarnda kresel bir boyut dalmna sahip olduklar grlmektedir (Resim 6-g).
Lamel boy/en oran yaklak 10/1 ve lameller aras mesafenin bir nceki aamaya gre (12 saat MA) zaman zaman
kapand zaman zamanda 0,5 m civar olduu grlmtr. 24 saat MA ilemi sonunda elde edilen tozlarda ise
(Resim 6-h) souk kaynak sonucu oluan lameller aras mesafenin nerdeyse tamamen kapand ve tozlarn kresel yapy koruduklar dikkat ekmektedir. Lameller, 12 ve 16 saat tlm toz yapsndaki lamellere gre daha
ince olduklar grlmektedir. Lamel boy/en orannn yaklak 10/1 civarnda olduu tespit edilmitir.
720

Resim 6. Farkl srelerde mekanik alamlanm tozlarn SEM grntleri.

a- saat, b- 1 saat, c-2 saat, d- 4 saat, e- 8 saat, f- 12 saat, g- 16 saat, h- 24 saat
721

3.2. Mekanik Alamlama Sresine Bal Toz Boyutu Deiimi

MA sresine bal toz boyut deiimi ekil 1de grafik olarak verilmitir. Bu grafie gre saat alamlanan tozlar
11,43 m olup genelde elemental halde ve souk kaynaklamann etkin olmamas nedeni ile toz paracklarnn irilemedii grlmtr. 1 saatlik alamlama sonunda, toz paracklar arasnda zaman zaman meydana gelen kaynaklamalar toz boyutunun artmasna (16,09 m) neden olmutur. 2 saatlik mekanik alamlama sonunda tozlarda
kaynaklamann hakim olmasyla birlikte toz boyutunda gzle grlen bir art (24,14 m) tespit edilmitir. 4 saatlik
MA sonunda, kaynaklaan tozlar da deformasyon peklemesine bal sertlik art nedeni ile krlmann (22,55 m)
balad tespit edilmitir. 8 saat MA uygulanm tozlarda krlmann daha etkin olmas sonucu boyutlarnda gzle
grlen bir azalma (16,11 m) tespit edilmitir. 12 saat sonunda, pekleme sonucu toz sertliindeki arta bal krlmann devam etmesiyle toz boyutlarnn 10,96 m olduu tespit edilmitir. 16 saat MA ilemi sonunda da tozlardaki
krlmann dzenli olarak devam ettii grlmtr (6,51 m). 24 saat MA ilemi uygulanm tozlardaki krlmann
devam ettii ve nceki aamalara gre daha az oranda olduu grlmtr (4,95 m).
ekil 1. Mekanik alamlama sresine bal toz boyutu deiimi.

Bu sonulara gre MA ileminin ilk aamas olan souk kaynaa bal parack boyutlarndaki art 2 saat MA
sonrasnda gereklemi ve parack boyutu 24,14 mna ykselmitir. 4 saat tlen tozlardaki krlma ve kaynaklamann belli bir dengede devam ettii ve peklemeye bal krlma aamasnn henz balad grlmtr.
nk, 2 saat sonunda 24,14 m olan toz parack boyutu, 4 saat sonunda 22,55 ma dm ve toz parack
boyutunda gzle grlr bir azalma olmamtr. 8 saat MA sonunda peklemeye bal krlmann daha hakim olmas
ile toz parack boyutu 16,11 mna dmtr. MA ileminin ikinci aamas 4 saat sonunda balam ve 8 saatte
ekil 2. MA sresine bal lameller aras mesafe deiimi
722

kadar youn bir ekilde devam etmitir. Ayn zamanda MA ileminde nc aama olan kararl hal aamasnn da
8 saat MA sonunda balad ve 12-16 ve 24 saat MA ileminde de belli oranda devam ettii sylenebilir. nk 8
saat MA sonunda tozlarda lamelli yapnn hakim olduu grlmektedir (Resim 6-e). Artan MA sresi lamelli parack
boyutunu kltrken, lameller aras mesafenin de kapanmasn salamtr. 8 saat sonunda lameller aras mesafenin yaklak 2 m ve lamel boy/en oran 15/1 olduu tespit edilmitir. 12 saat sonunda lameller aras mesafe (1 m)
ve lamel boy/en orannn azald (10/1) grlmtr. 16 saat sonunda, tozlarn kresel yapy koruduklar, lameller
aras mesafenin kapanmaya devam ettii (0,5 m) ve lamel boy en orannn 10/1 civarnda olduu grlmtr. 24
saat sonunda da tozlar kresel yapda olup, lameller aras mesafenin neredeyse tamamen kapand ve lamel boy
en orannn 10/1 civarnda olduu grlmtr. ekil 2de artan MA sresine bal lameller aras mesafe deiimi
verilmitir. Bu konu ile ilgili yaplan almalarda, artan tme sresine bal olarak lamelli yapnn inceldii ve
lameller aras mesafenin azald belirtilmitir [13].
Bu konu ile ilgili elik kazanda yaplan benzer bir almada Ni esasl speralam tozlar farkl srelerde (-1-2-4-7
ve 8 saat) mekanik alamlanm ve toz boyutlar saatlik alamlama sonunda 9,42m, 1 saatlik alamlama sonunda 11,03m, 2 saatlik mekanik alamlama sonunda 8,67m, 4 saatlik mekanik alamlama sonunda 20,87m,
7 saatlik mekanik alamlama sonunda 11,34m ve 8 saatlik mekanik alamlama sonunda da ise 10,38 m olarak
tespit edilmitir. Bu almada mekanik alamlamann ilk aamasna 4 saat MA sonunda, ikinci aamasna 7 saat
MA sonunda ve nc aamasna da 8 saat MA sonunda ulald belirtilmitir [3]. Nikel esasl bir speralam
zerinde yaplan baka bir almada da, dnme hz 710 dev/dak olan bir atritrde, farkl bilye aplar ile farkl
srelerde MA ilemi denenmitir [14]. 10 mm apnda elik bilye ve kazan ile 2, 5 ve 10 saat MA ilemi sonunda
ortalama toz boyutu sras ile 18,84 m, 27,52 m ve 23,20 m olduu belirtilmitir. Demir esasl bir speralam
zerinde yaplan baka bir almada ise dnme hz 1200 dev/dak olan bir atritrde, ap olan bilyelerle farkl
srelerde MA ilemi denenmitir [15]. mm apnda elik bilye ve kazan ile 1 saat MA ilemi sonunda ortalama
toz boyutu 72,63 m, 2 saat MA ilemi sonunda ortalama toz boyutu 62,84 m, 10 saat MA ilemi sonunda ortalama
toz boyutu 12,54 m, 24 saat MA ilemi sonunda ortalama toz boyutu 6,18 m ve 48 saat MA ilemi sonunda ise
ortalama toz boyutu 12,05 m olduu belirtilmitir.
3.3. Mekanik Alamlama Sresine Bal Mikro Sertlik Deiimi
Mekanik alamlama sresine bal toz mikro sertlik deerleri grafik halinde ekil 2de verilmitir. saat MA ilemine tabi tutulmu tozlar genelde elemental halde olup sertlikleri 143 HV olarak llmtr. 1 saat MA ilemi sonunda
tozlardaki deformasyon miktarnn artmasyla sertlik 173 HV ye kmtr. 2 saat MA ilemi sonunda hakim olan
souk kaynaklama nedeniyle toz parack boyutu artarken serlikleri de 189 HV ye kmtr. 4 saatlik MA ilemi
sonunda artan deformasyon peklemesi nedeni ile toz parack boyutlarnda azalma, sertliklerinde ise artma tespit
edilmitir (210 HV). 8 saat MA ilemi sonunda tozlarda lameli yap hakim olup, sertlik deeri 239 HV olarak tespit
edilmitir. Tozlardaki lamelli yapnn artmas, artan MA srelerinde toz sertlik lmlerini zorlatrmtr. nk, sertlik cihaznn batc ucu lameller arasna geldiinde sertlik deerlerinin dk kmasna neden olmutur. Bu nedenle
sertlik lmleri titizlikle yaplmtr. 12 saatin sonunda tozlardaki krlma ve sertlik artnn devam ettii tespit
edilmitir (276 HV). 16 saat MA ilemi sonunda, souk kaynak sonucu oluan toz paracklarndaki lameller aras
mesafenin ve parack boyutlarndaki azalmann devam ettii grlm ve artan deformasyon peklemesi nedeniyle sertlik 301 HV olarak tespit edilmitir. 24 saat MA ilemi sonunda toz paracklarnn krlmaya devam etmesi ve
zaman zaman da mikron alt seviyelerde olmalar nedeniyle mikro sertlik lmleri yaplamamtr.
Bu konu ile ilgili elik kazanda yaplan benzer bir almada Ni esasl speralam tozlar farkl srelerde mekanik
alamlanm ve mikro sertlikleri 2 saat MA ilemi sonunda 102 HV, 4 saat MA sonunda 128 HV, 7 saat MA sonunda
sertlik 212 HV, ve 8 saat MA sonunda ise 218 HV olarak bulunmutur [3]. Ayn almada toz parack sertliinin 8
saat MA sonunda kararl hale geldii ifade edilmitir. Baka bir almada demir esasl sper alam tozlar dikey bir
atritrde deiik srelerde (1-2-10-24 ve 48) saat) tlm ve artan MA sresi ile toz mikro sertliklerinin artt belirtilmitir. 1 saat MA ilemi sonunda tozlarn mikro sertlii 292 HV, 2 saat sonunda 313 HV, 10 saat sonunda 323 HV,
24 saat sonunda 382 HV ve 48 saat sonunda ise 525 HV olduu tespit edilmitir [15]. Bu konu ile ilgili yaplan baka
bir almada da, nikel esasl sper alam tozlar deiik aptaki (6-5/6 ve 10 mm) bilyelerle deiik srelerde (510-15 ve 24 saat) dikey bir atritrde tlm ve artan MA sresi ile toz mikro sertliklerinin de artt belirtilmitir
[14]. Botcharova E., ve arkadalar bakr ierisine deiik oranlarda niobyum ilave etmiler ve farkl srelerde bilyeli
tcde tmlerdir. Artan MA sresi ile beraber tozlarn mikro sertliklerinin arttn ve toz parack boyutunun
da kldn tespit etmilerdir[16]. Adabavazeh Z. ve arkadalar %50 Fe, %25 Ni ve %25 Al tozlarna oda scaklnda farkl srelerde(5-20-40-80 saat) 20mm apndaki bilyelerle (bilye toz oran 10/1) mekanik alamlama ilemi
yapmlar ve artan MA sresine bal olarak tozlarn mikro sertliinde art tespit etmilerdir[17].
723

ekil 3. Mekanik alamlama sresine bal mikro sertlik deiimi.

3.4. Tozlarn X-RD analizleri
tme esnasnda tozlar arasnda meydana gelebilecek muhtemel bileikleri tespit etmek amacyla seramik kazanda, farkl srelerde (4, 8, 12, 16, 24 saat) tme ilemi uygulanan tozlarn X-RD analizleri yaplmtr. X-RD
analizinde Cu K n (k = 0.1542 nm) kullanlmtr. .Elde edilen sonular ekil 4-8de sras ile verilmitir. X-RD
analizleri, 4, 8, 12, 16 ve 24 saat sonunda toz yaplarnda farkl bir bileik yada amorf yapnn henz olumadn
gstermitir. Bu konu ile ilgili yaplan bir almada, n alamlanm iki farkl toz bileimi, (Ni-%13,3Al- %2,1 Y2O3
ve Ni-%50Al- %2,1 Y2O3) titreimli bilyeli tcde 50 saat tlm ve XRD analizleri yaplmtr. MA esnasnda
tozlarn tamamen B2-NiAl bileiine dnt tespit edilmitir [18]. PM 1000 ile benzer bileim ve mikro yapya
sahip olan MA 754 alamnda saf Y2O3in yerine yitrium alminann var olduu belirtilmitir [19]. Bu bileiklerin alamn retimi esnasnda, Y2O3 paracklarnn bir ou Al ile kat zelti ierisinde reaksiyona girmeleri ile olutuu
belirtilmitir [20].
ekil 4. 4 Saat MA sonras tozlarn X-RD analizi
724

725

4. BULGULAR VE NERLER
Seramik kazanda elik bilye kullanlarak yaplan MA ileminde MA sresinin Ni esasl speralam toz boyutu, ekli
ve sertliine etkisi incelenmi ve aadaki sonular elde edilmitir.
1. Yaplan MA ileminde toz paracklarnn souk kaynak sonucu irilemesi aamas olan birinci aamaya 2 saat
MA sonunda, deformasyon peklemesi nedeniyle toz paracklarnn krlma aamas olan ikinci aamaya 4 saat
MA sonunda ve kaynaklama ve krlmann dengede olduu kararl hal aamas olan nc aamaya da 8 saat MA
sonunda ulalmtr. Ayrca 8 saat MA sonrasnda tozlarda lamelli yaplarn hakim olduu grlmtr.
2. 8 saat MA sonras ulalan kararl hal aamasnn 12-16 ve 24 saat MA sonrasnda da devam ettii tespit edilmitir. 8 saat MA sonrasnda itibaren toz paracklarnn ortalama toz boyutunun klmesiyle lamel boy/en oranlarnn 15/1den 10/1 seviyelerine dt, toz paracklarndaki lamel saysnn artt ve lameller aras mesafenin
azald tespit edilmitir .
3. Artan MA sresine bal olarak parack boyutlarnn kld 24 saat MA sonunda zaman zaman mikron alt
byklklere ulald grlmtr. Ayrca artan MA sresi ile toz paracklarnn deformasyon peklemesine bal
olarak mikro sertliklerinin de artt tespit edilmitir.
4. Tozlara 4, 8, 12, 16, 24 saat MA ileminden sonra uygulanan X-RD analizlerinde farkl bir bileik yada amorf
yapnn henz olumad grlmtr. Uzun sreli ( 50 saat ve zeri) yaplacak tme ilemlerinde, Ni-Al- Y2O3
alam sistemlerine ait bileiklerin oluabilecei dnlmektedir.
5. Farkl aplarda tc biyelerle ve farkl tme hzlarnda uzun sreli (50 saat ve zeri) MA ilemi yaplabilir
ve olumas muhtemel bileik yada amorf yaplarn analizleri yaplabilir.
5. KAYNAKA
1.
Schelleng, R.D., and Donachie, S.J., Mechanical alloyed aluminum, Metal Powder Report, 38:357-359,
1983.
2. El-Eskandarany, M. S., Aoki, K., Suziki, K. J. Less Common Metals 167:113-118, 1990.
3. Erdem. M., Trker, M., Farkl srelerde mekanik alamlanan nikel esasl speralam tozun karakterizasyonu, 13th International Metalurgy & Materials congress, stanbul, 930-936, November 09-11, 2006.
4. Suryanarayanan, C., Ivanov, E., Boldyrev, V. V., The Science and Technology of Mechanic Alloying, Mater.
Sci. Eng. A304-306:151-158, 2001.
5. Trker, M., zdemir, A.T., el, B. ve Yavuz, A., Al-SiC tozlarnn alamlama deirmeninde tme zamannn kompozit toz yapsna etkisinin aratrlmas, 2. Ulusal Toz Metalurjisi Konferans, 425-431, 15-17 Eyll
ODD, Ankara, 1999.
6. Suryanarayana, C., Ivanov, E., Noufi, R., Contreras, M.A., Moore, J. J., Phase selection in a mechanically
alloyed Cu-In-Ga-Se powder mixture J. Mater. Res., 14: 377-383 (1999).
7. Gonzales, G., Sagarzazu, A., Villalba, R., Ochoa, J., DOnofrio, L., Effect of the milling media on the phases
obtained in mechanically alloyed equiatomic Fe-Co, Mater. Sci. For., 360-362:355-360 (2001).
8. Park, Y.-H., Hashimoto, H., Watanabe, R., Morphological evolution and amorphization of Ti/Cu and Ti/Al
powders mixtures during vibratory ball milling Mater. Sci For., 88-90: 59-66 (1992).
9. Padella, F., Paradiso, E., Burgio, N., Magini, M., Martelli, S., Guo, W., Iasonna, A., Mechanical alloying of the
Pd,Si system in controlled conditions of energy transfer, J. Less Common Metals 175: 79-90 (1991).
10. Suryanarayana, C., Internalt. Mater. Rev., 40:41-64, 1995.
11. Schaffer, G.B.,McCormick, P.G., Metal Transaction A, 22:2789, 1990.
12. Bostan, B., Synthesis of Al-C by MA Process, Ph.D. Thesis., G.U. Enst. Of Sci. And Techn., Ankara,
(2003).
13. Suryanarayana, C., Mechanical alloying and milling, Marcel Dekker, New York, 1-466 (2004).
14. Evin, E., Nikel Esasl Bir Sper Alamn Mekanik Alamlama Yntemi le retilmesi Ve Mikroyap-Oksitlenme zelliklerinin Aratrlmas, Doktora Tezi, Frat ., Fen. Bil. Enst., 2003.
15. Kln,Y., Demir bazl speralamlarn mekanik alamlama metodu ile retilmesi ve zelliklerinin aratrlmas, Doktora tezi, G..Fen Bil.Enst., Ocak 1999.
16. Botcharova E., Heilmaier M., Freudenberger J., Drew G., Kudashow D., Martin U., Schultz L., Supersaturated
solid solution of niobium in copper by mechanical alloying Journal of Alloys and Compounds 351 (2003)
119125
17. Adabavazeh Z., Karimzadeh F., Enayati M.H., Synthesis and structural characterization of nanocrystalline
(Ni, Fe)3Al intermetallic compound prepared by mechanical alloyin, Advanced Powder Technology xxx
(2011) xxxxxx (article in press).
18. Grahle, P., and Arzt, E., Microstructural development in dispersion strengthened NiAl produced by mechanical
alloying and secondary recrystallition, Acta Mater., 45(1): 201-211(1997).
19. Howson, T. E., Stulga, J.E., Tien, J.K., Creep and stres rupture of a mechanically alloyed oxide dispersion and
precipitation strengthened nicel-base superalloy, Metall. Trans., 11A: 1599 (1980).
20. Sha, W., Bhadeshia, H. K. D. H., Characterization of mechanically alloyed oxide dispersion-strengthened
nicel-based superalloy MA760, Matall. Trans., 25A: 705-714 (1994).
726

AL MATRSL VE Al2O3 PARACIK TAKVYEL KOMPOZTLERN FARKLI

MEKANK ALAIMLAMA SRELERNDE RETLMES VE KARAKTERZE
EDLMES
Hasan KARABULUT*, Ramazan ITAK**
*
Ankara Altnda Siteler Mesleki Eitim Merkezi, Metal Teknolojisi retmeni, Siteler, 06500, Ankara,
karabulut.hasan@hotmail.com
**
rcitak@gazi.edu.tr
ZET
Al matrisli Al2O3 parack takviyeli kompozitler farkl srelerde mekanik alamlanm ve mekanik alamlama sresinin alamlanm tozlarda, parack dalm, toz boyutu, sertlik, younluk ve gzeneklilik gibi karakteristik zelliklere etkisi incelenmitir. Mekanik alamlama sonras numunelerde homojen bir parack dalm elde edilmitir.
Alamlama sresinin artmasyla toz boyutu klrken, sertlik artmtr. Ayrca artan alamlama sresi ile younluk azalm, gzenek oran da artmtr.
Anahtar Kelimeler: Kompozit, Al2O3, Mekanik alamlama, Sertlik.
PRODUCTION AND CHARACTERIZATION OF AL MATRIX AND Al2O3

PARTICLE-REINFORCED COMPOSITES FOR DIFFERENT MECHANICAL
ALLOYING DURATIONS
ABSTRACT
Composite materials with Al2O3 particle reinforcement and Al matrix were produced by using mechanical alloying
methods for different periods of time. Effect of time on particle distribution, particle size, hardness, density and
porosity ratio were investigated. A homogeneous particle distribution was obtained in samples mechanical alloyed.
While particle size was decreasing with alloying time hardness was increased. In addition, the density decreased
with alloying time and porosity increased.
Key Words: Composite, Al2O3, Mechanical alloying, Hardness.
1. GR
Gelien teknoloji ile tm mhendislik dallarnn ve insan ihtiyalarnn da deimesi metalurji ve malzeme alanndaki aratrmaclarn yeni malzeme retme almalarnn nemini artrmaktadr. Kompozit malzemeler ve zellikle
metal matrisli kompozit malzeme retimi bu almalardan sadece bir tanesidir. Kompozit malzemeler, kimyasal
bileimi ve zellikleri bakmndan farkl olan birden daha fazla sayda malzemenin makro dzeyde birletirilmesi ile
bir araya getirilen malzemelerdir [1]. Kompozit malzeme ierisindeki bileenler ara yzeylerle birbirinden ayrlr ve
yap ierisinde kendine has zelliklerini muhafaza ederler [2]. Kompozit malzemeler bir ok yntemle retilebilir. Bu
yntemlerden bir tanesi de Mekanik alamlamadr (MA). MA yntemi, yksek enerjili bir deirmen ierisinde toz
ve paracklarn kartrlmas esnasnda kaynaklanmas, paralanmas ve yeniden kaynaklanmasn ieren bir kat
hal ile tekniidir [3]. Mekanik alamlama ilemi ile dkm ynteminde karlalan homojenlik, slatlabilirlik, birbiri
ierisinde karmama vb. problemler ortadan kaldrlabilir [1-7].
727

Bu almada, Al matrisli Al2O3 seramik parack takviyeli kompozitler mekanik alamlama yntemiyle retilmitir.
Farkl alamlama srelerinde, mikroyap dalm, tane boyutundaki deiimler, younluk, gzeneklilik ve sertlik
gibi zelliklerin incelenmesi amalanmtr.
Matris malzemesi olarak, gaz atomizasyon yntemi ile retilmi, % 99,7 saflkta, 72,24 m ortalama toz boyutunda
alminyum toz kullanld. Takviye eleman olarak ise 15,40 m ortalama toz boyutunda Al2O3, seramik tozlar kullanld. MA ilemi, szegvari modeli dikey bir atritr ierisinde 10/1 bilye/toz orannda, 10 mm apnda elik bilye ve
% 1,5 yalayc ilave edilerek yapld. MA ilemi 350 rpm hzda akan argon atmosferinde 2, 6 ve 10 saat srelerde
uyguland. MA srasnda snmay nlemek iin silindir akan souk su ile srekli soutuldu.
MA sresinin toz boyutu zerindeki etkisini belirlemek iin toz boyut analizi yapld. Mekanik alamlanan tozlar 700
MPa basn altnda 12 x 15 mm boyutlarnda blok paralar oluturacak ekilde tek ynl olarak preslendi. Blok
paralar 600 C scaklkta akan argon atmosferinde 1 saat sreyle sinterlendi.
Sinterleme ncesi ve sonras younluk lmleri yaplarak gzenek deerleri belirlendi. Sinterlenen numunelerdeki
sinterleme kalitesini ve faz dalmn grebilmek iin, uygun numuneler alnarak, zmparalama, parlatma ve dalama ilemleri uyguland.
retilen kompozitlerin mikro yaplar Optik Mikroskop ve Taramal Elektron Mikroskobu ile incelendi. Brinell sertlik
deerleri 2,5 mm bilye ve 31,25 kgf yk uygulanarak gerekletirildi. Her numune iin 6 sertlik lm uygulanarak
ortalamas alnd.
3. DENEYSEL SONULAR
3.1. Tane Boyut Analizi
Matris olarak kullanlan saf alminyum tozlarn ve takviye eleman olarak kullanlan Al2O3 tozlarnn SEM fotoraflar
Resim 1de verilmitir. Bu resimlerden Al matris malzemesinin ounlukla dzensiz ekilli olduu, ancak keskin
kelerin olmad, Al2O3 tozlarnn da dzensiz bir geometride ve keskin keli olduklar grlmektedir.
Resim 1. (a) Saf Al tozunun ve (b) Al2O3 tozunun SEM grnts

Ortalama toz boyut analiz sonular ekil 1.de verilmitir. MA uygulanmam, ancak bilyesiz olarak eksenli
turbula cihaznda homojen karm yaplm (TK) kompozitlere gre, 2 saat MA ilemi uygulanan numunelerde toz
boyut oran ksmen artmaktadr. Ancak MA sresinin 6 ve 10 saate kmasyla toz boyut oran srekli olarak klmektedir. zellikle MA sresi 10 saate kartlmasyla toz boyutundaki klme oran daha da fazlalamtr. Bunun
sebebi artan deformasyon ve peklemenin sonucunda krlma mekanizmasnn etkili olmasdr.
Benzer ekilde, Ark ve Trker MA yntemi ile rettikleri Fe-Fe3C kompozitlerde alamlama sresinin artmasyla
toz boyutunda azalmalar tespit etmilerdir [10, 11]. Gemite yaplan baz almalarda aratrmaclar, kk paralarn byk paralarla kaynaklama eiliminde olduklarn ve MA sresinin artmasyla tekrar tane klmesinin
olutuunu tespit etmilerdir [12, 13].
728

ekil 1. MA sresine gre toz boyutu deiimi

Resim 2.de verilen SEM fotoraflar da MA sresinin artmasyla tane boyutunda oluan klmeyi ak bir ekilde
ifade etmektedir. Ayrca bu resimlerde TK numunesinde herhangi bir deformasyon etkisi grlmezken, MA ilemi
uygulanan tozlarda oluan deformasyon belirgin olarak grlmektedir
Resim 2. (a) TK, (b) 2 saat MA, (c) 6 saat MA, (d) 10 saat MA ilemi uygulanm tozlarn SEM resimleri
729

3.2. Mikro Yap zellikleri

Resim 3te kompozitlere ait mikro yap resimleri verilmitir. Bu resimlerde grld gibi tm numunelerin parack
dalm homojene yakndr. TK numunesinde gzeneklerin neredeyse tamamen kapand sylenebilir. 2 saat MA
yaplm numunede tane snrlar neredeyse kaybolmuken, dier numunelerde ksmen tane snrlar belirgindir.
2 ve 6 saat sreyle MA ilemi yaplm numunelerde tane snrlarna yakn yerlerde ksmen kk topaklamalar
mevcuttur. Tm numuneler iin ounlukla takviye elemanlar matris ierisinde gmlm olmakla birlikte, ksmen
tane snrlarnda kk birikmelerin olduu da grlmektedir. zellikle 10 saat MA yaplm numunelerde gzenek
miktarlarndaki art belirgindir.
Resim 3. Kompozitlerin Optik Mikroskop resimleri (a) TK ilemi yaplm, (b) 2 saat, (c) 6 saat ve
(d) 10 saat MA ilemi yaplm.
Bunun yannda 10 saat MA yaplm numunelerde mikro yapda grlen karartlarn kirlenmeler olabilecei dnlerek bu numunelerin SEM ve EDS analizleri alnmtr (Resim 4). 10 saat MA yaplm kompozitin optik mikroskop
resimlerinde kirlenme varm gibi grnen yzeylerin aslnda klm seramik paracklar ve gzeneklerden ibaret olduu kompozitlerden alnan SEM ve EDS analizleriyle tespit edilmitir. Bu analizlerde kompozitin yapsnda
herhangi bir reaksiyon rn element ya da faz olumad belirlenmitir.
(a) SEM grnts

(b) Genel EDS analizi
Resim 4. 10 saat MA yaplm Al+%10 Al2O3 kompozit numuneler iin SEM resmi ve EDS analizi
730

3.3. Younluk ve Gzeneklilik

Younluk ve gzeneklilik deerleri ekil 2de verilmitir. Beklendii gibi tm deneylerde sinterleme sonras llen
younluk deerleri ham younluk deerlerine oranla artmtr. MA uygulanmam, ancak bilyesiz olarak eksenli
turbula cihaznda homojen karm yaplm kompozit numunelerin sinterleme ncesi ve sinterleme sonras younluk deerleri, MA yaplm kompozit numunelere gre daha yksektir ve gzenek deeri de daha dktr. MA
sresinin artmasyla numunelerin younluk deerleri derken, gzenek miktarlar da ksmen artmtr. MA sresinin artmasyla oluan souk deformasyon ve pekleme, tane boyutunu klterek malzemelerin sktrlabilirliini
olumsuz etkilemitir. Dolaysyla bu durum, MA sresinin artmasyla younluun dmesine ve gzenekliliinde
ksmen artmasna neden olmutur. Sarta ve arkadalarda, kk tozlarn sktrmaya diren gsterdiini ve
bundan dolay zellikle nano boyutlu tozlarn sktrlabilirliinin ok zor olduunu belirtmitir [9].
ekil 2. Al+%10 Al2O3 blok numuneler iin younluk ve gzeneklilik deerler

3.4. Sertlik
Brinell sertlik deerleri ekil 3te verilmitir. Beklendii gibi saf alminyumun sertlik deeri 28 BSD iken MA ile
numunelerin sertlik deerleri doal olarak ykselmitir. MA sresinin artmasyla genel olarak tm numunelerin sertliklerinde bir art olduu grlmektedir. Bu artn, MA srasnda yksek deformasyonun etkisiyle oluan tane klmesinden kaynakland dnlmektedir. Benzer ekilde Ark, MA ile rettii kompozitlerde sertlik iin en nemli
faktrlerden birinin MA sresi olduunu belirtmitir. Ancak, yksek sinterleme scaklnn ve sresinin de sertlii
etkiledii belirtilmitir. 10 saate kadar MA ilemlerinde 650 C de 20 saat sinterlenen numunelerin sertlik deerinde
dzenli bir art grlrken, 10 saat MA ileminden sonra keskin bir art gzlemi ve bu artn kompozit yapsnda
oluan Al4C3 varlndan kaynaklandn belirtmitir [10]. Ayrca gzenekliliin mekanik zellikleri olumsuz etkiledii
bilinmektedir. Resim 3.(c)de grld gibi MA sresinin artmasyla gzeneklilik bir miktar artsa da, gzeneklerin
ok kk olmas ve dzgn dalmas sebebiyle kompozitlerin mekanik zelliklerinde olumsuz bir etki olumamtr. Gzeneklerin ok kk ve kresel ekilli olmas tercih edilmektedir. Baz seramik malzemelerde gzenek
deeri % 45lere kadar ksa bile, gzenekler ok kkse tam youn dayanma yakn deerler elde edilebileceini
belirtilmitir [9].
ekil 3. Sertlik (BSD) lm sonular
731

4. SONULAR

MA sresinin artmasyla toz boyutu klmtr.

retilen blok numunelerde homojen bir parack dalm olumaktadr.
MA sresinin artmasyla younluk azalrken, gzeneklilik artmaktadr.
MA sresinin artmasyla sertlikte srekli bir art meydana gelmektedir.
TEEKKR
Gazi niversitesi BAP Birimine 07/2010-58 nolu proje kapsamnda yapt katklardan dolay teekkr ederiz.
Kaynaklar
1. Kaw, A.K., Mechanics of Composite Materials, Crc Press, Washington, 1997.
2. Hull, D. ve Clyne, T.W., An Introduction to Composite Materials, 2nd Edition, Cambridge University Press,
Cambridge, 1996.
3. Suryanarayana, C., Mechanichal alloying and milling, Progress in Materials Science, 46: 1-184 (2001).
4. Ylmaz, O. and Buytoz, S., Abrasive wear of Al2O3 reinforced aluminum based MMCs, Composites Science and Technology, 61: 2381-2392, 2001.
5. Abenojar, J., Velasco, F. and Martinez, M. A., Optimization of processing parameters for the Al + 10 % B4C
system obtained by mechanical alloying, Journal of Materials Processing Technology, 18, 441-446, 2007.
6. Kennedy, A. R. and Brampton, B., The reactive wetting and incorporation of B4C particles into molten aluminum, Scripta Materialia, 44, 1077-1082, 2001.
7. Toptan, F. ve Kerti, I., B4C ile takviye edilen Alminyum matrisli kompozitlerin dkm yntemi ile retimi, 12.
Uluslar aras Metalurji-Malzeme Kongresi, 808-812, stanbul, Kasm-2006.
8. Akn, G., Mindivan, H., imenolu, H. ve Kayal, E. S., Toz metalurjisi yntemiyle retilen Alminyum matrisli
bor karbr takviyeli kompozitlerin anma davrannn incelenmesi, 12. Uluslar aras Metalurji-Malzeme
Kongresi, 735-740, stanbul, Kasm-2006.
9. Sarta, S, Trker, M, Durlu, N,.Toz Metalurjisi ve Parackl Malzeme lemleri, Trk Toz Metalurjisi Yaynlar: 05, Ankara, 2-9, 15-34, 206, 237, 379-387, 404-410, 2007.
10. Ark, H., Production and characterization of in situ Al4C3 reinforced aluminum based composite produced by
mechanical alloying technique, Materials and Design 25, 1-4, 2004.
11. Ark, H., Trker, M., Production and characterization of in situ Fe-Fe3C composite produced by mechanical
alloying, Materials & Design, 28: 140-146 (2005).
12. Lee, W., Kwun, S. I., The effects of process control agents on mechanical alloying mechanisms in the Ti---Al
system, Journal of Alloys and Compounds, 240: 193-199, South Korea, (1996).
13. Lu, M.O. Lai, C.W. Ng, Enhanced mechanical properties of an Al based metal matrix composite prepared using
mechanical alloying, Materials Science and Engineering A252: 203211, Singapur, (1998).
732

MECHANICAL
PROPERTIES
www.turkishpm.org
733

Production of Ni3Al-Fe Composite and Investigation of

Mechanical Properties
1
Ayhan Erol, 1smail Yldz, 2Ahmet Yonetken
Afyon Kocatepe University, Technology Faculty, 03200, Afyonkarahisar/ Turkey

Afyon Kocatepe University, Engineering Faculty, 03200, Afyonkarahisar/ Turkey
aerol@aku.edu.tr, iyildiz@aku.edu.tr, yonetken@aku.edu.tr
1
2
ABSTRACT
In intermetallics high resistance to creep and oxidation, high strenght, low density are desired properties. Sintering
process was used in this study by adding different amounts of Fe powder to Ni-Al powder mixture. When the properties of the sample after sintering were examined 40% weight Fe added composition was found as the most suitable
ratio in terms of mechanical properties. Analyses were conducted metallographically on the samples after sintering,
the densities were calculated, hardness and shear strengths were determined. According to the data 40% Fe added
composition had 5,82 gr/cm3 of density, 92,8 HB hardness values and displayed 221 MPa shear strength.
Keywords: Sintering, intermetallic, powder, composition
1. ntroducton
The intermetallic compound, Ni3A1, has many advantages such as high melting point, low densities, high strength,
as well as good corrosion and oxidation resistance, which make it an attractive candidate for high-temperature
structural use [1-4]. Furthermore, the high strength and work hardening ability of these alloys mean that they
can perform well in a variety of wear environments [5]. Because of the potential use of nickel aluminides at high
temperatures, it is imperative to understand and study their oxidation behaviour [6]. However, low ductility, brittle
fracture and processing problems seriously handicapped its application [7]. Its indicated that high temperature alloys should resist to corrosive affect of service atmosphere, should have enough strength in addition should protect
its microstructure at elevated temperatures and stay durable [8]. AlFeNi alloys have been employed as the basis
of the Ni-Al-Co permanent magnets because of their good magnetic properties and as high-temperature materials
due to high melting points and excellent oxidation resistance [9-11]. Due to their good magnetic properties, Ni-Al-Fe
alloys have been employed as the basis of the Alnico permanent magnets. Later on, they were improved by major
additions of Co and minor additions of Cu, Ti and traces of other elements [12,13].
Figure 1. Ni-Al-Fe ternary phase diagram [13].
734

The purpose of this study is to obtain Ni3Al-Fe composite by heat threatening at 600 C. It is known that the intermetallics obtained with addition of Fe have low density, high hardness, and high shear strength. In the light of this
information the mechanic properties of obtained Ni3Al-Fe will be investigated.
2. expermental method
In this study properties of raw materials are; the nickel is in 99.8% purity and has particle size lower than 40 , the
aluminum is in 99.95% purity and has particle size lower than 75 and Fe is in 99.9% purity and has particle size
lower than 150. For obtaining 11 gr rectangle sample according to the formula (NixAly)(Fe)100-(x+y) (x+y= %80, 70,
60 weight) Al and Fe as well as Ni material were mixed homogenously for 24 hours in certain proportions in order
to produce a Ni based intermetallic. For this process the raw material powders mixed in mixer has single phased
electric motor. This mixer is a mixer that circular motion.
The mixture was shaped by one axis cold hydraulic pressing in a suitable container. In shaping process the pressing pressure was 300 bar. Pressed samples have undergone sintering for 2 hours at 600 C in a tube oven within
Argon gas atmosphere. They were left to free cooling after sintering, their hardness, density and shear strengths
were measured. Also XRD and SEM were applied to samples after sintering.
The XRD analyses carried out in Shimadzu XRD-6000 the radiation chosen is Cu k-alfa the scan range is 2 teta and
scanning rate is 2degree/minute. The SEM microanalyses performed in Leo 1430 VP secondary electron detector
and the W used as filament of electron gun.
3. EMPIRIC RESULTS
3.1. Density: The densities of the samples obtained after sintering were calculated by using (d=m/V) calculation
formula (Figure 2). Here m is the mass of sintered sample; v is the volume of sintered sample, calculated geometrically. When Figure 2 is examined highest density is in 40% Fe added mixture as 5.82 gr/cm3 and the lowest density
has 5.57 gr/cm3 values in 20% Fe added mixture.
Figure 2. Density graphic of Ni3Al-Fe composite materials

3.2. Hardness: Hardness values of samples which were obtained in connection with sintering effect were measured
as Brinell (Figure 3). In Brinell hardness measurement method 10 mm spherical ball tip used. The approximate data
has taken that performed any 3 places on rectangle sample. The reason is obtaining the exact hardness data.
When Figure 3 is examined while the highest hardness was obtained in 40% Fe added mixture as 92.8 HB, the
lowest hardness was obtained in 20% Fe added mixture as 86.2 HB.
735

Figure 3. Hardness graphic of Ni3Al-Fe composite materials

3.3. Volumetric Change: The volumetric changes of Ni3Al-Fe composite material after sintering were calculated by
using (d=m/V) calculation formula (Figure 4). The volume of pre-sintered and post-sintered samples was measured
with Archimedes principle that volume changing in liquid.
Figure 4. Volumetric change graphic of Ni3Al-Fe composite materials

When Figure 4 is examined it can be seen that decreases in volumetric changes of composite materials occur
inversely proportional to increases in density values when compared to pre-sintering.
While the highest volumetric change was obtained in 40% Fe added mixture with 1.75 cm3, the lowest volumetric
change was 2.06 cm3 in 20% Fe added mixture. The increasing in density is changing diametrically with decreasing
in volume change. This situation shows that the desired sintering occurred.
3.4 Shear Strength: Shear strength values (Figure 5) for the samples obtained after sintering were measured by
Shimadzu AG-IS 100KN device. Shear strength performed via connecting shear apparatus to jaw of tensile testing
device and the rectangle samples placed in this apparatus and testing performed.
736

Figure 5. Shear strength graphic of Ni3Al-Co composite materials

While the highest shear strength value was obtained as 221 MPa in 40% Fe added mixture, the lowest shear
strength value was 133 MPa in 20% Fe added mixture.
3.5 Xrd Analysis: After sintering, XRD analysis was performed upon the samples (Figure 6 and Figure 7). When
the analysis results were examined, the highest peak value was observed in Ni3Fe phase among the sintered composite materials. Following this phase, FeAl phase has the second highest peak value. It is anticipated that Ni3AlFe
peak value indicates the reaction of Ni with Al within the composite material.
Figure 6. XRD graphic of Ni-Al-20% Fe composite material

The XRD analysis result of 40% Fe added mixture is seen in Figure 7. As it is seen in the Figure as well, Ni3Fe
phase has the highest peak value. It is anticipated that this case indicates that Ni element may be formed within
the composite material.
Figure 7. XRD graphic of Ni-Al-40% Fe composite material

When Figure 6 and 7 are examined it is seen that intermetallic phase formed in Ni3Al-Fe composition after sintering
is Ni3Al, Ni3AlFe, Ni3Fe, NiAl, FeAl, Ni, FeNi.
737

3.6 Sem Analysis: SEM analysis of the composite materials obtained depending upon sintering effect was performed (Figure 8). When SEM images were examined, it is observed that more homogenous and less porous
structure 20, 30 and 40% Fe added materials. The reason of obtaining less-porous structure is more sintering. It is
thought that this situation indicates that Fe material in the composite material could increase the sintering temperature by reacting with other materials.
Figure 8. SEM images of Ni3Al-Fe composite materials, a) SEM image of Ni-Al-20% Fe added composite
material, b) SEM image of Ni-Al-30% Fe added composite material, c) SEM image of Ni-Al-40% Fe added
composite material
The following results were obtained from the experimental findings;
The highest density value was calculated in 40% Fe added composite material as 5.82gr/cm3 (Figure 2).
The highest hardness value was measured as 92.8 HB hardness in 40% Fe added composite material among
the sintered composite materials.
The highest shear strength was measured in 40% Fe added composite material as 221MPa.
When SEM analysis were examined, it was seen that 20, 30 and 40% Fe added composite material has a more
spaceless and homogenous structure.
While the flow charted followed in empiric studies is similar to the one used by Yonetken et al. in their studies,
there are some differences in the values [14].
Decreasing in volume change is changing diametrically with the increasing in density, by the way the desired
sintering quality occurred.
5. Acknowledgement:
It was supported by Afyon Kocatepe University SRPC Project no 10.TEF.01. We would like to thank to Scientific
Research Project Commission for their support.
REFERENCES
[1] Morsi, K., Review: Reaction synthesis processing of NiAl intermetallic materials, Mater Sci Eng A; vol. 299,
pp.115, 2001.
[2] Sikka, V. K., Deevi, S. C., Viswanathan, S., Swindeman, R. W., Santella, M. L., Advances in processing of
Ni3Al-based intermetallics and applications, Intermetallics, vol.8, pp. 132937, 2000.
738

[3] Li, S., Feng, D., Luo, H., Microstructure and abrasive wear performance of chromium carbide reinforced Ni3Al
matrix composite coating, Surface & Coatings Technology, vol. 201, pp. 45424546, 2007.
[4] Peng, L. M., Fabrication and mechanical properties of microalloyed and ceramic particulate reinforced NiAlbased alloys, Journal of Alloys and Compounds, vol. 440, pp. 150153, 2007.
[5] Li, S. P., Luo, H. L., Feng, D., Cao, X., Zhang, X. E., Abrasive Performance of Chromium Carbide Reinforced
Ni3Al Matrix Composite Cladding, Journal of Iron and Steel Research, vol. 16(5), pp. 87-91, 2009.
[6] Moussa, S. O., Morsi, K., High-temperature oxidation of reactively processed nickel aluminide intermetallics,
Journal of Alloys and Compounds, vol. 426, pp. 136143, 2006.
[7] Deevi, S. C., Sikka, V. K., Nickel and iron aluminides: an overview on properties, processing, and applications, Intermetallics, vol. 4, pp. 35775, 1996.
[8] Akdoan, A., Superalloys, Access: www.yildiz.edu.tr/~akdogan/lessons/malzeme2/Super_Alasimlar.pdf.,
2010.
[9] Zhang, L., Du, Y., Xu, H. etc., Phase equilibria of the AlFeNi system at 850 C and 627 C, Journal of Alloys and Compounds, vol. 454, pp. 129-135, 2008.
[10] Marcon, G., Lay, S., Ann. Chim. Sci. Mater. vol. 25, pp. 2140, 2000.
[11] Bitterlich, H., Loeser, W., Schultz, L., J. Phase. Equilib. vol. 23, pp. 301304, 2002.
[12] Eleno, L., Frisk, K., Schneider, A., Assessment of the Fe-Ni-Al system, Intermetallics, vol. 14, pp. 12761290, 2006.
[13] Raghavan, V., Al-Fe-Ni (Aluminum-Iron-Nickel), Section II: Phase Diagram Evaluations, vol. 29, pp. 180184, 2008.
[14] Yonetken, A., Erol, A., Talas, S., Microwave Sintering of Electroless Ni Plated SiC Powders, Material Science and Engineering Conference, 1-4 September 2008, Nunberg, Germany.
739

TOZ METALURJS LE RETLEN Fe-26Al ve Fe-50Al TOZ

KARIIMLARININ ISIL LEM SONRASI MKROYAPI VE MEKANK
ZELLKLERNN ARATIRILMASI
Mehmet AKMAKKAYA* ve kr TALA**
**
*
AK, Teknoloji Fakltesi, Otomotiv Mhendislii Blm, 03030, Afyonkarahisar, cakmakkaya@aku.edu.tr
AK, Teknoloji Fakltesi, Metalurji ve Malzeme Mhendislii Blm, 03030, Afyonkarahisar, stalas@aku.edu.tr
ZET
Bu almada, Fe, Al tozlar atomik % oranlarda Fe-26Al ve Fe-50Al kompozisyonlar oluturularak tek eksenli presle preslenmitir. Numuneler 550, 600, 650, 700, 750, 800 C de mikrodalga frnda argon gaz atmosferlerinde 0,5, 1
ve 1,5 saat srede sinterlenmitir. Sinterleme ileminden sonra konvansiyonel frn kullanlarak atmosfer artlarnda
450 0Cde 5,10, 15, 30 saat sreyle sl ilem uygulanmtr. Yaplan sl ilem kesme mukavemet deerini artrrken
artan sl ilem sresine bal olarak kesme mukavemetinde azalma olduu grlmtr. Bununla birlikte artan
alminyum oran da kesme mukavemetini aa ekmektedir. En yksek kesme mukavemet deeri 5 saat sl ilem
yaplan numunelerde llmtr. Sinterleme scaklnn 650 C nin zerinde seilmesi durumunda numunelerde
hacimsel genleme gzlenmitir. SEM sonularna gre; matris faz Al oluturmakta ve Fe,Ti tozlarnn sinterlenmi
olarak dalm grlmtr. Sinterlenmi numunelerin XRD sonularnda FeTi, AlTi, Ti3Al, Fe3Al, FeAl intermetalik
bileiklere rastlanmtr.
Anahtar Kelimeler: Toz Metalurjisi, Sinterleme, Mekanik zellikler.
PRODUCED BY POWDER METALLURGY POWDER MIXTURES Fe-26Al and

Fe-50Al Microstructure AFTER HEAT TREATMENT AND MECHANICAL
PROPERTIES OF INVESTIGATION
ABSTRACT
In this study, Fe, Al powders atomic% Fe-26Al and Fe-50Al composition rates by creating pressed under uniaxial
presses. Samples 550, 600, 650, 700, 750, 800 C in a microwave oven atmosphere of argon gas, 0.5, 1 and 1.5
hours, sintered time. After sintering, atmospheric conditions using a conventional oven 5, 10, 15, and 30 hour 450 C
heat treatment were applied. Increasing the heat treatment increased the shear strength shear strength, depending
on the duration of heat treatment were reduced. However, the increasing rate of shear strength of aluminum draws
down. The highest shear strength value of the samples were measured 5 h heat treatment. Sintering temperatures
at around 650 C, if you select on the volumetric expansion observed in the samples. According to the results of
SEM, the matrix phase of the Al and Fe to create, as the distribution of Ti powders were sintered. XRD results of
samples sintered Fe3Al, FeAl Intermetallics compounds were found
Keywords: Powder Metallurgy, Sintering, Mechanical Properties
1.Giri
Toz metalrjisi parack boyutu 0,1 ila 200 m aralnda deien metal esasl tozlar paralarn ekil ve boyutlarna uygun olarak presleyip, (0.750.86)Tm scaklnda vakum veya koruyucu gaz atmosferinde sinterleyerek tipik
740

mhendislik paracklarndan (metaller, seramikler ve plastikler) son ekle yakn para imal etme yntemidir[1, 2].
Toz metalrjisi metal, seramik tozlarnn retimi ve bu tozlarn mekanik ve termik etkilerle birletirilerek kullanl
mhendislik paralara dntrlmesini amalayan bir imalat srecidir[3]. retilen paralarda son ilemden sonra
%1030 arasnda gzenek mevcutsa gzenekli, %13 arasnda gzenek varsa bu rne kompakt malzeme denilir[4, 5]. Karm tozlar oluturmak iin paracklar homojen bir ekilde kartrma, toz tanelerinin birbiriyle ba
oluturmalar iin kalpta presleme ve atmosfer kontroll sinterleme ilemi basamaklarn ierir[6]. Sktrlm toz
paralar arasndaki ba, yapma, mekanik kilitleme ve benzeri trden zayf balar olup kristal kafes ierisindeki
ba dayanmna gre ok zayftr. Sktrlm tozlar bir birleriyle temas etseler bile bir birlerinden bamsdrlar.
Sinterlemede scakln etkisi ile bu tozlar arasndaki temas noktalar artrlmakta, atom ve iyonlar arasnda bir ba
oluturulmaktadr. Tek bileenli sistemlerde sinterleme tamamen kat fazda gerekleir. ok bileenli sistemlerde
sinterleme ilemi sktrlm parann kat formunu (iskeletini) koruyacak ekilde kat veya sv fazda gerekleir[7]. Gerekte sinterleme ilemi de bir scak basn kayna ilemi olup, tozlarn birbirleriyle birlemesi difzyon
mekanizmasyla olmaktadr. Toz metalrjisi, ana imalat yntemleri olan dkm, plastik ekil verme, talal imalat
ve kaynakl imalata (ergitme kayna) gre daha farkl bir imalat yntemidir ve bu yntemin kendine has zellikleri
vardr. Bunlar, retimi zor olan alamlarn daha kolay retilebilmesi, karmak ekilli paralarn imalatnn kolayl,
younluk kontrolnn yaplabilmesi ve ekonomiklik gibi zelliklerdir. Toz metalrjisi genelde kalite ve maliyet asndan dier yntemlerle retilemeyen paralarn imalatnda yaygn olarak kullanlr[8]. Toz metalrjisi ile elde edilmesi
dnlen bir parann malzemesi ve elde edilecek para, kalite ve maliyet asndan dier yntemlerdekilerle
karlatrlmal ve elde edilen sonuca gre toz metalrjisinin uygulanp, uygulanmamasna karar verilmelidir. Toz
metalrjisi teknolojisi, makine ve elemanlarnn yapmnda istifade edilen nceki teknolojilerden farkldr. En nemli
farkll, istenilen zellik ve ekle sahip rnlerin elde edilmesine imkn vermesidir. Kaliteli ve karmak paralarn
ekonomik olarak retilebilmesi toz metalurjisini daha da cazip klmaktadr[9, 10]. Toz metalurjisi malzemeleri ierisinde demir esasl toz metal malzemeler nemli bir yere sahiptirler. Bu malzemelerin eidini arttrmak ve uygulama
alann geniletmek iin eitli yntemler vardr. Bu yntemlerden en nemlisi eitli alam elementlerinin ilavesi
ile malzemelerin alamlandrlmasdr[11, 12]. Daha karmak ekillere ve zelliklere sahip olan paralarn retimi,
toz metalrjisinin presleme, piirme (sinterleme) ve sl ilem operasyonlarndan baka ek ilemlerin yaplmasn
zorunlu klar. Bu paralarn malzemelerinin fiziksel, mekanik ve dier zelliklerinin iyiletirilmesi iin malzeme younluunun uygun ekilde ayarlanmas, yeterli alamlamann ve sl ilemin yaplmas gereklidir. Bununla birlikte,
ergime scakl dk olan metaller sayesinde retilecek paralarn gzeneklerinin yeterli derecede doldurulmas
da salanmaldr. Karmak ekle sahip bir rnn elde edilmesi, bazen byk boyutlardaki hammaddeden dier imalat yntemleri kullanlarak, bazen de toz metalrjisi yntemi kullanlarak yaplr. Toz metalrjisi ynteminde
presleme, piirme (sinterleme) ve az sayda talal imalat gerekebilir. Parann btn olarak hazrlanmas gerekli
zaman arttrmakta, daha byk boyutlu preslere ve pres kalplarna ihtiya gerektirmekte ve bunlarn yannda bir
ok teknik ve ekonomik zorluklara neden olmaktadr[13]. Gnmzn vazgeilmez bir paras olan TM rnleri
hayatmzn birok yerinde karmza kmaktadr.
TM teknolojisi yntemiyle mhendislik malzemelerinin kullanm sresini artrmak, maliyetini drmek ve mukavemetlerini artrmak iin birok alma yaplmaktadr[1](German 2007). Toz metalrjisi prosesleri kullanlarak retilen
tm yapsal paralarda %100 teorik younluklara eriilmek istenir. stenilen bu deerlere ulamak balang toz
zelliklerine, kullanlan proses parametrelerine ve en ok da kullanlan sinterleme koullarna baldr. Tm koullar
ne kadar ideal olursa olsun uygun seilmeyen sinterleme parametreleri dk teorik younluklu paralar sunar.
Yksek teorik younluklu paralarn elde edilmesinde en ok kullanlan sinterleme teknii sv faz sinterleme tekniidir. Bu teknikte yksek teorik younluklu ve buna bal olarak stn mhendislik zelliklere ulaan paralar elde
edilebilir. Balang tozlar ierisine katlan dk miktardaki ilaveler, sinterleme esnasnda yap ierisinde sv faz
oluturarak sinterleme mekanizmasn hzlandrrlar. Oluan sv faz yapy daha sk hale getirerek younluk deerlerinin artmasna sebep olur. Yap ierisinde oluan sv faz sadece younluk deerlerini arttrmaz ayn zamanda
sv fazn karakteristiine bal olarak parann mhendislik zelliklerini deitirir[14]. Hui-Zhen Kang ve arkadalar
Fe Al toz karmlarnn tepkisel davranlarn aratrmlardr. Sinterleme ileminde toz bileenleri glenir ve
daha mukavemetli yaplar oluur. Fakat ime problemi serbest katlaabilen demir alminyum tozlarnda grlr.
%29 Fe ieren Fe3Al intermetaliinde serbest boluklar katlarken Fe2Al5 bileiindeki gibi katlar. %71 demir ieren Fe2Al5 dk scaklkta katlamas srasnda gzenekli mikro yaplarda art olur. nk bu scaklkta FeAlun
ekzotermik reaksiyonun sonucu hzl ve iddetli sveren bir yapda olmasndan kaynaklanmaktadr[15]. Demir alminat ailesini ieren stratejik elementlerin dnm salanm ve malzemelerin maliyeti ve scaklk uygulamalar
aratrlm, dikkatli bir ekilde gelien yapsal malzemelerin ucuz olduu bir snf oluturulmutur. almalarda
600 C scaklklarda elikten daha hafif ve daha mukavetli, bununla beraber evresel korozyondan korunabilen
oksidasyon direnci yksek yap malzemesi retilmitir. Bu yzden Fe3Al alamlar termal uygulamalarda kullanlabilen potansiyel bir malzemedir[16]. Maziasz, McKaamey ve arkadalar FeAl komposizyonlarn B2 D03 yapsal
dnmlerdeki etkiyi aratrmlar. Bu almalarnda Fe-28Al alm 530670 C scaklkta B2 D03e dnm
salad belirlenmitir. ntermetalik tozlarn demir alminyum ksmn Godlewska ve arkadalar almtr. Burada demir alminyum malzemeleri %40 alminyum ieren metal tozlar, 25 40 m tane boyutuna sahip tozlarn
belirli oralarda karmlar salanarak mekanik alamlama allmtr. Fe Al toz karmlar alminyumun ergime
scaklna yakn 660 C de argon ve hidrojen karm gaz atmosferinde sinterlenmi, bylelikle oda scaklnda
dayankl ve snek intermetalik malzeme retilmitir[17].
741

2. Deneysel almalar
Sinterleme malzemelerin performanslarn artrmak iin termal enerji kullanlarak yaplan bir ilemdir. ekil 1de
malzeme bilimcilerinin malzeme zerimde urat drt temel grlmektedir. Bu temel prensipleri istenilen ynde
deitirmek iin kullanlan yntemlerden birisi de sinterleme ilemidir. Sinterleme ileminde takip edilen genel aamalar ekil 2de verilmitir.
ekil 1. Malzeme bilimi ve mhendisliin drt temel esas
ekil 2. retim ynteminde sinterleme blmlerinin basamaklar.

Sinterleme, birbirine temas eden paracklarn yksek scaklklarda birbirine balanmasn salar. Bu balanma,
ergime scaklnn altnda kat halde atom hareketleriyle oluabilir. Fakat pek ok durumda, sv faz oluumu ile
birlikte gerekleir[1]. Sinterleme, toz halindeki malzemenin erime scakl altndaki bir scakla belli bir sre maruz braklarak tozlarn birbirlerine dedikleri noktalardan balayarak kaynamasna denir. Baka bir ifadeyle teknik
terminolojide sinterleme terimi, metalik veya metalik olmayan anorganik tozlardan oluan kat rnlerin ergime
scaklklarnn veya ne kadar stlmalar anlamna gelmektedir. Bu ilem esnasnda taneler farkl difzyon
mekanizmalar ile bir araya gelirler. Zamanla yap iindeki boluklar kapanr ve bu nedenle parada ekmeler oluur. Sonuta youn bir yap elde edilir[18]. Sinterleme, yksek scaklkta atomlarn yaynm ve kk paracklarn
yzey enerjisinin azalmasyla gerekleir. Kristal yapl katlarda, hemen hemen btn parack temas noktalar snrlar enerjisine sahip olan tane snrlarn oluturur. Sinterleme esas olarak itici gler, mekanizmalar ve aamalar
asndan incelenir:
Sinterlemenin itici gleri balanmaya neden olan mikroskobik erilikleri tanmlar.
Sinterleme mekanizmalar itici glere tepki olarak oluan atom hareketlerinin yolunu tanmlar.
Sinterleme aamalar atom hareketleri sonucu oluan geometrik geliimi tanmlar. Bu aamalar da dier taraftan itici gleri deitirir.

tici gler veya sinterleme gerilmeleri mikroyapdaki eriliklerden kaynaklanr. Sinterleme mekanizmalar genellikle
yzey, tane snr veya kristal kafesinde oluan yaynm ilemleridir. Sinterleme aamalar etkin itici gcn ve kinetiin aklanmasna yardmc olur ve ilemin matematik modellenmesinde kullanlr[1]. Tm toz metal ve seramik
paralar mukavemet kazandrmak amacyla yksek scaklklarda sinterlemeye tabi tutulurlar. Sinterleme ile preslenmi toz paralarda younluk artna neden olan boyutsal (veya hacimsel) klme meydana gelir. Sktrlm
toz paralar arasndaki balant yapma, mekanik kilitleme ve benzeri trden zayf balar olup kristal kafes ierisindeki ba dayanmna kyasla ok zayf kalmaktadr. Sktrlm toz yaplar ierindeki partikller bir biri ile temas
742

ediyor olsa da her bir partikl dierinden bamszdr. Sinterleme ile partikl temas noktalar artmakta ve atomlar
ve iyonlar arasnda fiziksel bir ba olumaktadr. Bu trden ba oluumu kristal kafes sistemi ierisindeki yksek
dayanml atomsal balanma ile benzetir. Tek fazl sistemlerde (saf toz kullanmnda) sinterleme tamamen kat
fazda gerekleir. ok fazl sistemlerde (birden fazla trde toz bir arada kullanlmas durumunda veya toz ierisinde
bulunan safszlklar) sinterleme ilemi sktrlm parann kat formunu (iskeletini) koruyacak ekilde sv fazda
gerekleebilir. Bu durum zellikle ok ince taneli tozlarda daha fazla grlr[7]. Kat durum sinterlemesi, kompakt
hale getirilen tozlarn btnln bozmayan scaklkta kat bir durumda meydana gelir, sv faz sinterlemesi, kompakt tozlar sv faz scaklna gei durumunda yaplan sinterlemedir. Bu iki olay ekil 3de gsterilmektedir[19].
ekil 3. Sinterleme trleri [19].

3. Fe26Al Bileiin XRD Analizleri
Deneysel almalar sonucunda oluan mikroyaplarn XRD analizleri yaplmtr. Bu almada seilen 1 saatlik
sinterleme sresine daha ok nem verilmitir ve dier mikrodalga sreleri iin yaplan XRD krnm desenleri iin
snrl XRD ve hesaplama yaplmtr. Bu analizlerde farkl sinterleme scaklk deerleri, sinterleme sresi ve toz
bileimlerine gre oluturulan numunelerin sonular deerlendirilmitir. XRD pikleri aada ekil 4 de verilen tipik
XRD deseninde gsterilmitir. Burada f ana pikleri temsil etmektedir ve dier pikler ise alamda grlen sperlatis
pikleridir.
Fe26Al kompakt numunelerin 550 C 1, mikrodalga frn Argon atmosferinde sinterleme ilemlerinden sonra 450
C tp frn argon atmosferinde 5, 10, 15, ve 30 saat srelerde sl ilem yaplarak oluan yaplarn XRD analizleri
grlmektedir(ekil 5). almalarda tek eksenli presleme yaplarak sinterlenmi numunelerin XRD sonularnda
D03, B2, FeAl, Fe(110), Fe(200), Al(200), Al(220) fazlar tespit edilmitir. Ayn ekilde Robin ve arkadalar bu fazlar
scak presleme reaksiyonlarnda da elde edilmitir[20]. Krnm deseninde verilen kutucuklarda sadece DO3 (Fe3Al)
ve B2 (FeAl) alamlarnda grlen pik pozisyonlar verilmitir(ekil 4). Pik dzlemleri bilinmeyen durumlarda hesaplanabilirken genellikle XRD krnm veri tabanndan piklere karlk gelen deerler bulunabilir.
Sktrlan tozlarn yaplan sl ilemleri sonucu elde edilen XRD krnm desenlerinde sinterleme srasnda ortaya kabilecek DO3 ve veya B2 fazlarnn tespit edilmesi, DO3 faz iin, krnm desenlerinde uzun mesafeli
dzen(UMD) yaps aadaki formlle ifade edilebilir:
SD03 = (I111/I220)obs / (I111/I220)calc and SB2 = (I200/I220)obs/(I200/I220)calc
3. 1
S, UMD parametresi, Iobs ve Ical ise normalize edilmi srasyla llen ve hesaplanm pik iddetleridir. (111)DO3
sperlatis ve (220)DO3 ana piklerine ait iddetlerin hesaplanmas Ihkl = |F| 2 mhkl Lp(), forml ile gerekletirilmitir. Burada, F is yap faktr ve mhkl ise ilgilenilen dzleme ait pikin arpm faktrdr ve son olarak Lp is Lorentz
polarizasyon faktr olarak bilinmektedir. Bu hesaplamalardaki scaklk faktr deney yaplan (XRD) scakln
btn deney numuneleri iin ayn olmas nedeniyle dikkate alnmamtr. UMD sonular Fe ve Al elementleri iin
Sinterlenmemi ve 0,5, 1 ve 1,5 saat deiik srelerde sinterlenmi numuneler iin hesaplanmtr. rnein Fe ve
Al iin atomik fraksiyonlar XFe ve XAl (XTi ) olarak ifade edilsin ve dolaysyla bu terimlerin toplam sistemdeki toplam
fraksiyon orann yan 1 i verecektir. Yani, XFe+XAl+XTi+XCu=1. Tam olarak UMD yapsna sahip olan Fe3Al sisteminde, kristal yaps drt ana sperlatise ayrlabilir: a, b, c ve d; ayrca bu sperlatislerin toplam fraksiyonlar ise
Ya+Yb+Yc+Yd=1. c ve d sperlatisleri sekiz Fe atomlar tarafndan tamamen doldurulur ve b sperlatisi ise drt Fe
atomu tarafndan ksmen doldurulur geri kalan d sperlatisi ise Al tarafndan doldurulur. Dolaysyla, sperlatis pik
yansmas iin b sperlatisi yap faktrlerinin hesaplanmasnda nemli bir kstas olacaktr. nk bu sperlatiste Al
ve Fe tarafndan paylalmaktadr.
743

Fe3Al latisinde, yani, b sperlatisinde ortalama yap faktrleri D03 ve B2 speryaplar iin srasyla FDO3= 4(fa-fb) ve
FB2 = 4(2fc-fb-fa) olarak verilir ve ayrca ortala sapma faktrleri ise fb = (qfFe -zfAl) ile temsil edilir. Burada q ve z (0 veya
1 arasnda bir say ile ifade edilebilen molar fraksiyonlara gre dzeltilmi yer igal arpm fraksiyonudur (rnein
b sperlatisindeki durumda q 0,5 ve Al da 0,5 ile ifade edilir)ve fa fb ve fc ise her bir pik dzlemine ait hesaplanan
sapma faktrleridir. Bu formllerle UMD faktrleri hesaplanmaktadr(izelge 1). Bu almada (111)/(400) piklerinin
oran DO3(Fe3Al faznn) kristal yapsnn ve (200)/(400) oran ise B2 (FeAl) faznn kristal yapsnn dzen oranlarn vermektedir. (200)/(400) oran paylalan latiste Fe/Al oran 0,5 olduu iin, en yksek B2 dzen oran 0,5
olacaktr buna karn DO3 kristal yapsnn ise 1 olabilir[21]
Bu bilgiler nda aada izelge 1 verilen UMD sonular deerlendirildiinde sinterleme srelerinde 1 saatlik
bir sinterlemenin yeterli olduu grlmektedir ancak en iyi sinterleme performans UMD deerleri dikkate alndnda 2 saatlik bir sinterlemenin verdiini grmekteyiz. Ancak 2 saatlik bir sinterleme fizibil olmamaktadr ve maliyeti
artrmaktadr. lave olarak sl ilemler dikkate alndnda ise istisnasz olarak 5 saatlik bir sl ilemin yeterli olduu
grlmektedir.
izelge 1 Fe-26Al karm iin deiik sinterleme zaman ve takip eden sl ilem sreleri iin UMD deerleri
1/2 saatlik Mikrodalga Sinterleme
1,5 saatlik Mikrodalga Sinterleme
Sinter. Sr.(Saat)
DO3
B2
Sinter. Sr.(Saat)
DO3
B2
0,5
0,01
0,03
0,06
0,14
30
0,01
0,07
0,08
0,19
10
0,01
0,01
15
0,01
0,01
30
0,01
0,02
1 saatlik Mikrodalga Sinterleme

Sinter. Sr.(Saat)
DO3
B2
0,01
0,09
2 saatlik Mikrodalga sinterleme
0,01
0,11
Sinter. Sr.(Saat)
DO3
B2
10
0,01
0,06
0,06
0,14
15
0,03
0,08
0,24
0,32
30
0,04
0,11
10
0,09
0,04
Artan sl ilem sreleri ile beraber ksmen Fe3Al faznda art oluturmaktadr ancak genel olarak sonulara ok
fazla bir etkisi olmamaktadr. Isl ilemle belirlenen UMD deerlerinde deiim iin deiik mekanizmalar nerilebilir.
Sinterleme ardndan yaplan sl ilemler 450 C de yapld iin daha ok DO3 yapsn glendirilmesi amalanmaktadr ancak ilk sinterleme scakl ise B2 yapsnn baskn olduu 550 C yaplmtr. Genel olarak B2 kristal
yapsnn daha fazla bulunmas aslnda fiziksel olarak Fe ve Al arayzeylerinin daha fazla temas halinde olmasndan kaynaklanmaktadr[22].
Dybkova gre Fe ve Al un reaksiyonu sonucu ilk oluacak fazn Al ve Fein faz diyagramndan anlalaca gibi
doyum limitlerine yakn olan Fe2Al5 bileii ile balayacan ve artan sre ile beraber Fe3Al ve daha sonra ise FeAl
ikili bileie dnecei belirtilmektedir. Bununla birlikte Jozwiak ve ark ise yaptklar DSC(Differential Scanning Calorimetry) almalarnda ise sralamann FeAl3Fe2Al5FeAl2FeAl eklinde olutuunu gstermilerdir[23].
Ancak bu almada Fe2Al5 bileiine ait herhangi bir pik tespit edilememitir buna karn Fe3Al faza ait piklerin az
olmas Dybkovun nerdii mekanizmann bu durumda scakla ar baml olduunu nermektedir. Gerekten
Dybkov deneylerini olduka yksek scaklklarda (700 C ve zeri) scaklklarda yapt iin bu almada yaplan
deneylerin sonular iin nerilebilecek uygun bir mekanizma olmad grlmektedir.
Buna karn, Turmezey elektron mikroskopi almalarnda FeAl ve Fe3Al bileiklerinin ayn anda bulunabileceini
tespit etmi ve souma hzna bal olarak Fe3Al faznn daha az bir byme hzna sahip olduu iin FeAl oluumunun daha ok sistem tarafndan tercih edildiini ispatlamtr[24].
744

ekil 4. Tipik Fe26Al alamnda grlen ana ve sperlatis pikleri
ekil 5. 550 Cde 1 saat n Sinterleme yaplm ve 5, 10, 15 ve 30 saat sl ilem uygulanm numunelerin
XRD analizleri verilmitir
4. Fe26Al ve Fe50Al ntermetaliklerin Kesme Mukavemeti
nsinterleme zerine yaplan btn sl ilemler sinter dayanmn artrma ynnde almtr ancak sinter sresi
arttka dayanm deerlerindeki d olduka bariz olarak karmza kmaktadr. Artan sinter sresi, toz boyut
dalmn ve temas yzey orann deitirecektir ve genel olarak dayanmdaki dme ise reaksiyon rnlerinin
eitliliine balanmaktadr[25, 26].
Gerekten de, en iyi sonular XRD krnm deseni ile elde edilen sonularda 1 saat nsinterleme ile elde edilmi ve
dier srelerin etkisinin ok az olduu gzlemlenmitir. izelge 1de verilen deerler dikkate alnrsa B2 piklerinde
meydana gelen deiimin aslnda FeAl faznn artmas ile sonuland ve dolaysyla daha krlgan bir faz olan
FeAlun genel dayanm artan sl ilem scakl ile drd nerilebilir.
ekil 9, 10da Fe26Al ve ekil 11de ise Fe50Al numuneler 550 Cde 1saat Mikrodalga sinterleme yapldktan
sonra ayn numunelere mikroyapda intermetalik oranlarndaki ve mekanik zelliklerinde oluabilecek deiimin
aratrlmas amacyla 450 C de 5-10-15 ve 30saat sl ilem uygulanmtr. Sinterleme ileminde sinterleme sresinin kesme mukavemetine etkisinin fazla olmad llmtr. Fakat sl ilem sresindeki artlarda kesme
mukavemetinde azalma olduu belirlenmitir. En yksek kesme mukavemet deeri 1saat n sinterleme ve 5 saat
sl ilem grm Fe26Al oranna sahip numunelerde llmtr. Toz karmda Alminyum oran arttka kesme
mukavemet deerlerinde belirgin azalma olumaktadr(ekil 5).
745

ekil 6. 550 Cde n Sinterleme Sonras Isl lem Sresine Bal Fe26Al Kesme Mukavemeti
ekil 7. 550 Cde n Sinterleme Sonras Isl lem Sresine Bal Fe50Al Kesme Mukavemeti
5. Fe26Al ve Fe50Al Numunelerinde Isl lem artlarnn Etkisi
Numunelerde sinterleme ileminden sonra mikroyapda intermetalik orannn deerlendirilmesi ve mekanik zeliklerdeki deiimin aratrlmas amacyla nceki almada belirlenen ideal sinterleme scaklk ve sresi seilerek
numuneler retilmitir.
Bu almada Fe26Al ve Fe50Al numuneleri Mikrodalga frn argon atmosferinde 550 Cde 1, 1,5 ve 2 saat sinterleme yaplmtr. Sinterlenmi bu numuneler tp frn atmosferinde 450 Cde 5101530 saat bekletilerek frn
iinde oda scaklna kadar soutularak mikroyap deiimleri aratrlmtr. Sinterleme ileminden sonra numunelerde nceden oluan intermetalik oranlardaki deiim 10 saat 450 Cde bekletilen numunelerin analizlerinde
grlmektedir(ekil 5).
ekil 8. Fe-26Al 550 C de mikrodalga 1saat sinterleme ve 10saat 450 C de sl ilem, a) SEM ve b)EDX elementel haritalama grnts analizi
746

ekil 9. Fe-26Al 550 C de 1 saat sinterleme ve 15 saat 450 C de sl ilem SEM grnts
ekil 10 Fe-26Al 550 C de mikrodalga 1 saat sinterleme ve 30saat 450 C de sl ilem SEM grnts
747

ekil 11. Fe50Al, 550 C de 1 saat sinterleme ve 450 C de 15 saat sl ilem mikroyap SEM ve EDX
spektrometre analizleri.
KAYNAKLAR
1. Rveall M.German, Toz Metalurjisi ve Parackl Malzeme lemleri, Trk Toz Metalurjisi Dernei Yaynlar, 1.basm, Ankara, 2007.
2. krov R.., Metalnaslq. Bak: aolu Yaynevi, 2002.
3. Kang, Hui-Zhen., Hu, Chen-Ti., Swelling behavior in reactive sintering of Fe-Al mixtures, Materials Chemistry
ve Physics 88, s. 264 272, 2004.
4. Avc A.U., Toz metalrjisi ders notlar. Yldz Teknik niversitesi, stanbul, 1993.
5. Bishop D.P., Diffusion-based micro alloying via reaction sintering. Ph.D. Thesis, Dalhousie University, 1998.
6. Schneibel, H.J., Devi, S.C., Processing ve mechanical Properties of iron Aluminides composites containing
oxide particles, Materials Science ve Engineering A364, s.166-170, 2002.
7. Kurt A.O., Toz retim yntemleri ve sinterleme. Sakarya niversitesi, Mhendislik Fakltesi, Metalrji ve Malzeme Mhendislii Blm Ders Notlar, s. 19-20. Sakarya, 2005.
8. Babayev Y., Karadeniz S. ve Memmedov A., FeCu karm toz malzemenin tribolojik zelliklerinin incelenmesi.
3. Makina Tasarm ve malat Teknolojileri Kongresi, 16-17 Eyll, s. 127-130, 2005.
9. Federenko .M. ve Pugina L.., Kompoziionne speenne antifrikionne material. Kiev: Nauk, 1980.
10. Radomselskiy .D., Porokove konstrukionne detali. Sovremennoe sostoyane, perespektne razvitiya. Porokovaya Metallurgiya, (10), s. 37-41, 1985.
11. Skoroxod V.V., Sostoyane i perispektiv razvitiya naunx osnav porokovoy metallurgii. Porokovaya Metallurgiya, (10), s. 20-24, 1995.
12. Zavolotny L.V., evuk Y.F., Begun K.., Kolinienko A.F. ve Varenko V.T., Porokove antifrukionne material
na osnove matallokonentrata iz lifovalnx lamov. Porokovaya Metallurgiya, (7/8), s. 89-92, 1995.
13. Ordenko V.B., Proizvodstvo i primeneniya izdeliy iz metallieskix poroikov. Kiev, 1987.
14. Al-Qureshi, H.A., Galiotto, A., Klein, A.N., On the Mechanics of the Cold Die Compaction for Powder Metallurgy,
Journal of Materials Processing Technology, 166, 135-143, 2005.
15. Kang, Hui-Zhen., Hu, Chen-Ti., Swelling behavior in reactive sintering of Fe-Al mixtures, Materials Chemistry
ve Physics 88, s. 264 272, 2004.
748

16. Hui-Zhen Kang, and Chen-Ti Hu., Materials Science and Engineering Material Chemistry and Physics, 88(2-3),
pp.264-272, 2004.
17. Godlewska, E., Szczepanik, S., Mania, R., Krawiatz, J., Kozinski, S., FeAl Materials from Intermetallic powders,
Intermetallics11, pp.307 312, 2003.
18. . Burke J.E. ve Rosolowski J.H., Sintering J. Eur. Ceram. Soc. 08, 758-769, 2000.
19. Suk-Joong L. Kang Sintering Densification, Grain Growth, and Microstructure Butterworth-Heinemann Publication Date: 2005-01-19.
20. B. H. Rabin and R. N. Wringht, Micrustructure and tensile Properties of Fe3Al Produced By compustion Synthesis/ hot Isostatic Presing Metallurgical and Materials Transsctions A Volume 23, Number 1, 35-40, 1991
21. Yang ZR, Wang SQ (Wang, Shu Qi)1, Cui XH (Cui, Xiang H.)2, Zhao YT (Zhao, Yu T.)1, Gao MJ (Gao, Ming
J.)1, Wei MX (Wei, Min X.)1 Formation of Al3Ti/Mg composite by powder metallurgy of Mg-Al-Ti system
Scence And Technology Of Advanced MateralsVolume: 9Issue: 3Article Number: 035005Published:
SEP 2008
22. Dybkov, VI, Reacton Dffuson And Sold State Chemcal Knetcs, The IPMS Publications, Kyiv, 2002
23. Stanislaw Jzwiak, Krzysztof Karczewski and Zbigniew Bojar., Kinetics of reactions in FeAl synthesis studied
by the DTA technique and JMA model ., ntermetallics. , Volume18, Issue 7, P. 1332-1337, July 2010.
24. Turmezey, T, AlFe and AlFeSi intermetallic phases in Al alloys, Materials Science Forum, Vol 13/14, pages 121131 ttp publications, London, NY., 1987.
25. Pease L.F. III, West W.G., Fundamentals of powder metallurgy, Metal Powder Industries Federation, Princeton, USA, 2002
26. Randall M. German., Sintering Theory and Practice, pp. 568. ISBN 0-471-05786-X. Wiley-VCH , January
1996.
749

TOZ METAL MALZEMELERN MEKANK ZELLKLERNE

YOUNLUK VE BAKIRIN ETKS
Nihat YILMAZ*, Remzi VAROL**
* Sleyman Demirel niversitesi, Teknik Eitim Fakltesi Makine Eitimi Blm, 32260, Isparta,
nihatyilmaz@sdu.edu.tr
** Sleyman Demirel niversitesi, Mh.-Mim. Fakltesi, Makine Mhendislii Blm, 32260, Isparta,
remzivarol@sdu.edu.tr
ZET
TM paralarn mekanik zellikleri, dvme ve dkm malzemelerde olduu gibi kimyasal kompozisyondan olduka
fazla etkilenmektedir. Bunun yannda TM paralarda younluk, parack boyutu ve dalm ile dier TM proses
parametreleri de mekanik zellikleri etkilemektedir. Bu almada demir esasl TM alamlarnn mekanik zellikleri
zerine younluk deiimi ve bakr ilavesinin etkisi deneysel olarak incelenmitir. lk olarak ASTM standardna gre
Fe-C ikili alamdan 210, 350 ve 700 MPa basnta 3 farkl younlukta (6.0,-6,5-7,1g/cm3) numuneler hazrlanm,
daha sonra bu karmlara %2 bakr ilave edilmitir. Hazrlanan numunelere standart eme deneyi ve krk yzey
SEM analizi, mikrosertlik lm ve mikroyap incelemesi yaplmtr. Bylece farkl younluun mekanik zellikler
zerine etkisi incelenmi, daha sonra da bakr ilave edilmi numunelerle karlatrlmtr. Sonular gstermitir
ki, Fe-C ikili alamlarnda younluk arttka eme mukavemeti ve mikrosertlik artm, %2 bakr ilavesi de eme
mukavemeti ve sertlik deerlerindeki art daha st mertebeye tamtr.
Anahtar kelimeler: TM malzeme, younluk, bakr ilavesi, mekanik zellikler
EFFECT OF DENSITY AND COPPER ON MECHANICAL

PROPERTIES OF P/M MATERIALS
ABSTRACT
Identically to wrought and cast metals, the chemical composition of PM parts strongly influences the mechanical
properties. In PM parts, however, properties are dependent on additional factors such as density; particle size; pore
size, shape, and distribution; and other PM process parameters. In this study, Effect of density variety and copper
(Cu) addition on mechanical properties of ferrous PM alloys was experimentally investigated. Firstly, the samples
prepared that three different density (6.0-6.5-7.11 g/cm3) Fe-C binary alloys. Later, Cu was addition to these alloys.
Some standard tests carry out to the samples such as traverse rupture test and SEM analyze of crack surfaces,
microhardness measurement, and microstructure investigations. Thus, effect of different density on mechanical
properties and Cu addition has been investigated. Results showed that bending strength and microhardness increased with increasing density and addition of w%2 Cu at Fe-C binary alloys,
Keywords: PM material, density, Cu addition, mechanical properties
1. GR
Sinterlenmi paralarn karakteristik zellii olan porozite, geleneksel ergitme prosesiyle retilen malzemelerin
aksine, TM malzemelerde eitli malzeme zelliklerini kimyasal kompozisyon ve yapdan daha fazla etkiler. Bu
750

nedenle, sinterleme ve sktrmayla elde edilen younlama derecesinin belirlenmesi, sinterlenmi malzemelerin
test edilmesinde nemli bir unsurdur. Younlamann miktar kompaktlanm veya sinterlenmi parann gzenek
(gzenek hacmi) veya younluu olarak belirtilir. Porozite boyutu ve ekli ile bnye ierisinde heterojen dalma
sahip olmas, younluk veya porozitenin deerlendirilmesinde gz nne alnmaldr [1]. TM malzemelerin porozitesi, Arimet yntemiyle belirlenen younlua gre hesaplanr. Younluun malzeme zellikleri zerine etkileri
genel olarak bilinmektedir. rnein, younluk azaldka (porozite arttka), mekanik zellikler der, sl iletkenlik
azalr, sertlik der, elektrik ve manyetik zellikler olumsuz etkilenir. Ancak bunlarn hangi seviyede etkiledii, her bir
malzeme iin, TM proses deikenlerine (tozla ilgili parametreler, sktrma- sinterleme parametreleri v.b.) gre ayr
ayr belirlenmesi iin daha detayl almalarn yaplmas gerekmektedir. Bu almann ana temasn da belirlenen
bir malzeme grubunun baz mekanik zelliklerine, farkl younluk seviyesinin ve bakr ilavesinin etkilerinin detayl
olarak incelenmesi oluturmaktadr.
Bu konuda literatrde, baz kimyasal ilavelerin mekanik zelliklere etkisini inceleyen almalar vardr ve bunlarn
zellikle son on ylda yaplanlar ilenebilirlik ilaveleri zerine younlamaktadr. Ayrca younluun mekanik zellikler zerine etkisini inceleyen olduka eski almalara rastlanrken, bunlarn gnmz teknolojisiyle retilen TM
paralar iin detayl incelemesini ieren almalar olduka azdr. Bu konuda yaplan baz almalar yledir.
Sulowski ve Cias (2011) yaptklar almada, Fe-3%Mn-(Cr)-(Mo)-0.3%C TM eliklerinin younluk, mekanik zellikler ve mikroyaps zerine, kimyasal kompozisyon, sinterleme atmosferi ve soutma hznn etkisini incelemilerdir.
almada n alaml Astaloy CrM ve CrL ile ferromanganez ve grafit tozlar kullanlarak karm hazrlanm
ve preslendikten sonra 1120 ve 1250 C scaklkta, farkl oranlardaki H2/N2 sinterleme ortamnda 60 dakika
sinterlemilerdir. Ayrca iki farkl soutma hznda (frnda 1,4 C/dak., cebri soutma ile 65 C/dak.) soutma ve
200 C de temperleme yapmlardr. Tm numunelere ekme, TRS, darbe tokluu, grnr yzey sertlii yaplm
ve mikroyapsal inceleme gerekletirilmitir. alma sonucunda daha yksek sinterleme scaklnda ve %Cr
orannn artmasyla zelliklerin iyiletii ifade edilmitir [2].
Lindsley ve Rutz (2008) demir-esasl TM malzemelere molibden ilavesinin etkilerini inceledikleri almasnda, olduka yaygn kullanlan Mo ilavesinin TM malzemelerde sktrlabilirlii ok az etkiledii, oksijen duyarllnn
olmadn ve zellikle eliklerin sertleebilirliini arttrdn ifade etmilerdir. almada % 0-1,5 aralnda n
alaml Mo ilavesinin etkileri incelenmi ve genel olarak Mo ilavesinin TM eliklerde mukavemet ve sertlik art
saladn ifade etmilerdir. almada sonu olarak, % 0,5 Mo alamlarnn sinter sertlemesinin hem Cu hem
Ni ilavesiyle mmkn olmasna ramen, tavsiye edilen Ni ve Cu ilavesiyle beraber minimum % 0,85 Mo ilavesi
nerilmitir. Isl ilem paralar iin % 0,3 kadar az bir Mo orannn bile paralarn sl ilem tepkilerini iyiletirecei
belirtilmi ve Fc-20x serisi alamlara yakn maliyetteki alamlarda, nalaml % 0,3 Mo ilavesinin yalnzca daha
iyi sl ilem tepkisi salamad ayn zamanda boyutsal hassasiyeti de iyiletirdii ifade edilmitir. Yksek Mo ve
dk karbon ieriinin karburizasyon iin olduka uygun olduu belirtilmitir [3].
Chawla ve Deng (2005) almalarnda sinterlenmi Fe-0,85Mo-Ni eliklerinin mekanik zellikleri ve mikroyapsn
younluun bir fonksiyonu olarak incelemilerdir. Sonu olarak ekme mukavemeti, Young modl, krlmaya kadar
gerinme ve yorulma zelliklerinin porozitenin azalmasyla arttn tespit etmilerdir. Ayrca 2-boyutlu sonlu elemanlar tabanl mikroyap modeli gstermitir ki, daha youn parann iyiletirilmi ekme ve yorulma davranlar, daha
homojen, kk ve daha kresel poroziteye ve malzemedeki azalm gerinme lokalizasyonuna dayandrlabilir [4].
Bergmark ve Bengstsson (2001) ise Cu-C ilaveli TM eliklerin yorulma zellikleri zerine iki farkl younluk (%7,157,4 g/cm3), karbon (% 0,2-0,8) ve bakr orannn (% 0-2) etkisini inceledikleri almada, en yksek yorulma
performansnn yksek bakr (%2) yksek C (%0,8) ve yksek younluktaki (%7,4) numunelerde elde etmilerdir
[5].
Chagnon ve Trudel (1998) almalarnda sinter sertletirilmi dk alaml (% 2Cu ve %0,65 ve 0,8 kombine Ca
ilave olarak % 0,45 Mn- %0,45 Cr-% 0,90 Ni-% 1,0 Mo ieren) elik alamndan % 6,8-7,0-7,15 ve dvme ile tam
youn olmak zere 4 farkl younlukta numuneler hazrlamlar ve 1120 Cda 25 dakika sinterlemilerdir. Numuneler zerinde yaplan testler gstermitir ki, grnr sertlik her iki karbon oran iin younluun artmasyla lineer
olarak artm ancak art oran % 0,65 C orannda daha fazla olmutur. Younluun etkisinin, tam youn olarak
benzer sertlie sahip %0,65 C oranndaki malzemede daha belirgin olduu, ayrca maksimum ve ekme mukavemetlerinin de her iki karbon orannda, younluun artmasyla lineer olarak artt belirtilmitir. Sonu olarak % 0,65
C orannn daha yksek mukavemet deerleri verdii vurgulanmtr [6].
Literatrdeki almalar incelendiinde younluun ve bakrn genel olarak mekanik zelliklerde iyileme salad
ancak bu iyilemenin dier alam elementlerinden zellikle de C oranndan etkilendii grlmektedir. Ayrca bakr
ve younluun etkisinin birlikte incelendii bir almaya da rastlanmamtr. Bu almada iki grup TM yapsal
demir-esasl malzeme grubunda numuneler hazrlanmtr. lk grupta Fe-C ikili alamndan oluan ve MPIF TM
yapsal para standardna [7] gre F-0005 ile gsterilen %0,6 C ieren alam 3 farkl younlukta numuneler
751

retilmi daha sonra bunlara %2 Cu ilave edilerek 3 farkl younlukta ikinci grup numuneler hazrlanmtr. Numuneler zerinde, sertlik lm, apraz krlma testi (transverse rupture strength-TRS) yaplm, ayrca krk yzey
analiz ve makroyap incelemesi yaplmtr. Bylece iki grup numune ile yalnzca younluk deiiminin etkisiyle
bakr ilavesinin etkisi detayl olarak incelenmitir.
2.1. Malzeme ve Metot
Deneysel almalar iin elementel demir, grafit, bakr tozlar ile yalayc olarak inko-stearat tozu kullanlmtr.
Numuneler her bir karmn younluuna gre ayr ayr hassas terazi ile tartlarak ift konili kartrc ierisinde %
60 doluluk salanacak ekilde, torna tezghnda en dk devir olan 22,4 devir/dakika dnme hznda 20 dakika
kartrlmtr.
almada demir esasl 6 farkl karm elde edilmitir. Kullanlan karmlarn tmnde yalayc olarak inko-stearat kullanlm ve ilave miktar % 0,8 orannda sabit tutulmutur. almada ilk grup numune ASTM standardna
gre Fe-C ikili alamlardan F-0005 standart karmna uygun ve farkl younlukta hazrlanmtr. Bu ilk grup
A1, A2, ve A3 ile gsterilmitir. Bylece A grubu karmlarda (A1-A2-A3) kimyasal bir farkllk olmayp (Fe+%0,6C)
yalnzca younluk farll vardr. kinci grup numunede B grubu olarak kodlanmtr. B grubu karmlarda (B1B2-B3) A grubundan farkl olarak tmne % 2 orannda elementel bakr ilave edilmi (Fe+%0,6C+%2Cu) ve yine 3
farkl younluk elde edilmitir. Numunelerin ierikleri aadaki izelge 1de verilmitir.
izelge 1. Toz Karmlarna Ait Kodlamalar ve Karm Oranlar (Arlka-%)
Karm
Cu
A1
A2
A3
B1
0,6
B2
B3
Zn-stearat
Fe
0,8
Kalan
Belirlenen oranlarda kartrlan tozlardan numune elde edilmesi iin hazrlanan kalp ile tozlarn blok numune
haline getirilmesi gerekletirilmitir. Btn numuneler ekil 1.ada verilen kalp sistemiyle hidrolik preste tek etkili
olarak sktrlarak elde edilmitir. Numunelerin geometrisi ve boyutlar, standart eme test numuneleri gz nne
alnarak belirlenmitir. Deneylerde kullanlan numunelerin geometrisi ve boyutlar ekil 1.bde verilmektedir.
ekil 1. a) Toz sktrma kalp konstrksiyonu b) Numune geometrisi

Preslemede 3 farkl younluk iin, 210 MPa, 350 MPa ve 700 MPa olmak zere 3 farkl basn uygulanmtr. Presleme sonras blok numuneler ayr ayr kodlanm ve numune kodu olarak toz karmlarda kullanlan kodlamalar
esas alnmtr. izelge 2de numunelere uygulanan sktrma basn deerleri ve younluk lmlerinden elde
edilen sonular ortalama deer olarak Tablo 1de verilmitir. Toz numunelerin sinterlenmemi younluk lmleri TS
2305 standardna uygun olarak Arimet prensibine gre yaplmtr.
752

izelge 2. Numune gruplarna uygulanan basn deerleri ve elde edilen younluklar

KARIIM
A1
A2
A3
B1
B2
B3
Sk. Basnc (MPa)
210
350
700
210
350
700
Younluk (g/cm3)
6.0
6.50
7.1
6.0
6.50
7.1
Sinterleme ilemi elektrik stmal, otomatik atmosfer kontroll MAHLER marka endstriyel srekli bant frnda,
doalgaz (Metan) kullanlarak endotermik atmosferde yaplmtr. Sinterleme esnasnda metan gaz paralanarak
(C ve H2 olarak)redkleyici bir atmosfer oluturulmakta ve sktrlm toz kompakt bnyesindeki oksidi alnp, CO2
ve H2O eklinde dar atlmaktadr.Sinterleme ilemi 1120 Cde 20-30 dakika srede gerekletirilmitir Parann
frnda kalma sresi ise (n stma, sinterleme ve soutma toplam) 1,5 saat mertebesindedir.
2.2. Bulgular ve Tartma
retilen demir esasl TM kompaktlar sinterlendikten sonra malzeme karakterizasyonu iin sertlik ve apraz krlma
testleri uygulanm, ayrca krk yzey analizi yaplmtr. T/M numunelerinin presleme ynnde ve buna dik ynde
toplam drt yzeyinden Vickers sertlik lmleri alnmtr (ekil 2.). Sertlik lmleri bu drt yzeyde enine ve
boyuna olarak ayr ayr alnmtr. izelge 3de gsterildii gibi, presleme ynne dik A ve A yzeylerinin enine ve
boyuna sertlik lmleri ayr ayr verilirken, presleme ynne paralel B ve B (yan) yzeylerdeki lm sonular
enine ve boyuna lmlerin aritmetik ortalamas (AO) olarak verilmitir.
ekil 2.a) Sertlik lmnn gsterimi b) apraz krlma numunelerinin hazrlanmas

izelge 3. Numune yzeylerindeki mikrosertlik sonular (HV10)
A1
A2
A3
B1
B2
B3
AE
110-200
145-250
210-283
210-265
215-260
270-340
AB
120-220
131-248
225-255
210-265
215-290
265-340
A'E
120-170
150-205
182-230
210-242
202-255
240-315
A'B
110-170
140-200
165-220
204-245
204-240
240-285
Bort
130-205
139-231
170-215
230-290
265-320
240-290
B'ort
130-170
160-186
175-220
240-285
270-300
250-315
ORT
120-200
144-220
187-240
220-265
230-280
250-315
ekil 3. Mikrosetlik sonular a) grafik gsterimi b) Younlua ve bakr oranna bal
753
AO
160
182
215
243
255
282

izelge 3 ve ekil 3 incelendiinde genel olarak u sylenebilir; Yalnz A younluk grubunda %76-91 arasndaki
bal younluun artmasyla sertlik % 25 orannda artmtr. B bakr ve younluk grubunda bakr ilavesi genel olarak
sertlii A grubunun ayn younluk dzeyine gre %25-40 arasnda bir art salam, ancak bakr ilaveli B grubun
kendi iinde %76-91 younluk deiiminin sertlie etkisi, yalnz karbon ieren A grubundan daha az olmu ve % 13
seviyesinde kalmtr.
apraz krlma (TRS) deneyi MPIF 35/41 standardna gre yaplmtr. Bu standartta (MPIF 35/41) apraz krlma
iin standart numune geometrisi ve boyutlar kalnlk 6,35mm x uzunluk 31,7mm x genilik 12,7mm verilmitir.
apraz krlma deney numuneleri ekil 2.b.de grld gibi kompaktn tel erozyon tezghnda boyuna kesilmesiyle elde edilmitir. Bylece bir kompakttan 2 adet apraz krlma numunesi elde edilmitir. Ayn malzemeden retilen
bu iki numune iin uygulanan apraz krlma test sonular ortalamas alnarak ekil 2de toplu olarak verilmitir.
ekil 4. apraz Krlma sonular ve grafik gsterimi

apraz krlma test sonularna genel olarak bakldnda, TM malzemelerin younluu arttka hem apraz krlma
mukavemeti (TRS) hem de sneklii artmaktadr. Bu sonu apraz krlma deneyi esnasnda yk-sehim grafiinden
bakldnda A younluk grubunda younluun artmasyla TRS ve sneklii artmaktadr. A Younluk grubunun en
dk younlua sahip A1, A younluk grubunun en gevrek malzemesi olarak belirlenmitir. Ayn ekilde B younluk
ve Bakr Grubunda da benzer eilim grlmektedir. Yani younluun artmasyla TRS ve sneklik artmaktadr. Bu
sonular genel literatr yorumlaryla uyumludur [8];[9]. Bu sonular SEM krk yzey analizleriyle ilikilendirildiinde,
A Younluk grubunda en dk younlua sahip A1 ile ayn grupta daha youn A3n krk yzey SEM grntleri
ekil 5.a ve bda verilmitir.
ekil 5.a) 6.0 g/cm3 younluklu A1 (Fe+%0,6C) numunesinin krk yzey SEM grnts b) 7.1 g/cm3 younlua
sahip A3 (Fe+%0,6C) numunesinin krk Yzey SEM grnts
ekil 5.a ve 5.bden grld gibi sar izgilerle belirtilen blgeler partikller aras balarn olutuu ve partikller aras krlmalarn grld blgelerdir. Daha dk younluktaki A1 numunesinde nispeten ba oluumunun
daha az ve kk temas alanlarnda, dolaysyla daha gevrek bir yapda olduu, daha youn A3 numunesinde ise
daha youn partikller aras boyun olutuu ve bu boyun blgelerinin okluu grlmektedir. Literatrde dk
younluklarda mukavemetin partikller aras boyun oluumuyla snrl olduu belirtilmitir [10]. Partikl temas
alanlarnn daha byk olmas, apraz krlma srasnda hem TRS deerini arttrd hem de A1e gre deforme
olana kadar daha fazla plastik ekil deitirmeye msaade ettii anlalmaktadr.
754

ekil 6.a) 6.0 g/cm3 younluklu B1 (Fe+%0,6C+%2Cu) numunesinin krk yzey SEM grnts b) 7.1 g/cm3
younlua sahip B3 (Fe+%0,6C+%2Cu) numunesinin krk Yzey SEM grnts
Ayn ekilde B (younluk + bakr) grubunun (Fe+0.6C+0.2Cu) en dk ve en yksek younlua sahip B1 ve B3
numunelerinin ekil 6.a ve bde gsterilen TRS krk yzey SEM analizlerinin karlatrlmas gstermektedir ki,
partikller aras temas alanlarnn says ve temas alannn genilii younluun artmasyla artmaktadr. Yine B1 ve
B3 arasndaki younluk fark da ekillerden grlmektedir. nk ekil 6.ada partikller arasndaki boluk alanlar
daha fazla, ekil 6.bde ise nisbeten daha azdr. Ayrca bu grupta A younluk grubundan farkl olarak bakrn ilave
edilmi olmas da yapda partikller arasndaki balarn oluumuna ve kuvvetlenmesine katkda bulunmu ve TRS
deerlerini artrmtr [11]. Bakr ilavesiyle TM malzemelerdeki sertlik ve apraz krlma mukavemetinin artmasnn
nedeni; bakrn ferritte maksimum zlebilirlii % 1.5-2 Cu oranna kadardr, bu orandan fazla bakr ilavesi tipik
olarak tane snrlar ve kk gzeneklerde kelir. Bunun sonucunda partikller arasndaki boyun blgesinde
gerilme konsantrasyonunu azaltan ve atlak balangcn geciktiren kresel gzenek oluumu ile sertlik ve mukavemet deerleri artmtr [12].
3. SONULAR
i.
T/M malzemelerin younluu ve bakr oran, sertlik ve apraz krlma mukavemeti, zerine nemli bir etkiye
sahiptir.
ii. Younluun artmas apraz krlma mukavemeti ve sertlii arttrr. Bal younluun % 76-91 aralnda
artmasyla, Fe-C ikili sisteminde sertlik art % 25 ve apraz krlma mukavemeti %40 artarken, ayn bal younluk
aralnda, Fe-C-Cu l sisteminde sertlik %13 apraz krlma mukavemeti % 115 orannda artmtr. Bylece ayn
oranlardaki younluk artnn sertlie etkisi yalnzca Fe-C ikili alamna (A grubuna) etkisi Fe-C-Cu l sisteminden oluan B grubuna etkisinden daha fazladr. Yani bakr ilavesi younluk artnn sertlie etkisi azaltmtr
iii. Krk yzey SEM grntleri gstermitir ki, daha yksek basnla sktrlan numunelerde, partikller
arasndaki temas blgeleri artm ve bu blgeler sinterleme sonras boyun oluumunu artrmtr. Younluk arttka
partikller arasnda boyun oluumu artm bylece yap bileenleri arasndaki ba glenerek mekanik zelliklerin
artmasna neden olmutur.
4. KAYNAKLAR
1. Schatt, W., Wieters, K.P., Powder Metallurgy: Processing and Materials, European Powder Metallurgy Association (EPMA), Germany, 1997.
2. Sulowski, M., Cias, A., Microstructure and Mechanical Properties of Cr-Mn Structural PM Steels, Archives of
Metallurgy of Materials, Vol. 56, Issue 2, 2011.
3. Lindsley, B., Rutz, H., Effect Of Molybdenum Content In Pm Steels, PM 2008, Washington, DC, 2008.
4. Chawla, N and Deng, X., Microstructure And Mechanical Behavior Of Porous Sintered Steels, Materials Science and Engineering A Volume 390, Issues 1-2, 15 January 2005, Pages 98-112, 2005.
5. Bergmark, A., Bengtsson, S., Fatigue Properties of Cu-C alloyed PM Steel at two density levels, EURO
PM2001, in Nice, France, 2001.
6. Chagnon,F., Trudel,Y., Effect of Density on Mechanical Properties of Sinter Hardened P/M Materials, PMTEC
98, May31-June4, Las Vegas, Nevada, USA, 1998.
7. MPIF Standart35, Materials Standards for P/M Structural Parts, MPIF, USA, 2000.
8. alak, A., Ferrous Powder Metallurgy, Cambridge International Science Publishing, 450, England, 1995.
9. Hgans AB, Design and Mechanical Properties Volume 3:. Hgans Handbook for Sintered Components,
Sweden, 2004a.
10. German, R.M., Powder Metallurgy Science, MPIF, Princeton, NJ, USA, 1994.
11. Hgans AB, Machining Guidelines Volume 5. Hgans Handbook for Sintered Components, Sweden,
2004b.
12. Brnduan, L., 2004. Researches Regarding the Influence of Cu Content on Static and Dynamic Properties
of Sintered Steels. Leonardo Electronic Journal of Practices and Technologies, ISSN 1583-1078, Issue 4,
January-June, 30-37.
755

DOAL TA KESME LERNDE KULLANILAN ALTERNATF KBK BOR

NTRRL KESC TAKIMLARIN MKROYAPI VE MEKANK ZELLKLER
Durmu KIR *, Serkan ISLAK **, Halis ELK*, Erturul ELK***
Frat niversitesi, Teknoloji Fakltesi, Metalurji ve Malzeme Mh. Blm, 23100 Elaz,
durmuskir@gmail.com, hcelik@firat.edu.tr
**
Kastamonu niversitesi, Cide Rfat Ilgaz Meslek Yksekokulu, 37600 Kastamonu sislak@kastamonu.edu.tr
***
Tunceli niversitesi, Mhendislik Fakltesi, Makine Mh. Blm, 62000 Tunceli
ecelik@tunceli.edu.tr
*
ZET
Bu almada, doal ta kesme ilerinde kullanlan elmasl kesici takmlarda elmasn yerine alternatif olarak kbik
bor nitrrn (cBN) kullanlabilirlii aratrlmtr. Bu amala soketlere farkl oranlarda kbik bor nitrr ilave edildi.
Tm soketler 35 MPa basn altnda, 600 C scaklkta ve 3 dakika sinterleme sresinde scak preste retildi.
Soketlerin mikroyap ve faz bileimi taramal elektron mikroskobu (SEM), X-n difraktogram (XRD), X n enerji
dalm spektrometresi (EDS) ile belirlenmitir. Soketlerin mekanik zellikleri noktal eme testi kullanlarak tespit
edilmitir. Eme testi sonular kbik bor nitrrl soketlerin eme mukavemetlerinin elmasl soketlerinkinden daha
yksek ktn gstermitir.
Anahtar Kelimeler: Kbik bor nitrr, scak presleme, noktal eme testi
MICROSTRUCTURE AND MECHANICAL PROPERTIES OF ALTERNATIVE

CUBIC BORON NITRIDE CUTTING TOOLS USED CUTTING NATURAL
STONE
ABSTRACT
In this study, the usability of cubic boron nitride (cBN) as an alternative in stead of diamond in cutting tools used to
cut natural stones was investigated. For this purpose, cBN with different proportions was added into the segments.
All the segments were manufactured under 35 MPa pressure at 600 C with a 3 minutes sintering time. Microstructure and phase composition of segments were determined by scanning electron microscopy (SEM), energy
dispersive spectroscopy (EDS) and X-ray diffraction (XRD) analysis. The mechanical properties of segments were
determined using three-point bending test. The results of the bending test demonstrated that the bending strength
of the segments with cBN were higher than that of the segments with diamond.
Keywords: Cubic boron nitride, hot pressing, three-point bending test
1. GR
Kbik bor nitrr (cBN), elmastan sonra en sert malzemedir. Bu iki malzemeyi oluturan elementler periyodik cetvelde birbirine yakn olduundan elmas ile kbik bor nitrrn kristal yaplar benzerdir [1]. Kbik Bor Nitrr, 2597 C
scaklk ve 7,7 GPa basn altnda 60 saniye ierisinde gBN (Grafit Bor Nitrr) malzemeden dorudan hBNcBN
dnmyle retilen yeniden kristallemi malzemedir. Younluu 3,47-3,48 gr/cm3 dr [2].
Elmas yksek scaklklardaki almalarda grafitlemeye sebep olur. Bylece performansnda d meydana gelir.
Fakat cBNnin yksek kimyasal kararllk, yksek sl iletkenlik ve mkemmel anma direnci gibi zelliklerinden
756

tr elmasl takmlardaki grafitleme probleminin nne geilmi olur [3-5]. Ayrca cBN, elmasa gre daha ekonomiktir.
Sentetik elmas, yksek basn ve scaklk altnda ok ksa srede yumuak olan grafitin ok sert kristal yapl karbon atomuna dnmesi ile elde edilir. Grafit, karbonun kristal formundan birisi olup; dierleri elmas ve ergiyik
halidir. Grafit normalde 2500 C scakla kadar dayanr. Sentetik elmas retiminde alternatif bir yntem olarak
yksek scaklk ve dk basn (CVD) yntemi de kullanlr. Grafit, karbonun dk younluklu allotropu olup;
genellikle yumuak ve siyah renklidir. Sentetik elmaslar bakrdan be kat daha fazla termal iletkenlie sahiptirler.
Kbik Bor Nitrr (cBN) de elmasa benzer ekilde retilir. cBN, gnmzde daha ok demir esasl metallerin ilenmesinde yaygn olarak kullanlan polikristalli bor nitrrl (PCBN) takmlarn retiminde kullanlr [6]. Elmas ve cBNin
kristal yaplar benzer olup; yapda bulunan her bir atom dier drt atom ile 10928 a yaparak mkemmel bir tetrahedral dzen olutururlar. Elmasta, her bir karbon atomu dier drt karbon atomu ile saf kovalent ba yapar. cBNde
ise kovalent ba hkim olmakla birlikte bor ve azotun farkl atomlar olmalar nedeniyle az miktarda iyonik bada
bulunmaktadr. cBNde her bir azot atomu drt bor atomu ile balanrken, her bir bor atomuda drt azot atomu ile
balanarak tetrahedral karakter gsterir [7].
Soketler, kesici diskin apna ve kesme artlarna bal olarak deiik geometri ve zelliklerde imal edilirler. Soket
zelliklerinin belirlenmesinde kesme parametreleri ile kesilecek olan doal tan mineral yaps ve mekanik zelliklerinin bilinmesi gerekir. Soketlere ait matris karmnn hazrlanmas srasnda metal tozlarna ilave olarak 50-500
m tane boyutunda elmas yada cBN tozlar da matrise kartrlarak soket retimi yaplr.
Doal ta kesme ileminde arlkl olarak dikdrtgen kesitli elmasl soketler tercih edilmektedir. Soketler, matris ve
elmas ya da cBN tozlar olmak zere iki paradan olumaktadr. Matris, elmas ya da cBN taneciklerini matriste tutma ilevini yerine getirirken; elmas ya da cBN ise kesme ilevini yerine getirir [8,9]. Baarl bir elmas soket tasarm
iin nitelikli metal tozlarnn kullanlmas gerekmektedir. Matriste elmas yada cBN tanelerini tutmas iin Co, Ni, Cu,
Fe veya bunlarn kombinasyonlarndan yararlanlr. Dolgu evresi iin genellikle Cu-Sn kullanlr [10,11]. Kesilecek
doal tan zelliklerine, kesme parametrelerine ve kesme koullarna bal olarak ana ve balayc fazlarn oluturulmas deimektedir.
Bu gne kadar doal ta kesici takmlar ile ilgili yaplan almalar, genellikle mevcut elmasl soketlerin anmas,
kesme performans ve kesme srasnda oluan kuvvetler, kesici soketteki hasar durumlar, matris karakterizasyonu,
analitik/nmerik modellemeler ile elmasl kesici disklerin dinamik davranlarnn incelenmesi ve elmas kesici tellere
ait alsmalar zerine younlam bulunmaktadr. Literatrde doal ta kesici takmlarda elmas yerine kbik bor
nitrr de dhil olmak zere alternatif bir andrc kullanldna dair bir almaya henz rastlanlmamtr. Yaplan
bu almada, doal ta kesici takmlarda kbik bor nitrrn alternatif andrc olarak kullanlmasnn aratrlmas
amaland. Bu amala soketlere kesici tanenin arlka % 0-100 arasndaki orann cBN ilave edildi. Soket matrisinin
brinel cinsinden sertlii ve sktrlabilirlik zellikleri iin younluu lld. Soketin mikroyaps ve krk yzeyinin
incelenmesinde taramal elektron mikroskobu (SEM), enerji dispersive spektograph (EDS) faz eitleri iin X-n
difraktometresi (XRD) kullanld. Soketlerin eme mukavemeti deerleri noktal eme testi ile tespit edildi.
Doal ta kesici takmn retiminde matris olarak -325 mesh tane boyutuna ve % 99.9 safla sahip Cu-15Sn tozu
kullanlmtr. Kesici olarak 40/50 ve 50/60 mesh tane boyutuna sahip MBD.6 ticari sentetik elmas ve yine ayn
tane boyutuna sahip kbik bor nitrr matrise ilave edildi. Her iki tane boyutu eit miktarda kullanld. ki farkl tane
boyutuna sahip kesici taneciin kullanlmasnn sebebi takmn kesme performansn arttrmaktr. Kullanlan kesici
konsantrasyonu her bir numune iin toplam olarak 30 olarak seildi. Elmasl/cBNli soketlerin retiminde kullanlan
numune gruplar ve retim parametreleri Tablo 1de verilmitir. ekil 1de soket retiminde kullanlan elmas, cBN ve
CuSn tozunun ve SEM fotoraflar grlmektedir.
Tablo 1. Soket retiminde kullanlan matris gruplar ve retim parametreleri
757

ekil 1. Soket retiminde kullanlan tozlarn SEM fotoraf: (a) elmas, (b) cBN ve (c) CuSn tozu
Tablo 1de ki gibi hazrlanan matris/elmas/cBN karm mikserde 30 dakika sre ile 20 d/d hzda % 1 orannda parafin ya eklenerek krom kaplanm elik bilyeler ile birlikte kartrlmtr. elik bilye kullanmndaki ama karma
katlan parafin yann topak oluturmasn engellemektir. Toz halindeki soketler 15 MPa basnla souk olarak
preslendi. Biskvi eklindeki soketler grafit kalplarda scak presleme teknii kullanlarak preslendi. Her bir soket 35
MPada 600 C scaklkta 3 dakika sinterleme sresinde elde edildi. ekil 2de sinterleme grafii verilmitir.
ekil 2. Sinterleme grafii

Scak presleme yntemi ile retilen soket matrisin sertlii BAHA marka sertlik lme cihaznda 62,5 kg yk ve
2.5 mm apnda bilye ile Brinell cinsinden llmtr. Soketlerin eilme dayanmlar, 40 mm x 7 mm x 3.2 mm
lsndeki numuneler kullanlarak noktal eme testi ile tespit edilmitir. noktal eme testi sonras elde edi-
758

len krlma numunelerinin mikroyap zellikleri taramal elektron mikroskobu (SEM-JEOL Ltd., JEM-2100F model),
enerji dispersive spektograph (EDS), X- n difraksiyonu (XRD- Bruker AXS Inc., D8 Advance model) ve spektral
analizleri ile deerlendirilmitir. XRD analizleri 30 kV ve 15 mAde CuK radyasyonu kullanlarak Rigaku Geigerflex
X-n difraktometresi ile elde edilmitir.
Sktrlabilirlik ve younlama hususunda bir fikir vermesi asndan soket numunelerinin younluk lmleri yaplmtr. Yaplan lmler sonucunda 600 C sinterleme scakl iin soket younluunun 8,5866 gr/cm3 olduu
tespit edilmitir. Teorik ve deneysel younluk kullanlarak elde edilen bal younluk ise % 98.855dir. Karl Frank
marka sertlik lme cihaz ile 62.5 kg yk ve 2.5 mm apl bilya kullanlarak elde edilen matris sertlik deeri ortalama
75.46 HB olarak lld.
600 Cde retilen soket matrisinin mikroyapsnda tane snrlarnda XRD analizleri (ekil 4) ile de tespit edildii gibi
Cu3Sn gevrek fazn olutuu tahmin edilmektedir (ekil 3). Matris % 85.461 Cu ve % 14.539 Snden olumaktadr
(EDS analizine gre). Mikroyapdan soket matrisinde sinterleme koullarnn yeterli olmayndan dolay gzeneklerin olutuu tespit edilmitir.
ekil 3. CuSn matrisin SEM fotoraf ve EDS analizi

ekil 4de soketlerden alnan XRD grafikleri verilmitir. XRD analizleri sonucunda, soketlerde cBN, elmas, -Cu,
Cu3Sn bronzu fazlar tespit edilmitir. Matrikse katlan cBN miktarnn artmas ile cBN piklerinin iddetlerinde artlar
meydana geldii gzlenmitir.
ekil 4. cBN/elmasl soketlerin XRD grafii

Her bir soket grubuna ait numunelerin eilme mukavemetleri, noktal eme deneyi yaplarak llmtr. Yaplan deneylerde ASTM B 528-83a standardna gre imal edilen zel olarak yaplm aparatlar kullanlmtr. Instron
marka ekme deney makinesinde yaplan deneylere ait sonular ekil 5de grlmektedir.
759

ekil 5. Arlka % cBN miktarnn eme mukavemetine etkisi

ekil 5de verilen grafik incelendiinde, cBN katkl numunelerin eilme mukavemetlerinin elmas katkl numuneye gre daha yksek olduu grlmektedir. Arlka % 0, 20, 40, 60, 80 ve 100 cBN ilavelerinde srasyla eme
mukavemetleri 222 MPa, 305 MPa, 280 MPa, 260 MPa, 294 MPa ve 297 MPa olarak belirlendi. % 100 cBN katkl
numunenin eilme mukavemetinin, % 100 elmas katkl numuneye gre yaklak % 30 daha byk olduu grlmektedir. Genel olarak tm cBN katkl numunelerin eilme mukavemetlerinin % 100 elmas katkl numuneye gre
daha yksek olduu grlmektedir. Bunun sebebi olarak elmasa nazaran cBNin 85/15 bronz malzeme ile iyi bir
ba yapt sylenebilir.
ekil 6daki krma yzeylerinin SEM fotoraflar incelendiinde matris ile cBN arasndaki arayzey balantsnn,
matris ile elmas tanesi arayzey balantsndan daha kuvvetlii olduu grlmektedir. Tm krk fotoraflarndan
matris ile kesici tanecik arasnda sz konusu balanmann arzu edilenden daha zayf olduu anlalmaktadr. Ayrca
krk yzeylerde matristeki gzeneklerde dikkat ekmektedir. Bu durum sinterleme scaklnn ve presleme basncnn dk olmas ve matrisin elmas bu scaklkta slatma kabiliyetinin dk olduu dnlmektedir.
760

ekil 6. noktal eme testi sonras oluan krk yzeylerin SEM fotoraflar: (a) % 0 cBN, (b) % 20 cBN, (c) %
40 cBN, (d) % 60 cBN, (e) % 80 cBN, (f) % 100 cBN
4. GENEL SONULAR
CuSn matrisine farkl oranlarda elmas/cBN ilave edilerek 600 C sinterleme scaklnda, 35 MPa presleme basncnda ve 3 dakika sinterleme sresinde doal ta kesici soketler retildi. Soket matrisinin nispeten gzenekli olduu
SEM fotoraflarndan belirlendi. Bu durum sinterleme scaklnn dk olduunu gstermektedir. Ayrca soketlerin
XRD analizlerine gre mikroyapda -Cu, Cu3Sn, elmas ve cBN fazlar olutu. noktal eme testi ile en yksek
eme mukavemeti deerine % 100 cBNli soketin sahip olduu tespit edildi. Bunun sebebi olarak elmasa nazaran
cBNin matris ile iyi bir ba oluturduu dnlmektedir.
5. TEEKKR
Bu almann yrtlmesi ve sonulandrlmas ile ilgili konularda FBAP-2020 nolu proje ile maddi destek salayan Frat niversitesi Bilimsel Aratrmalar Projeleri Birimine (FBAP), teekkr ederiz.
6. KAYNAKLAR
1. Brookes, C.A., The mechanical properties of cubic boron nitride a perspective view, Inst Phys Conf. Ser.,
Vol. 75, pp. 20720, 1986
2. Petrusha, I.A., 2000, Features of a cBN-to-graphite-like BN phase transformation under pressure, Diamond
and Related Materials, Vol. 9, pp. 1487-1493, 2000
3. Wentorf, R.H., De Vries, R.C., Bundy, F.P., Sintered superhard materials, Science, Vol. 208, pp. 87380,
1980
4. Tomlinson, P.N., Wedlake, R.J., The current status of diamond and cubic boron nitride composites, Proceedings of the international conference on recent developments in specialty steels and hard materials,
Oxford: Pergamon; pp. 17384, 1983
5. Brook, B., Principles of diamond tool technology for sawing rock, International Journal of Rock mechanics
and Mining Sciences, Vol. 39, pp. 41-58, 2002
6. ifti, ., Trker, M., eker U., CBN cutting tools wear during machining of particulate reinforced MMCs, Wear,
Vol. 257, pp. 1041-1046, 2004
7. Pierson, H.O., Handbook of Refractory Carbides and Nitrides, William Andrew Pub., Noyes, 1996
8. Konstanty, J., Production of Diamond Sawblades for Stone Sawing Applications, Key Engineering Materials,
Vol. 250, pp. 1-12, 2003
9. Konstanty, J., Powder Metallurgy Diamond Tools, Elsevier Ltd, The Metal Powders Technology Series,
pp. 106-107, 2005
10. Karagz, ., Zeren, M., The microstructural design of diamond cutting tools, Materials Characterization, Vol.
47, pp. 89-91, 2001
11. Zeren, M., Karagz, ., Defect characterization in the diamond cutting tools, Materials Characterization, Vol.
57, pp. 111-114, 2006
761

TM ALUMIX 231 VE %5 SiCp KOMPOZTE UYGULANAN EKSTRZYON

VE YKSEK BASINLI BURULMA LEMLERNN MEKANK
ZELLKLERE ETKS
Ceren GDE*, smail ZDEMR**, Hasan ALLIOLU*** ve Hakan YILMAZER****
*
Pamukkale niversitesi, Denizli Meslek Yksekokulu, Metal ve Makine Teknolojileri Blm, 20070, Denizli,
cgode@pau.edu.tr
**
Bartn niversitesi Mhendislik Fakltesi, Metalurji ve Malzeme Mhendislii Blm, 06500, Bartn,
iozdemir@bartin.edu.tr
***
Pamukkale niversitesi Mhendislik Fakltesi, Makine Mhendislii Blm, Denizli, 20070,
hcallioglu@pau.edu.tr
****
Tohoku niversitesi Mhendislik Enstits, Malzeme Bilimi Blm, 9808577 Japonya,
hakan@imr.tohoku.ac.ip
zet
Toz metalurjisi souk presleme (SP) yntemiyle retilmi Alumix 231 ve %5 SiCp takviyeli kompozitlere uygulanan
ekstrzyon (EKST) ve yksek basnl burulma (HPT) ilemlerinin mekanik zelliklere etkisi incelenmitir. retilen
numunelerin mikro sertlik ve mekanik zelliklerindeki deiimler aratrlmtr. ekme deneyi uygulanm ve mikro
sertlik deerleri llmtr. TM malzemelerin optik ve SEM incelemeleri de yaplmtr. Sonularda, SP numunelerine gre EKST ve HPT numunelerinde ekme dayanm ve sertlik deerleri art gstermitir. Alumix 231 ierisindeki %5 SiCp ilavesi ile ekme dayanm azalm, sertlik deerleri ise bir miktar art gstermitir. ekme deneyi
grafikleri ve krlma yzeyleri incelendiinde HPT ve EKST numunelerinde SP numunelerine gre daha snek
krlma olutuu grlmtr.
Anahtar Kelimeler: Toz metalurjisi, souk presleme, ekstrzyon, yksek basnl burulma, mekanik zellikler.
THE EFFECTS OF EXTRUSION AND HIGH PRESSURE TORSION ON THE

MECHANICAL PROPERTIES OF PM ALUMIX 231 AND 5% SiCp COMPOSITE
ABSTRACT
The effect of extrusion (EXTR) and high pressure torsion (HPT) on the mechanical properties of cold pressed (CP)
Alumix 231 and 5% SiC reinforced composites, produced by PM route, were examined. The changes on micro
hardness and mechanical properties of the specimens were investigated. For this purpose tensile and micro hardness tests were carried out. SEM and optical analysis of powder metallurgy materials were also examined. The
results showed that tensile strength and hardness values in extrusion and high pressure torsion samples increased
compared to cold pressed samples. The addition of 5%SiC reinforcement into Alumix 231 resulted in a decrease
in tensile strength whereas increased the hardness values. When examining the tensile test graphics and fracture
surfaces, it was seen that HPT and EXTR samples exhibited more ductile behavior than CP samples.
Keywords: Powder metallurgy, cold pressing, extrusion, high pressure torsion, mechanical properties.
1. GR
Teknolojinin hzl deiimi ve buna paralel olarak malzeme teknolojisinin srekli gelimesi karsnda aratrmaclar
yeni malzemeler aratrmaya ve mevcut malzemeleri de gelitirmeye ynelmilerdir. Son zamanlardaki gelimelere
762

bal olarak stn zelliklere sahip kompozit malzemelerin ileri mhendislik uygulamalarnn kullanld gnmzde nemi giderek artmakta ve bu alanda birok almalar yaplmaktadr [1,2].
Alminyum matrisli kompozitler (AMK), tedarik kolayl gibi stn zellikleri ile gelitirebilmekte ve dk arlklar, yksek mukavemetleri, stn anma dayanmlar sayesinde birok mhendislik uygulamas iin potansiyel bir
malzeme haline gelmitir [3]. Aratrmalar sonucunda ticari Al alamlar ile kyaslandnda, alminyum matrisli
parack takviyeli kompozitlerde artan sertlik, anma direnci, mukavemet, titreim azaltc ve dk sl yaynm
katsays gibi zellikleri olduunu ortaya kmtr.
Ksa fiber, srekli fiber ve klcal kristal takviyeli alminyum matrisli kompozitlerin retiminde zorluklar yaanmaktadr.
Son yllarda parack takviyeli alminyum matrisli kompozitlerin kullanmnda bir art grlrken, iletme giderleri
ve ilenebilirliklerindeki zorluklarla kyaslandnda bu kompozit paralarn uygulama alanlar kstlanmtr [4,5].
Kompozit malzemeler, yaygn olarak otomotiv, uak ve elektronik sanayilerinde, uzay endstrisinde ve talal imalat
sektrnde anma direnci, yksek scaklk zellii ve hafiflik istenen durumlarda tercih edilmektedir. Toz metalurjisi
(TM) rnlerinin en yaygn kullanld alan otomotiv endstrisidir [6]. zellikle dnyadaki petrol fiyatlarnn artmas
ile daha fazla yakt ekonomisi yaratmak otomotiv reticileri zerinde artan bir bask yaratmtr. Ara arln
azaltarak yakt tketimini en alt seviyelere indirmek iin gnmzde pek ok aratrma yaplmaktadr. Otomotiv uygulamalarnda TM yntemiyle retilen yksek performansl, dk younluklu paralarn hazrlanmasnda en ideal
malzemelerin banda alminyum gelir.
Ancak kalpta presleme ve sinterleme sreci sonunda %9095 teorik younlukta numuneler elde edilirken geride
kalan gzenek miktar dikkat ekmektedir. Bu gzenek miktarn drmek ve daha mukavemetli paralar elde
etmek iin TM yntemleri dnda numunelere ikincil ilemlerin uygulanmas ihtiyac duyulmutur. Parack takviyeli
AMKde, seramik paracklar metalik alamn mekanik zelliklerini gelitirmede son zamanlarda oka kullanlmaktadr.
Bu almada, toz metalurjisi yntemiyle retilmi Alumix231 ve %5 SiCp takviyeli kompozitlere uygulanan ekstrzyon (EKST) ve yksek basnl burulma (HPT) ilemlerinin ekme deneyi ile mekanik zellikleri ve mikro sertlik
lmleri ile sertlik deiimleri incelenmitir. Burada SiC ilaveli numunelerde ekme dayanm deeri azalmaktadr.
Mikroyap, SEM ve TEM incelemelerinde yapda SiC ilaveli numunede gzeneklerin dierlerine gre daha fazla
olduu ve en az gzeneklilik orannn HPT numunelerine ait olduu tespit edilmitir. Gzenekliliin ve parack
boyutunun azalmas ile HPT numuneleri en yksek mekanik zellikleri tad belirlenmitir
Bu almada ECKA Granulate Velden GmbH, Germany firmasndan temin edilen Alumix 231 (2,5 Cu, 0,5 Mg, 14
Si) tozu (<157 m) kullanlmtr. Toz ierisinde %1,5 orannda Amide-wax (Ethyle bisstearamide) yalayc mevcuttur. Alumix 231 tozuna % 5 oranlarnda (% arlk olarak) SiC (< 53 m ) tozu (Aldrich) ilave edilerek 30 dakika
sreyle 60 dev/dkda boyutlu turbula ierisinde kartrlmtr. Tozlar daha sonra kalp ierisinde 600 MPa basn
altnda 1 dk sreyle preslenerek ekme numuneleri ve 200 MPa basn altnda 1 dk sreyle preslenerek 100 mm
apnda silindir eklinde ktk numuneler elde edilmitir. Souk presleme (SP) yntemi ile retilen ekme numuneleri tp frnda ncelikle 410 C scaklkta 50 dakika sreyle yalayc uurma sonras 565 C scaklkta 90 dakika
sreyle stma ilemine tabi tutulmulardr.
SP sonras ekstrzyon (EKST) ilemi iin kullanlan ktk numuneler, ayn stma artlar sonras pres zerinde
565 Cye kadar stlan kalp ierisinde 4:1 orannda ekstrze edilmitir. EKST sonras elde edilen blok numuneler
ekme numunesi eklinde ve yksek basnl burulma ileminde (HPT) kullanlmas iin 0,80 mm kalnlnda ve
20 mm boyutlarnda para biiminde kesilmitir. Kesilen EKST numuneleri Tablo 1de verilen deney artlarnda HPT
ilemine tabi tutulmutur. HPT ilemine ait hidrolik pres ve kalplar ekil 1de verilmektedir.
HPT ilemi; uygulanan basn yardmyla, presleme ilemiyle malzemenin burulma srasnda ayrlmasn nlemek
amac ile alt ve st olmak zere iki takoz arasnda kuvvet uygulanarak gerekletirilmektedir. HPT cihazna yksek
basn altnda malzemeye burma ilemini gerekletirmek amacyla alt ve st kalplar taklr. Bu kalplarn malzeme
ile temas halindeki yzeyleri przlendirilmitir.
Para eklindeki malzeme alt kalptaki yerine yerletirildikten sonra kalbn d ksmna karbon yalayc srlr.
Yalaycnn ilem srasnda numuneye temas etmeyecek ekilde srlmesine dikkat edilir. Daha sonra alt takoz
tarafndan, kapal sistem ierisindeki iki kalp arasnda bulunan numuneye alt takoz vastasyla burulma ilemi
uygulanr. HPT cihazyla burulma ilemi, bir panel yardmyla uygulanacak basn ve burulma hz kontrol edilerek
gerekletirilmektedir.
763

ekil 1: HPT ileminde kullanlan hidrolik pres ve kalp

Tablo 1. Yksek basnl burulma numunelerin deneysel deerleri
Numune
Alumix 231
%5 SiC
Balang Presleme Deeri

(GPa)
5
5
Burulma Hz (dev/dk,
Derece)
0,5/180
0,2/72
Burulma Deeri
5 tam tur
5 tam tur
Elde edilen numunelerin younluk, sertlik ve ekme dayanm deerleri llmtr. Ayrca, SiC ilavesinin etkileri
aratrlmtr. Younluk lm: Numunelerinin gerek younluk deerleri ayn dijital terazi ve younluk lm
kiti kullanlarak Arshimet prensibine gre yaplmtr Her bir kompozit iin teorik ve deneysel (gerek) younluk
arasndaki farklar alnarak gzenek miktarlar (1)de verilen eitlikle hesaplanmtr. lm sonular Tablo 2de
verilmektedir.

(1)
ekme Deneyi: SP ve EKST ilemlerinden elde edilen ekme deneyi numuneleri MPFI10, 1998 standartlarnda
olup, HPT ilemi sonucunda elde edilen ekme numuneleri boyutlar ve ekme aparat ekil 2de verilmektedir.
ekme hz 0,5 mm/dk olarak deney uygulanmtr. Her bir grup numune iin maksimum ekme dayanm deerleri
elde edilmi ve ortalama ekme deneyi sonular Tablo 3de verilmitir.
ekil 2. ekme numunesi boyutu ve ekme cihazna yerletirilen ekme aparat
764

Mikrosertlik lm: Shimadzu mikro sertlik cihaznda iz alan temel alnarak lm yaplan Vickers sertlik yntemine gre numunelerden sertlik lmleri alnmtr. Mikro sertlik iin, 2000 gf kuvvet 10 s uygulanm, mikro sertlik
lmleri ortalama sonular Tablo 4de verilmitir.
3. DENEYSEL SONULAR VE TARTIM
3.1 Younluk lm
Tablo 2. Numunelerin gzenek miktar
Malzeme
SP
Gzenek Miktar (%)
EKST
Gzenek Miktar (%)
HPT
Gzenek Miktar (%)
Alumix 231
% 5 SiC
3,93
4,31
0,59
0,67
0,43
0,58
Numunelerinin gzenek miktar SiC ilavesi ile art grlmtr Bunun nedeni SiC parack younluunun Alumix
231 tozun younluundan yksek olmasdr. SiC paracklarnn sertliinden dolay karm tozun skmaya daha
direnli hale gelmesiyle preslenebilirliin ktlemesi, parack takviye miktarnn artmasna paralel olarak da artan
matris/takviye ara yzey alannn artmas ve bunun da gzeneklilii arttrmas gsterilebilir [7].
Tablo 2 incelendiinde numunelerde ulalan en dk gzenek miktar %0,43 ile HPT numunelerine aittir. Burada
SP numunelerine ikincil ilem olarak uygulanan EKST ve HPT ilemleri gzeneklilii en alt dzeye indirerek mekanik zellikler asndan nemli bir avantaj salamtr.
3.2 ekme Deneyi
Tablo 3. Numunelerin ortalama ekme dayanm deerleri (MPa)
Malzeme
SP
ekme Dayanm (MPa)
EKST
ekme Dayanm (MPa)
HPT
ekme Dayanm (MPa)
Alumix 231
92
% 5 SiC
69
253
212
537
418
Malzeme ierisinde SiC ilavesinin ekme dayanm deerlerini azaltt grlmtr. Dn sebebi, takviye hacim
oran art ile ekme dayanm der. Toz paracklarnn retimi srasnda presleme sonrasndaki oluan gzenekler ve matris/ara yzey ba iyi olmad durumda ara yzey alan artna bal olarak SiC tozlarn birleememesiyle artan ara yzey alannn kopmay kolaylatrmas gibi faktrler bu azalmada etkili olduu dnlmektedir.
EKST ve HPT ikincil ilemleri de uygulansa takviye maddesi ilavesi matris katk maddesi toz ara yzey etkileimin
yetersiz kalmasna ve ara yzeylerden ayrlma krlmasnn gelimesine ve hzla enine kesitte ilerleyerek erken
kopmaya neden olmaktadr.
Burada ikincil ilemler ekme dayanmmda EKTS ilemi SPye gre %400 art salarken HPT ilemi EKTS ilemine gre %200 art salamtr. Burada HPT tekniinin temeli; malzemenin ilem srasnda hacmi deimeden
malzemeye deforme etme amacna dayanr. Bu ekilde malzeme de tane yaps mikron seviyeden nano seviyeye
indirilerek nano seviyede bir yap elde edilir (ekil 46). retilen malzemeler mikron seviyedeki ayn malzemeye
gre daha iyi zellikler gsterir. Bu da bu ilemin ok iyi olduunu gstermektedir [8,9].
3.3 Mikro sertlik lmleri
Tablo 4. Numunelerin ortalama sertlik deerleri (HV0.2)
Malzeme
SP
Sertlik Deeri
EKST
Sertlik Deeri
HPT
Sertlik Deeri
Alumix 231
33
76
239
% 5 SiC
37
77
258
Burada, HPT uygulanm numunelerdeki sertlik deerlerinin EKST ilemine gre yaklak 3 kat artt grlmektedir. Bunun nedeni HPT ileminin paracklarn klmesi ve Si dalmnn artmasyla tane snrlarnn oalmas
olarak gsterilebilir. Kullanm koullarna bal olarak sertlik istenilmesi durumunda TM malzemelerdeki bu sertlik
art nemli olabilir.
765

ekil 3. Alumix 231 ve %5 SiC HPT numunelerinin sertlik deerlerinin merkeze olan uzakla gre deiimi
ekil 3te grld gibi numunenin merkezinden kenara gidildike homojen bir sertlik dalm olmad gzlemlenmektedir. Bunun nedeni, kenar blgelerde gerinim artndan dolay tane klmesinin daha fazla yaanmasyla
aklanabilir.
Tane klmesine sebep olan gerilme, alma sertlemesine, hz da sertlik artna sebep olmaktadr. Farkl
almalarda da belirtildii gibi ilemin etkisi merkezden kenar blgeye doru gidildike daha fazladr [10]. Dikkat
edilirse %5 SiC ilavesi sertlikte ciddi art oluturmamtr ve sertlik deiimi merkezden uzaklatka ilavesiz matris
malzemeye paralel gitmektedir.
3.4 Mikroyap ncelemeleri
EKTS ve HPT Alumix 231 matris malzemeye ait numunelerin yzeylerinden alnan XRD grnt analizi ekil 4de
verilmitir.
ekil 4. Alumix 231 EKST ve HPT numunesine ait XRD grafiinde Si pikleri
Grafikten de grld gibi 56. pikte Si paracklarnn HPT sonras kld hatta baz piklerde kaybolduu
tespit edilmitir. Alumix 231 alamnn EKST ve HPT (P=5GPa ve N=5) numunelerine ait SEM grntleri ve SEM
fotoraflarndan llerek (Clemex image analysis) belirlenen silisyum fazlarn boyut dalm ekil 5te gsterilmektedir.
766

ekil 5. Alumix231 iin (a) EKST ve (b) HPT numunesine ait Si dalm grafii ve SEM grntleri
Toz halindeki ilem grmemi Alumix231 matriste tektik alt ikincil silikon fazlar ~2030 m boyutlarndadr [11].
Alam, EKST alama gre HPT sonras daha modller ve kk tektik silisyum fazlar bulunmaktadr. Ayrca
silisyum fazlar HPT sonras Al metal matris ierisine daha homojen dalma gstermektedir. Hem EKTS hem de
HPT sonraki alam, ~0,33,8 m arasnda deien silisyum fazlarn boyut dalmna sahiptir. Fakat EKTS sonras
alam farkl boyut gruplarnda faz dalm gsterirken, HPT sonrasnda daha homojen ve kk boyutta silisyum
faz dalm gstermektedir. Bir mikron altnda (1,0 m) silikon faz oran HPT sonras %89,5 iken EKTS sonras
70,4 %tir. Yine 0,5 mikron altnda ( 0,5) silikon faz 58,6 % iken EKTS sonrasndaki 30,9 % oranndadr.
ekil 6. %5 parack takviyeli numunelerin SiC paracklarn SEM grntleri

HPT ileminde takviye faz zerinde ok fazla klerek EKST ilemindeki gibi matris ierisinde dalmnda farkllk
salanmamtr. Ayrca, parack baznda ekil 6.(d)de grld gibi parack evresinde az miktarda krlmalara
sebep olsa da SiCn matris malzemeden sert olmas nedeniyle takviye elemann klmesi ve daha homojen
dalm sz konusu olmamtr. Bu durum farkl almalarla da desteklenmektedir [12]. Burada ekil 6. (b) ve (d)
incelendiinde ikincil faz olan Si paracklar HPT ncesinde uzun ve yaygn iken sonrasnda daha yuvarlak ve dzgn hale gelmitir [13].ekme deneyi sonras krlma yzeylerinden alnan SEM grntleri ekil 7de verilmitir.
767

ekil 7. %5 parack takviyeli numunelerin mikroyap grntleri

Krlma yzeylerinin SEM grntleri incelendiinde, SiC ile ana malzeme arasnda SP numunelerinde yeterli slatma gereklemedii grlmektedir. Buna bal olarak matris takviye malzemesi arasnda oluan birlemenin yeterli
olmad ve krlmann daha dk kuvvetlerle gerekletii dnlmektedir. EKST ve HPT numunelerinin Alumix
231 ve %5 SiC parack numunelerinde snek krlma gzlenmitir. Mekanik zelliklere bakldnda HPT numunelerinin ekme mukavemetinin olduka ykseldii grlmektedir. Tahmin edildii gibi uygulanan burulma ileminin,
numunelerin mekanik zelliklerini iyiletirdii ynnde bilgi vermektedir [8]. SP numunelerine direk HPT ilemi yapldnda baarsz olunmutur. SP numuneleri HPT ilemi balangcnda gerekli sneklii tamad iin uygulama
balangcnda numuneler krlmtr. Dolaysyla SP numunelerinde direk HPT ilemi uygulanmamtr.
4. SONULAR
-
-
-
kincil ilemler ekme dayanmmda EKST ilemi SPye gre %400 art salarken HPT ilemi EKST ilemine
gre %200 art salamtr.
Alumix231 ierisindeki %5 SiCp ilavesi ile, ekme dayanm azalm, sertlik deerleri ise bir miktar art gstermitir.
HPT ve EKST numunelerinde TM numunelerine gre daha snek krlma olutuu grlmtr.
5. TEEKKR
Bu alma, Pamukkale niversitesi Bilimsel Aratrma Projeleri Komisyonu tarafndan, BAP 2009/032 nolu projesi
ile desteklenmitir. Prof. Dr. Mehmet TRKERe laboratuar imknlarn salad iin teekkrlerimizi sunuyoruz.
KAYNAKLAR
1. Akbulut, H., Almina Fiber Takviyeli Metal Matrisli Kompozitlerin retimi ve Mikroyap-zellik likilerinin ncelenmesi, Doktora Tezi, T Fen Bilimleri Enstits (yaymlanmam), stanbul, 1995.
2. gel, B. Kompozit Malzemelerde Son Gelimeler ve leriye Dnk Beklentiler, 9. Uluslararas Metalurji ve
Malzeme Kongresi, stanbul, Vol. 33, pp. 639650, 1997.
3. Toptan, F., Alminyum Matrisli B4C Takviyeli Kompozitlerin Dkm Yntemiyle retilmesi, Yksek Lisans
Tezi, YT Fen Bilimleri Enstits, stanbul, 2006.
4. ODonnell, G., Looney, L., Production of Aluminium Matrix Composite Components Using Conventional PM
Technology, Materials Science and Engineering, Vol. A303, pp. 292 301, 2001.
5. Wlodarczyk-Flger A., Dobrzansk L.A., Kremzer M., Adamak M., Manufacturing of aluminium matrix composite materials reinforced by Al2O3 particles, Journal of Achievements in Materials and Manufacturing
Engineering, Vol. 27, pp. 99-102, 2008.
768

6. ahin, S., Akgn, S., Uzkut, M., Kksal, N.S., T/M Yntemi ile retilmi Al Esasl SiC, Al2O3, SiC + Al2O3
Takviyeli Kompozitlerin Anma Davrannn ncelenmesi, 10. Denizli Malzeme Sempozyumu ve Sergisi,
Denizli, pp.442 449, 2004.
8. Cepeda-Jimnez, C.M., Garca-Infanta, J.M., Zhilyaev, A.P., Ruano, O.A., Carreno, F., Influence of the Thermal Treatment on the Deformation-induced Precipitation of a Hypoeutectic Al7 wt% Si Casting Alloy Deformed by High-pressure torsion, Journal of Alloys and Compounds, Vol. 509, pp. 636643, 2011.
9. Rajinikanth, V., Venkateswarlu, K., Sen, M. K., Das, M., Alhajeri, S.N. and Langdon, T.G., Influence of scandium on an Al2% Si alloy processed by high-pressure torsion, Materials Science and Engineering A, Vol.
528, 17021706, 2011.
10. Edalati, K. and Horita, Z., Universal Plot for Hardness Variation in Pure Metals Processed by High-Pressure
Torsion, Materials Transactions, Vol. 51, pp. 1051-1054, 2010.
11. Heard, D.W., Donaldson, I.W. and Bishop, D.P., Metallurgical Assessment of A Hypereutectic AluminumSilicon P/M Alloy, Journal of Materials Processing Technology, Vol. 209, pp. 5902-5911, 2009.
12. Sabirov, I., Kolednik, O. and Pippan, R., Homogenization of Metal Matrix Composites by High-Pressure Torsion, Metallurgical and Materials Transactions A, Vol. 36A, pp. 2005-2861, 2005.
13. Edalati, K. and Horita, Z., Application of high-pressure torsion for consolidation of ceramic powders, Scripta
Materialia, Vol. 63, pp. 174177, 2010.
769

METALLIC FOAM
www.turkishpm.org
770

ALSi7, ALSi14 VE ALSi14CU4,5 KARIIM TOZLARDAN ALMNYUM

SANDV KPK RETLEBLRLNN ARATIRILMASI
Hseyin DEMRTA * ve Mehmet TRKER**
*
Karabk niversitesi Mhendislik Fakltesi, Metalurji ve Malzeme Mhendislii Blm, 78050, Karabk,
hdemirtas@karabuk.edu.tr
**
mturker@gazi.edu.tr
zet
Bu almada toz metalurjisi yntemi ile dk ergime derecesine sahip farkl Al alamnn sandvi kpk retimi aratrlmtr. Kullanlacak malzemelerin kimyasal bileimi AlSi7, AlSi14 ve AlSi14Cu4,5 olarak belirlenmitir.
Deneyler sonucunda alamn da saf alminyumdan olduka dk scaklklarda kprd ve sandvi retimi
iin uygun olduu belirlenmitir.
Anahtar Kelimeler: Toz metalurjisi, alminyum sandvi kpk.
INVESTIGATION OF THE REPRODUCTIBILITY OF ALUMINIUM SANDWICH FOAM FROM ALSi7, ALSi14
AND ALSi14CU4,5 PREMXED POWDERS
ABSTRACT
In this study, reproducibility of sandwich foam by using three different Al alloys, which have low melting points,
have been investigated. The chemical compositions of the powder were chosen as AlSi7, AlSi14 and AlSi14Cu4.5.
Experimental results has show that each three alloys foaming lower temperature than pure aluminum and detected
as suitable for sandwich production.
Keywords: Powder metallurgy, aluminum sandwich foam
1. GR
Sandvi yaplar kemiklerde ve yetikin aa dallarnda grld gibi tabiatta var olan bir malzeme trdr. Bu
noktada tabiatn mkemmelliini gz nne alrsak sandvi yaplarn gerekliliini ve nemini daha iyi anlarz. Bu
yaplar genel olarak hafif ekirdek malzemesinin sert iki d tabaka arasna yerletirilmesi ile retilir ve ayn llerdeki yekpare malzemeye gre zgl mukavemeti daha yksektir. zgl mukavemetinin salad arlk kazancnn
yan sra ses ve s yaltm, titreim emme, darbe absorbsiyonu ve daha uzun yorulma mr gibi zelliklerin bir
ksmn veya hepsini ihtiva edebilir [1,2]. Genel olarak baktmzda bu tr yaplarda minimum malzeme kullanlarak
maksimum performans, yapsal optimizasyon prensibi grlmektedir [3].
Sandvi yaplarn i ksmlarnda kullanlan ekirdek malzemesi olarak genelde polimer, metal, aa ve bunlarn
eitli ekiller verilmi trevleri kullanlmaktadr. Fakat bu malzemelerden dolay sandvi yaplarn olumsuz ynleri
genel olarak; neme duyarl olmalar, yanma direnlerinin dk olmas ve burulma riskinin klasik malzemelerden
daha yksek olmas eklinde sralanmaktadr [4]. Bahsedilen olumsuzluklar gelitirilen yeni malzeme trleri ile almaya allmaktadr. Bu konuda iyi bir alternatif olarak baklan metal kpkler akademik olarak youn bir ekilde
aratrlan, ksmen sanayi uygulamalar olan ve umut vadeden bir malzeme snfdr.
771

Metal kpkler inko, kurun, titanyum, elik gibi eitli metal ve alamlar ile retilebilmekle birlikte dk younluk, yksek korozyon direnci, uygun maliyet ve dier metallere gre kolay retilebilirlik gibi birok stn avantajlar
sebebi ile alminyum ve alamlar daha fazla tercih edilmektedir [5,6].
Alminyum kpkler ksaca zetlenecek olursa; tam olarak karakterize edilmemi, dk younluklu ve allmn
dnda mekanik, termal, elektrik, akustik zellikler barndran bir malzeme snfdr. Bu malzemeler, enerji absorbsiyonu, s kontrol, yaltm, hafif yaplar gibi eitli alanlarda kullanm potansiyeline sahiptir. Ayrca geri dnml
olmalar ve toksik zellik iermemelerinden dolay evreye zararlar yoktur [5,7,8]. Bunlarn yan sra dier malzemelerin kpk yaplar ile mukayese edildiinde; mekanik dayanm, sertlii ve enerji absorbsiyonu polimer kpklerden daha yksektir. Termal ve elektrik iletkenlikleri vardr ve mekanik zelliklerini polimer kpklere gre daha
yksek scaklklara kadar srdrebilirler. Ayrca zorlu artlarda polimer kpklere gre daha kararldr. Seramik
kpklerin aksine plastik deforme olabilir ve bylece enerji absorbe edebilirler [9].
Alminyum kpk kullanarak sandvi yap retiminde yzey levhalar kpe eitli yntemlerle balanabilmektedir. Bu yntemler kpn trne ve retim yntemine gre deimektedir. Farkl alamlardaki alminyum kpk
ve alminyum levha kullanarak sandvi yap retimi, balanma mekanizmalar ynnden temel olarak kprtme
esnasnda oluturulan doal balanma (in-situ bonding) ve kprtme sonras ilave balayclar yardm ile yapay
balanma (ex-situ bonding) olarak ikiye ayrlabilir [10,11]. Bu yntemlerden ilave arlk iermeme, sya duyarl
olmama, kolay geri dnm gibi birok sebeple doal balanma ynteminin kullanlmas daha avantajldr.
Bahsedilen doal balanma ile alminyum sandvi kpk (AFS) retiminde d tabaka ve kpren malzeme e
zamanl stlmaya tabi tutulmaktadr. Bu sebeple alminyum levha ergimeden kprmenin gerekletirilmesi gerekmektedir. Bunun iin izlenen yol kprtlecek alminyumun alamlandrlarak ergime scaklnn drlmesidir.
Yaplan almalarda genelde silisyum ve bakr kullanlarak alminyumun alamlar oluturulmaktadr [10-12]. Bu
almada saf alminyuma silisyum arlka %7, %14 ve AlSi14e %4,5 bakr ilave edilmi farkl toz karmnn
kprtlebilirlii incelenmitir. Ayrca btn alamlara kprtc madde olarak arlka % 0,6 TiH2 katlmtr.
Deneylerde toz olarak ECKA firmasndan temin edilen %99,9 saflktaki AS 91/S kodlu alminyum tozu kullanlmtr. Ayrca alminyumu alamlandrmak iin ortalama 63m boyutunda bakr tozu ve 10m boyutunda, %99,9
saflkta silisyum (AEE SI 102) tozu kullanlmtr. Kprtc madde olarak, Aldrich firmasndan salanan - 325
mesh boyutunda ve %98 saflkta TiH2 tozu kullanlmtr. Sandvi yap retimi iin, yzey tabakas olarak piyasada
yaygn olarak bulunan ticari saflktaki alminyum plakalar tercih edilmitir. lem basamaklar alttaki resimde (ekil
1) gsterilmektedir.
Sekil 1. Uygulama islem basamaklar
772

ekil 1deki ilem basamaklarnda grld gibi numune hazrlama ileminde, nce 1/10000 g hassasiyetinde
hassas terazi kullanlarak belirli oranlarda hazrlanan tozlar (a) Turbula marka T2 F tipi eksenli kartrc ile homojen bir dalm elde etmek amacyla kartrlmtr (b). Karm tozlar blok haline getirebilmek iin elik kalplar
kullanlarak tek eksenli preslenmi ve 30x50x10 mm boyutlarnda numuneler retilmitir (c). Presleme esnasnda
yalayc olarak inko stearat (Zn-55) kullanlm ve pres basnc olarak 600 MPa uygulanmtr. Blok haline getirilmi numunelere 450C de saatlik ksmi sinterleme uygulanmtr (d). Ksmi sinterleme sonras son ilem olarak
blok malzemeler 450C de %50 orannda deformasyona uratlmtr (e). Deformasyon sonras bloklar ikiye blnerek yaklak 30x30x5 mm boyutunda kprtlmeye hazr numuneler elde edilmitir.
Kprtlmeye hazr numuneler atmosfer ortamnda eitli scaklklarda kprtlmtr. Elde edilen kpk numunelerin 0,0001g hassasiyetindeki younluk lme cihaz kullanlarak Arimet prensibine gre younluklar belirlenmitir. Kpn gzeneklilii (p) aada verilen forml ile kpk younluunun (*) kpn hcre duvarlarn
oluturan malzemenin younluuna (s) oranlayarak elde edilmitir [13].
Son karakterizasyon ilemi olarak kpkler kprme dorultularnda kesilmi ve yzeyi klasik metalografik tekniklerle hazrlanan numunelerin, bilgisayar destekli Leica marka mikroskopta ortalama hcre duvar kalnlklar belirlenmitir.
3. DENEYSEL SONULAR
Kprmeye hazr numuneler 590C - 710C arasnda eitli scaklklarda en fazla 50 dakika sre ile kprtme ilemine tabi tutulmutur. Kprtme ilemi, frn camndan gzlemlenerek kprmenin ilk safhalar ve kmelerini iine
alan, eitli srelerde yaplmtr. Bu kprtme sreleri ierisinde numunelerden elde edilen en dk younluklar
aadaki grafikte verilmitir
ekil 2. Farkl alamlarda kprtme scaklnn younlua etkisi

Grafikte grld gibi en dk scaklk olan 590C de sadece bakr ilaveli olan karm 50 dakikalk bekleme
sonras verilen younluk deerine kadar kprme gstermitir. Ayn scaklkta dier karmlar 50 dakikalk sre
ierisinde yeterli kprme gstermemi ve daha fazla bekletilmemitir. AlSi14 alamnda 630C den sonra artan
scaklk ile younlukta belirli bir deiimin olmad dier iki alamda ise artan scaklk ile younluun ksmen
dt ve sonra tekrar ykseldii grlmektedir. Kpklerin viskoziteleri artan scaklk ile dmektedir ve buda
kpn kararlln olumsuz ynde etkilemektedir. Ayrca yine artan scaklk ile kprtme sresindeki bir dakikalk
deiiklik kp bariz ekilde etkilemektedir. Yaplan deneylerde ise en fazla bir dakikalk farklar gzlemlenmitir.
Sonuta artan scaklk ile younluk deiimleri anlk gzlemlenmedii iin yksek scaklklarda sonularn ksmen
yanltc olabilecei ngrlmtr. En dk younluk ise 690C de 9 dakikalk kprtme sonras AlSi7 alamnda
grlmtr. Dier alamlarda ise sras ile AlSi14Cu4,5; 670C de 11 dakikada ve AlSi14; 630C de 20 dakikada
en dk younluklar elde edilmitir. Sonuta genel olarak grafie baktmzda AlSi7 alaml kpklerde her scaklkta en dk younluun elde edildii grlmektedir. Aadaki ekilde farkl alamn en dk younluklar
ve bu younluklara ait makro grntleri verilmitir.
773

ekil 3. Farkl
alamlardaki kpklerin
en dk younluk
deerleri ve optik
grntleri
ekildeki grntlere baktmzda genel olarak homojen bir gzenek dalm grlmekte birlikte AlSi14 alam
dierlerine gre daha dzensiz bir yap sergilemitir. AlSi7 alamnda ise kpn kenarlarnda kk gzenekler
olumakla birlikte genelde iyi gzenek dalmna sahiptir. Bakr ilaveli alam ise yaklak her scaklkta iyi bir gzenek morfolojisi gstermitir.
Kpklerin greceli younluklarna baktmzda hcre duvarn oluturan malzemenin teorik younluunu belirlemek iin; kp oluturan malzemenin younluu (dk), karm oluturan malzemelerin ktleleri toplamnn
(m1+m2+mn) hacimleri (v1+v2+vn) toplamna blnmesi ile elde edilir. Daha sonra greceli younluk ( = */s) ve
yzde gzeneklilik [(1- )x100] belirlenir:
s = (m1 + m2) / (v1 + v2)
d(AlSi7) = 93 + 7 / [(93 / 2,698) + (7 / 2,33)] = 2,66 g/cm3
(AlSi7) = 0,389 / 2,66 = 0,146
Gzeneklilik = % 85,4
d(AlSi14) = 86+14 / [(86/2,698) + (14/2,33)] = 2,64 g/cm3
(AlSi14) = 0,512 / 2,64 = 0,194
d(AlSi14Cu4,5) = 81,5+14+4,5 / [(81,5 / 2,698) + (14 / 2,33) + (4,5/8,92)] = 2,724 g/cm3
(AlSi14Cu4,5) = 0,442 / 2,724 = 0,162
Hesaplamalarda grlecei gibi kpklerin gzeneklilikleri younluklarna paralel olarak deimektedir. Fakat kp oluturan bileenlerin younluklar hesaba katld iin ar bakr tozlar ieren karmn gzeneklilii beklenenden daha yksek kmaktadr. Yani bakr alaml kpk dier numuneler kadar, hatta daha fazla gzeneklilie
sahip olsa dahi younluu daha fazla kabilir. Buda younluu yksek alam katklarnn dezavantajdr. Ayrca
alminyuma katlan Cu, Si elementine gre tektik scakl daha fazla drmektedir. Fakat tektik noktaya ulamak iin olduka fazla bakr ilavesi gerekmekte (% 33 Cu, 548,2 C) ve bakrn bahsedilen olumsuzluu sebebiyle
bu alam cazip olmamaktadr [14].
Son olarak elde edilen kpklerin duvar kalnlklarna bakldnda ise mikroskop altnda hcre duvarlarnn dzgn
boyutlu olmamalarndan dolay ortalama duvarlarn ince ve kaln ksmlar ayr olarak llerek verilmitir. Aadaki
fotorafta AlSi14 alaml kpn hcre duvarnn mikroskop altndaki grnts verilmitir.
ekil 4. AlSi14 alaml

kpn hcre duvarnn
mikroskop grnts
774

Yaplan lmler neticesinde AlSi7 alaml kpn hcre duvarlar kaln blgelerde 82m, ince blgelerde 57m,
AlSi14 alamnda kaln blgelerde 145m ve ince blgelerde 84m ve son olarak AlSi14Cu4,5 alamnda ise
kaln ksmlarda 295m, ince ksmlarda ise 125m ve olarak belirlenmitir. Eit arlkl numuneler iin artan hcre
duvar kalnlnn azalan hcre duvar miktarn ve bu da artan gzenek boyutunu gstermektedir. Yani ortalama
gzenek boyutlar kkten bye; AlSi7, AlSi14 ve AlSi14Cu4,5 olarak sralanabilir. Yaplan dier akademik almalar da bu sonucu dorulamaktadr [15].
4. SONU ve NERLER
Yaplan almalar neticesinde farkl alamn da 630C civarnda yeterli kprme gsterdii gzlemlenmitir.
Bu da her alamn alminyum levha kullanarak kprtme esnasnda sandvi kpk retiminde kullanlabilecek
yeterlilikte olduunu gstermektedir. En dk kprme scakln ve en iyi gzenek morfolojisini AiSi14Cu4,5 alam gstermitir. AlSi7 alam da olduka iyi sonular vermi ve en dk younluk bu alamdan elde edilmitir
ki zaten birok akademik almada bu alam tercih edilmitir [10,11,16]. AlSi14 alaml kpk ise ok iyi sonular
vermemekle birlikte kullanlabilecek niteliktedir.
KAYNAKLAR
1. K.P. Jackson, J.M. Allwood, M. Landert, Incremental forming of sandwich panels, Journal of Materials Processing Technology, 114 2008.
2. Sandwich Data Sheet, Alulight international GmbH., Ranshofen, 2007.
3. S. Herrmann, P. C. Zahlen, and I. Zuardy, Sandwich Structures 7, Netherlands, Airbus Deutschland GmbH,
1326, 2005.
4. D. Gay, S. V. Hoa, S. W. Tsai, Composite Materials Design And Applications, United States of America, CRC
Press, 2003.
5. M.F. Ashby, A.G. Evans, N.A. Fleck, L.J. Gibson, J.W. Hutchinson and H.N.G. Wadley, Metal Foams: A Design
Guide, Boston, Butterworth-Heinemann 1, 2000.
6. J. Banhart, J. Baumeister, M. Weber, Powder Metallurgical Technology for the Production of Metallic Foams,
in Conf. Rec. 1995 European Conference on Advanced PM Materials, 201208.
7. R. Montanini, Measurement of strain rate sensitivity of aluminium foams for energy dissipation, International
Journal of Mechanical Sciences, 47: 2642, 2005.
8. J. Vogel, J. Keller, A. Sviridov, H.J. Feige, K. Kreyssig, J. Auersperg, P. Plass, H. Walter, Characterization of
Strength Behavior of Aluminium Foam Sandwiches Under Static Load, Strain, 19, 2009.
9. L. P. Lefebvre, J. Banhart, D.C. Dunand, Porous Metals and Metallic Foams: Current Status and Recent Developments, Advanced Engineering Materials 10 (9): 775787, 2008.
10. J. Banhart, H. Seeliger, Aluminium foam sandwich panels: manufacture, metallurgy and applications, Advanced Engineering Materials, 9: 793802 2008.
11. J. Banhart, H. Stanzick, L. Helfen, T. Baumbach, K. Nijhof, Real-time Xray Investigation of Aluminum Foam
Sandwich Production, Advanced Engineering Materials, 6: 407411 2001.
12. D. Schwingel, H.W. Seeliger, C. Vecchionacci, D. Alwes, J. Dittrich, Aluminium foam sandwich structures for
space applications, Acta Astronautica, 61: 326330 2007.
13. Y. Mu, G. Yao, H. Luo, Anisotropic damping behavior of closed-cell aluminum foam, Materials and Design,
31: 610612 2010.
14. H. Baker, ASM Handbook Volume 3, USA, ASM International, 3. Ed. 2.44, 2.51 1999.
15. H. Demirta, Toz metalurjisi yntemi ile alminyum esasl kpk sandvi yap retimi, Yksek Lisans Tezi,
Gazi niversitesi Fen Bilimleri Enstits, Ankara, 2010.
16. H. Yu, G. Yao, X. Wang, Y. Liu, H. Li, Sound insulation property of AlSi closed-cell aluminum foam sandwich
panels, Applied Acoustics, 68: 15021510 2007.
775

MEKANK ALAIMLANMI Al2O3 TAKVYEL AlSi7Mg0,6 ESASLI

TOZLARDAN METALK KPK RETM VE ZELLKLERNN
NCELENMES
Yasin PELT*, Mehmet TRKER**
**
*
Gazi niversitesi, Fen Bilimleri Enstits, Metal Eitimi Blm
mturker@gazi.edu.tr
ZET
Bu almada Al2O3 takviyeli Al esasl metalik kpk retimi iin Al, Si, Mg ve TiH2 tozlar 30 dakika sreyle
eksenli kartrma yapabilen turbula cihaznda kartrlmtr. Daha sonra Szegvari tip mekanik alamlama cihaznda, 1/10 toz bilye orannda ve argon atmosferi altnda, 350 dev/dk hzda, 15, 30, 60, 120 dakika srelerde MA
yaplmtr. MA yaplm tozlar 400 MPa basn altnda kalp ierisinde tek ynl olarak sktrlmtr. Sktrlan
numuneler 550C scaklkta ekstrzyon ileminden geirilmitir. Daha sonra 500C de haddelenerek kprmeye hazr levha eklinde numuneler elde edilmitir. Bu numuneler 690 C ve 7 dk sreyle kprtme ilemine tabi
tutulmutur. Kpk malzemeler mikro ve makro boyutta incelemeler yaplm ve MA sresine bal olarak kpk
malzemelerin younluunda artma, 15 ve 60 dk MA yaplm tozlardan elde edilen kpk malzemesinin gzenek
morfolojisinde daha homojen bir dalm gsterdii grlmtr.
Anahtar Kelimeler: Mekanik Alamlama, Al Kpkler, Toz Metalurjisi
Production of metallic foam from mechanically

alloyed Al2O3 reinforced AlSi7Mg0.6 powders and investigation
of its properties
Abstract
In order to produce Al2O3 reinforced Al based metallic foam Al, Si, Mg and TiH2 powders were mixed in a three
dimensional turbula for 30 min and then mechanically alloyed in a Szegvari type attritor for 15, 30, 60, 120 minutes
with the powder ball ratio of 1/10 at 350 rev/min in Ar atmosphere. Powders were compacted in a steel die by using
a uniaxial press at 400 MPa pressure. Compacted powders were extruded at 550C and then hot rolled at 500C to
produce foamable precursor sheet. Sheets were then subjected to foaming process at 690 C for 7 min. Macro and
micro examinations were carried out on the foamed materials. It was found that higher mechanical alloying duration
resulted in the formation of denser foam material however, foam produced from 30 and 60 minutes mechanically
alloyed powders showed more homogeneous pore morphology.
1. GR
Teknolojinin ilerlemesi ile birlikte malzeme biliminde nemli gelimeler yaanmaktadr. Malzeme biliminin son gelimeleri arasnda metalik kpkler nemli bir yer tutmaktadr. Metalik kpkler, gzenekli yapya sahiptir ve bu yap
retim esnasnda baz ilemler uygulandktan sonra ortaya kar. Doal kpk ile hibir ilgisi olmamasna ramen
grnm ve baz zelliklerinden dolay metalik kpk diye adlandrlr [1].
776

Toz metalurjisi (TM) yntemiyle Al esasl metalik kpk retimi toz haldeki Al, kprtc madde (genellikle TiH2) ve
dier alam elementlerinin preslenmesiyle elde edilen kompakt yapnn ergime scaklnn zerinde bir scakla
kadar stlmasyla devam eder. Sv metal ierisinde TiH2in ayrmasyla gzenek ekirdekleri olumaya balar ve
zamana bal olarak hcresel yaplar oluturur [2]. Hcresel malzemeler arasnda seramik, metalik ve polimer gibi
malzemeler saylabilir. Metalik kpkler, mekanik zelliklerin iyi olmasndan dolay gnmzde artan neme sahip
malzemelerdir [3].
Metalik hcreli malzemelerin yapsal kullanm alanlar arasnda otomotiv, demiryolu ve inaat endstrileri, uzay
aralar, gemi ve spor malzemeleri yapm ve biyomedikal uygulamalar; ilevsel kullanm alanlar arasnda ise
filtreleme ve ayrma, s dntrc, soutma sistemleri, elektrokimyasal uygulamalar, su artma, sv muhafaza
ve iletimi gibi uygulamalar saylabilir [4]. Fark zelliklere sahip malzemelerin iyi zelliklerini bir araya getirerek
stn zelliklere sahip kompozit malzemeler retilir. retimdeki bu eitlilik retim yntemlerine de yansmaktadr.
Mekanik alamlama (MA) yntemi ile metalik kpk retimi bu konuya rnek olarak verilebilir. MA bir kat toz retim
metodu olup, genellikle yksek enerjili deirmenler kullanlarak yaplr. MA deirmenine genellikle biri kolay sekilenebilen (snek) metal tozlar ve dierleri krlgan, metal veya seramik tozlar konularak alamlama/tme ilemi
yaplr. Atritr tipi MA deirmenleri genellikle su soutmaldr ve tme srasnda oksitlenmeyi minimuma indirmek
iin Ar, H veya N gaz kullanlr [5].
Bu almada MA yntemiyle homojen yapda Al2O3 takviyeli alminyum esasl metalik kpk retimi gerekletirilip
MA sresinin kpk malzemenin gzenek yapsna etkisi incelenmitir.
2. DENEYSEL ALIMA
2.1. Malzeme ve Yntem
Bu almada alminyum kpk malzeme retmek iin %99,7 saflkta Al, %7 Si, %0,6 Mg, %2 Al2O3, %0,8 TiH2
tozlar kullanlmtr. Tozlar turbola cihaznda homojen bir karm elde etmek amacyla 30 dakika sreyle kartrlmtr. Daha sonra Szegvari tip atritrde 1/10 toz bilye orannda ve Ar atmosferi altnda, 350 dev/dk hzda 15, 30, 60,
120 dk srelerde MA ilemine tabi tutulmutur. Tozlar daha sonra kalp ierinde 400 MPa basn altnda tek ynl
olarak sktrlmtr. Sktrlan numuneler 550 Cde 1/3 orannda ekstrzyona tabi tutulmu ve 500 Cde haddelenerek levha halinde kprtlmeye hazr numuneler elde edilmitir. Bu numunelerin kprtme ilemi 690 Cde
ve 7 dk sreyle gerekletirilmitir. Elde edilen kpk malzemelerin makro ve mikro yap incelemeleri yaplmtr.
Yaplan almalar sonucunda 15 dk MA yaplm malzemenin gzenek yapsnn dierlerine gre daha homojen
dalm sergiledii belirlenmitir.

3.1. MA Sresinin Lineer Genilemeye Etkisi
MA sreleri ve buna bal olarak kpk malzemelerin lineer genilemesi ekil 1de grlmektedir. 15 dk MA yaplm
numune %226 lineer genleme oranyla en fazla lineer genlemeye sahip kpk malzemesi olduu grlmektedir.
Karm tozlar 30 dk MA yapldnda ise kpk malzemenin lineer genilemesi belirgin bir ekilde azalarak %132
ye geriledii grlmektedir. MA sresi artrlp 60 dk ya karldnda ise kpk malzemenin lineer genilemesi
%193e kt grlmektedir. 120 dk MA yaplm tozlardan elde edilen kpk malzemenin lineer genilemesinde
tekrar bir d olduu ve %165 e geriledii grlmektedir. Bunun muhtemel sebebinin MA sresine bal olarak
deien toz tane boyutu olduu dnlmektedir. Ark ve arkadalar yaptklar almada MA iin kullandklar Al
ve Al4C3 tozlarn 0.5, 1, 2.5, ve 7.5 saat elik bilye ortamnda MA yapmlar ve 0,5 saatlik MA da ortalama toz boyutunun 150 m den 82 m ye dtn, 1 saatlik MA da ise ortamn ssndan kaynaklanarak toz boyutunda hzl
byme gstererek 172mye ktn ve 2.5 saatlik MAda ise toz boyutunun 53 mye dtn belirtmilerdir
[6]. Deien toz boyutlar presleme sonras elde edilen blok numunenin gzeneklilik orann etkileyecektir. Numunelerdeki gzeneklilik oran, kprme esnasnda kprtc maddeden ayran hidrojen gaznn kamasna neden
olacaktr. Dolaysyla MA sresine bal olarak deien toz boyutunun lineer genilemeyi etkiledii dnlmektedir.
Sarta ve arkadalar btn mekanik toz retim tekniklerinde olduu gibi mekanik alamlamada da kirlilik sorunu
oluabileceini belirtmilerdir [7]. MA sresinin artmasna bal olarak kpk malzemelerin lineer genilemesinde
greceli bir azalma olduu ekil 1 de grlmektedir. Burada lineer genilemedeki azalmann malzemedeki kirlenmelerden kaynaklanm olabilecei dnlmektedir.
777

ekil 1. Kpk numunelerde zamana bal % lineer genileme oran

3.2. MA Sresinin Younlua Etkisi
MA sresinin younluk zerindeki etkisi ekil 2de grlmektedir. 15 dk MA yaplm tozlara ait kpk malzemenin
younluunun 0,818 g/cm3 lk deerle en dk younlua sahip malzeme olduu grlmektedir. 30 dk MA ile retilmi kpk malzemenin younluu 1,144 g/cm3 lk deere kt ekil 2de grlmektedir. Buradaki ani younluk
artnn MA esnasnda kirlenmeler ve TiH2deki ayrmalar olabilecei dnlmektedir. 60 dk MA ile retilmi tozlara ait kpk malzemenin younluu ise 0,914 g/cm3e dt grlmektedir (ekil 2). 120 dklk MA ile retilmi
tozlara ait kpk malzemenin younluu ise 1,014 g/cm3 olduu grlmektedir. Kpk malzemelerdeki younluk
ve lineer genilemedeki deiimlerin aklanmasnda toz malzemelerin MA esnasndaki zamana bal olarak etki
eden baz kuvvetleri dikkate almak gereklidir. Suryanarayana, MA esnasnda oksit ve karbrlerle glendirilmi
alamlarn yksek enerjili deirmen ierisinde, srekli bir deformasyon, krlma, souk kaynak, tekrar krlma ve
ardndan kaynaklanma aamalarn ieren homojen dalml, kimyasal ya da sl ilem gerektirmeyen kat hal reaksiyonu olduunu belirtmitir (8). MA esnasnda meydana gelen bu deiimlerin, kpk malzeme zerinde gsterdii
younluk ve lineer genilemedeki dalgalanmalarn bu ekilde olmas yadrganamaz.
ekil 2. MA sresine bal younluk deiimi

3.3. Kpk Malzemelerin Makro Yap ncelemeleri
15 dk, 30 dk, 60 dk, 120 dk MA yaplm takviye elemanl tozlara ait kpk malzemelerin makro gzenek yaps
ekil 3te grlmektedir. ekil 3.aya bakldnda, kpk malzemenin gzenekleri ksmen iri ve hcre duvarlarnn
ise kaln olduu grlmektedir. Bu da gzenekler yap zerinde homojen bir dalm sergilediini gstermektedir.
ekil 3.b ye bakldnda malzemenin gzenek yapsnda homojen dalm olmad, gzeneklerin iri, gzeneklerde bir ynlenme ve hcre duvarlarnda girinti ve kntlarn hakim olduu grlmektedir. Malzemedeki bu hzl
deiimin nedeni MA esnasndaki toz tane boyutundaki deiimler, kirlenmeler, TiH2 tozlarndaki znmelerin ve
778

belirli bir ksmnn ise atritr eperine yapmas etkili olduu dnlmektedir. 60 dk lk MA yaplm tozlardan
elde edilen kpk yap ekil 3.cde grlmektedir. Burada malzemenin gzenek saysnda greceli olarak bir art,
gzeneklerinde klmeler ve hcre duvarnda incelme olduu grlmektedir. Asavavisithchai ve arkadalar kompakt malzeme stlmaya baladnda TiH2 deki ayrmalar ilk nce ekirdek gzenekleri ve bu ekirdek gzenekleri
birleerek hcresel yapy oluturduunu belirtmitir [2]. Burada gzeneklerin ksmen kk ve ok sayda olmas
yzey gerilim kuvvetlerinin ve Al2O3 takviye elemannn hcre ekirdeklerin byyerek birletirmesinde snrlayc
kuvvet olarak etki ettii dnlmektedir. ekil 3.dye bakacak olursak kpk malzemelerde istenen homojen dalml hcre morfolojisinden uzaklat grlmektedir. Gzenekler baz blgelerde iri yapda, baz blgelerde ise
kk olduu grlmektedir.
ekil 3. MA yaplm numunelere

ait makro gzenek yaplar.
a) 15 dk MA, b) 30 dk MA,
c) 60 dk MA, d) 120 dk MA
3.4. Mikro Yap ncelemesi

MA yaplm tozlardan elde edilen kpk malzemelerin SEM grntleri ekil 4te grlmektedir. ekil 4.ada 15 dk
MA yaplm tozlardan elde edilen kpe ait hrce duvar grlmektedir. Hcre duvarnn kaln olmas nedeniyle
hcre duvar zerinde kk gzeneklemelerin olduu grlmektedir. MA sresi 30 dkya ulatnda ise kpk
malzemenin hcre duvarnda girinti ve kntlarn hakim olduu ve homojen bir gzenek yapdan uzaklald ekil
4.bde grlmektedir. MA esnasnda toz malzemelere zamana bal olarak plastik deformasyon, krlma ve souk
kaynak kuvvetlerinin etki ettii bilinmektedir. Burada ise malzemeler henz plastik deformasyon aamasnda olduu
ve bu etkinin kpk malzemenin homojen gzenek yapsndan uzaklatrd dnlmektedir. 60 dk MA yaplm
tozlardan elde kpn hcre duvar grnts ekil 4.cde grlmektedir. Burada hcre duvarnda belirgin bir
ekilde incelme olduu grlmektedir. ekil 4.d de ise 120 dk MA yaplm tozlardan elde edilen kpk malzemenin
hcre yaps grlmektedir. Burada hcre duvar zerinde gzeneklemelerin olduu ve hcrelerin irili ufakl olduu
grlmektedir. Hcre duvarnda gene bir incelme olduu ve girinti kntlarn hakim olduu grlmektedir. Bu duruma malzemenin kprme esnasnda yzey gerilimi kuvvetlerinin dengesiz bir etki ettii dnlmektedir.
ekil 4. Farkl srelerde MA

yaplm tozlardan elde edilen
kpk malzemelerin SEM
grnts, a) 15 dk, b) 30 dk,
c) 60 dk, d) 120 dk
779

3.5. Sonular
Bu almada %2 Al2O3, takviyeli Al esasl Al-Mg-Si tozlarna %0,8 orannda TiH2 tozlar kartrlarak nce turbolada daha sonra farkl srelerde yksek enerjili atritrde MA ilemine tabi tutulmutur. Tozlar daha sonra presleme,
sinterleme, ekstrzyon ve scak haddelemenin ardndan kprtme ilemine tabi tutulmu ve aadaki sonular
elde edilmitir.
MA sresinin kpk malzemenin younluu, gzenek dalm ve gzenek duvar kalnlna etki ettii grlmtr.
MA sresi arttka younlukta greceli olarak bir d olduu ve 30 dakikalk alamlamann daha etkili olduu
grlmtr. Kpk malzemenin gzenek boyutu ve gzenek duvarna bakldnda ise MA sresi arttka gzeneklerin kld ve gzenek duvarnn inceldii tespit edilmitir. Bu durum 60 ve 120 dk MA ilemine tabi tutulmu
numunelerde daha belirgin olarak ortaya kmtr.
KAYNAKLAR
1. Yavuz, .,Metalik Kpk Malzemeler ve Uygulama Alanlar, Tat Teknolojileri Elektronik Dergisi (TATED),
Cilt: 2, No: 1, (49-58) 2010
2. S., Asavavisithchai, A.R. Kennedy., The effect Of Mg Addition On The Stability Of AlAl2O3 Foams Made By A
Powder Metallurgy Route, Scripta Materialia, 54 13311334 (2006)
3. Pelit, Y., Ayata, A., Kurt, A., Trker, M., Toz Metal Al Kpk Malzemelerin Kprtme ncesi Saplama Kayna
ile Birletirilmesi 6. Uluslar Aras Teknolojiler Sempozyumu, Elaz, 2011
4. Baspnar, M. S., Yurtcu, S., Metalik Kpk Malzemelerin Mekanik zelliklerini Belirlemede Kullanlan Matematiksel Modeller, Makine Teknolojileri Elektronik Dergisi, Cilt: 8, No: 1, 2011 (69-78)
5. Kaya, H., Spex Tip Mekani Alasmlama Cihaznn Tasarm, malat Ve
gtme Kabiliyetinin incelenmesi, 5. Uluslararas leri Teknolojiler Sempozyumu (IATS09), 13-15 Mays
2009, Karabk, Trkiye
6. Ark, H., Trker, M., Sarta, S., Mekanik Alamlama le Alminyum Matrisli Alminyum Karbr (Al4C3) Kompozit Malzeme retimi 2. Ulusal Toz Metalurjisi Konferans, Ankara, 1999
7. Sarta. S., Trker, M., Durlu, N., Toz Metalurjisi Ve Parackl Malzeme lemleri, Trk Toz Metalurjisi
Yaynlar, 05, Ankara, (2007)
8. Suryanarayana, C., Mechanichal Alloying And Milling, Progress in Materials Science, 46, (2001)
780

ALMNYUM TOZ TANE BOYUTUNUN KPK

oluumuna ETKSNN NCELENMES
Salim ahin*, Hlya DURMU**, Nilay YKSEL*
*
Celal Bayar niversitesi, Mhendislik Fakltesi, Malzeme Mhendislii Blm, Muradiye-Manisa.

salim.sahin@bayar.edu.tr, nilay.yuksel@bayar.edu.tr
**
Celal Bayar niversitesi, Turgutlu MYO, Makine ve Metal Teknolojileri Blm, Turgutlu-Manisa.
hulya.kacar@bayar.edu.tr
ZET
Bu almada, farkl boyutlara sahip alminyum tozlar kullanlmtr. Toz metalurjisi yntemi ile %98,23 saflkta
alminyum tozuna %1, 5 ve 10 SiC takviye eleman ve kprtc madde olarak ise TiH2 tozu %0.5, 1, 1.5, 2
oranlarnda eklenerek kpk numuneler retilmitir. Alminyum tozu, takviye elaman ve kprtc madde tozlar 3
saat sreyle kartrlm ve daha sonra sktrma, n stma, deformasyon ve kprtme ilemlerine tabi tutulmutur.
retilen kpkte alminyum tozu tane boyutuna bal olarak uygun kprtme sresi, kprme miktar, younluk ve
gzenek dalm aratrlmtr.
Anahtar Kelimeler : Al Kpk, SiC, TiH2, Al toz tane boyutu.
INVESTIGATION OF THE EFFECT OF ALUMINIUM POWDER PARTICLE

SZE ON FOAM FORMATION
Abstract
In this study, aluminium powders in different sizes have been used. Foam samples have been produced by powder
metallurgy method adding 1,5% and 10% SiC reinforcing member and TiH2 as foaming agent at the rate of 0,5, 1,
1,5, 2 % in aluminium powder at 98,23 % grade. Aluminium powder, reinforcing member and foaming agent powders
have been mixed for 3 hours and then subjected to pressing, pre-heating, deformation and foaming processes. On
produced foam, adequate foaming time, foaming gauge, density and pore distribution depending on granule size of
aluminium powder have been investigated.
Keywords: Al Foam, SiC, TiH2, Al powder particle size
1.Giri
Metalik kpkler, mekanik zelliklerinin iyi olmasndan dolay gnmzde byk bir neme sahiptir. zellikleri
arasnda, enerji emebilme kabiliyetinin yksek olmas, dk arlk, sl izolasyon, titreim azaltma ve kimyasal
szme saylabilir [1]. Daha ok alminyum esasl metalik kpkler, eitli mhendislik uygulamalarnda kullanm
alan bulabilen malzemeler olarak son yllarda olduka ilgi ekmektedir. Alminyum kpkler, darbe enerjisini plastik
enerjiye dntrebilirler ve birok metalden daha fazla enerji absorbe edebilirler. Tpler ierisine dolgu malzemesi
olarak konulduklarnda emilen toplam enerji hafifliin ve mukavemetin bir arada bulunmas gereken otomotiv, uzay
sanayi, demiryolu tamacl ve asansr gibi alanlarda kullanlmaktadr [2]. zellikle alminyum kpkler, kapal
hcre yaps ve ok hafif olmas ile gze arpmaktadr. Bundan dolay ses ve enerjinin absorbesinde alminyum
kpkleri fonksiyonel olarak kullanlmaktadr [3].
retim yntemleri arasnda ergiyik ierisine gaz enjekte edilmesi, ergiyik ierisine kprtc madde ilavesi ve toz
metalurjisi yntemleri saylabilir. Toz Metalurjisi (TM) yntemi, metal kpklerin retimi iin en yaygn kullanlan
781

yntemlerden biridir ve bu alanda youn almalar yaplmaktadr. TM yntemiyle, bilinen basit kpk retiminin
yan sra sandvi kpk, kresel kpk, ii bo kalp veya profil ierisinde kprtme yaplabilmektedir [4].
TM ynteminde metal tozlar, kprtc madde (genellikle TiH2) ile kartrlr ve preslenir. Kprtme ilemi srasnda
scakln artmasyla yap ierisindeki kprtc madde ayrr ve gaz kna neden olur. Ayrma ilemi esnasnda
yksek scaklktaki metalde genleme yani kprme meydana gelir [5]. Alminyum iin TiH2 tozu genellikle % 0.6-1
arasnda kullanlmaktadr [6].
Bu almada, alminyum kpk retiminde kullanlan alminyum tozunun tane boyutunun kpklemeye olan
etkisi incelenmitir.
2. DENEYSEL MALZEME VE METOD
2. 1. Malzeme
Bu almada, 53 m, 100 m ve 200 m altndaki boyutlarda %98.23 saflktaki alminyum tozlar (izelge 1), 53
mluk SiC (izelge 2) ve kprtc madde olarak TiH2 tozlar kullanlmtr.
izelge 1. Alminyum Tozunun Bileimi (%).
Al
98.23
Fe
0.0056
MgO
1.52
izelge 2. SiC Bileimi (%).

SiC
97.80
Si
0.65
SiO2
0.59
Fe
0.12
C
0.29
Dierleri
0.55
2.2. Deneysel Metot

2.2.1. Eleme, kartrma ve presleme
Alminyum tozlar elenerek 0-53 m, 53-100 m, 100-200 mluk, SiC tozlar elenerek 0-53 mluk tozlar elde
edilmitir. Al, SiC ve TiH2 den oluan 20 deneme ve 36 esas olmak zere 56 karm (izelge 3) 1/1000 g
hassasiyetindeki bir teraziyle (ekil 1) tartlarak homojen bir dalmn oluturulmas iin 3 saat sreyle kartrlmtr.
Hazrlanan karmlar 10 mm apl silindir kalba aktarlm, 600 MPa basn altnda sktrlarak 10x10 mm
silindirik numuneler (ekil 2) elde edilmitir.
ekil 1. Karm hazrlama
ekil 2. Sktrlm numuneler
782

izelge 3. Karmlar ve miktarlar.

Alminyum Tane Boyutu
Karm Miktarlar
0-53 m
53-100 m
100-200 m
Al (%)
SiC (%)
TiH2 (%)
A2
B2
C2
98.5
1
0.5
A4
B4
C4
94.5
5
0.5
A5
B5
C5
89.5
10
0.5
A8
B8
C8
98
1
1
A10
B10
C10
94
5
1
A11
B11
C11
89
10
1
A14
B14
C14
97.5
1
1.5
A16
B16
C16
93.5
5
1.5
A17
B17
C17
88.5
10
1.5
A20
B20
C20
97
1
2
A22
B22
C22
93
5
2
A23
B23
C23
88
10
2
2.2.2. n Istma ve Deformasyon lemi
Elde edilen silindirik numuneler 550 oC scaklkta 3 saat sreyle n stma ilemine tabi tutulmutur (ekil 3).
Ardndan %50 orannda preste sktrlarak deforme edilmitir (ekil 4).
ekil 3. n stma uygulanmas
ekil 4. Deformasyon uygulanmas

2.2.3. Kpkletirme lemi
Sktrlarak %50 deforme edilmi olan numunelerden, deneme numuneleri en iyi kprme sresinin belirlenebilmesi
iin 700 oC de 90 dakikaya kadar bir n teste tabi tutulmutur. 20 numune (ekil 5) belli periyotlarla frndan
alnmtr. kan sonular dorultusunda 36 numune 700 oC de 35 dakika bekletilmi ve frndan alnarak havada
soutulmutur.
ekil 5. Deneme numuneleri
783


Toz metalurjisi ile alminyum kpk retiminde TiH2 kprtc madde miktar (%0.5, 1, 1.5, 2), SiC oran (%1, 5,
10) ve alminyum tane boyutu (0-53 m, 53-100 m, 100-200 m) gibi farkl parametre kullanlmtr. n stma
scakl 550 oC, toz presleme basnc 600 MPa, deformasyon miktar %50, kprtme scakl 700 oC ve kprme
sresi 35 dakika olarak sabit tutulmutur.
3.1. Deneme Numunelerinde Kpkleme ve Gzenek Dalm Sonular
%98.23 Al, %2 SiC ve %1 TiH2 den oluan deneme numuneleri kprme sresinin tayin edilebilmesi amacyla
kullanlmtr. 20 numune 700 oC de, 2.5 dk, 5 dk, 7.5 dk, 10 dk, 15 dk, 20 dk, 25 dk, 30 dk, 35 dk, 40 dk, 45 dk, 50
dk, 55 dk, 60 dk, 65 dk, 70 dk, 75 dk, 80 dk, 85 dk ve 90 dk da frndan alnarak kpklemeleri incelenmitir. En iyi
gzenek yapsnn ve en dk younluun 35. dakikadaki numunede olduu belirlenmitir (ekil 6-7). Daha az ve
fazla srelerde numunelerde kpkleme az yada dzensiz olmutur. Artan sre ile numunelerde kabarma olmu
ama daha sonra kmeler gereklemitir.
ekil 6. Deneme numunelerinin gzenek dalm
ekil 7. Deneme numunelerinin younluk grafii

3.2. Kpk Numunelerin Kpklemeleri ve Gzenek Dalm Sonular
Hazrlanan numuneler 700 oC de 35 dakika kprmeye tabi tutulup gzenek dalmlar incelenmitir (ekil 8-11).
784

ekil 8. 35 dk kpren numuneler
ekil 9. A numunelerinin gzenek dalmlar
ekil 10. B numunelerinin gzenek dalmlar
ekil 11. C numunelerinin gzenek dalmlar
785

Arimed prensibine gre yaplan younluk lmnde, artan kprtc madde miktaryla younluun azald tespit
edilmitir. Bunun sebebinin TiH2 miktarnn artmasyla gzenek miktar artm, younluk azalmtr. Alminyum
toz tane boyutu kk olduunda, daha dk younluklar elde edilmitir. SiC miktarnn artmasyla younluklar
artmtr (ekil 12).
(a)
(b)
(c)
ekil 12. Alminyum toz tane boyutuna gre Al kpklerin younluk grafikleri
(a) 0-53 m (b) 53-100 m (c) 100-200 m.
4. SONULAR
1. Alminyum toz tane boyutu arttka kpkleme azalm, younluk artmtr. Alminyum toz tane boyutunun
artmasyla younluklar birbirine yakn elde edilmitir. En dk younluk 53 um altndaki boyuta sahip alminyum
tozunda %2 TiH2 eklenmi numunede elde edilmitir. Alminyum toz tane boyutu arttka younluklarda ok az
bir artma meydana gelmitir.
2. %50 deformasyon uygulamas ile numunelerde atlak olumadan ekil deiimi salanmtr.
3. En uygun kprme sresi 35 dk olarak bulunmutur. Gzenek dalm homojene yakndr. Kre formunda elde
edilmi tek numunedir.
4. Kpklemenin fazla olduu numunelerde younluk dktr. TiH2 miktar arttka younluk azalmtr.
5. SiC ve TiH2 oran %1 olan numunelerde uygun kpkleme yaps elde edilmitir. Gzenek dalmnn en iyi
olduu numune TiH2 oran %1 olan numunedir.
KAYNAKLAR
1. Seitzberger, M., Rammerstorger, F.G., Degischer, H.P., Crushing of axially compressed steel tubes filled with
aluminium foam, Acta Mechanica, 125: 95-103, (1997).
2. Davies, G.J., Zhan, S., Review metallic foams, their production, properties and applications, J.Mat. Sci., 18:
1899-1911, (1983).
3. Banhart, J., Manufacturing Routes for Metallic Foams, Journals of Materials 52(12): 22-27, (2001).
4. Trker, M., Toz Metalurjisi Yntemi le Alminyum Kpk retimi, 5. Uluslararas leri Teknolojiler
Sempozyumu (IATS09), 13-15 Mays 2009, Karabk, Trkiye.
5. Yavuz ., Bapnar M. S., Bayrakeken H., Metalik Kpk Malzemelerin Tatlarda Kullanm, Tat
Teknolojileri Elektronik Dergisi (TATED), (3), 43-51, 2009.
6. Kennedy, A.R., The Effect of TiH2 Heat Treatment on Gas Release and Foaming Al-TiH2 Preforms, Scripta
Materilia, 47: 763-767, (2002).
786

SiC LAVESNN ALUMIX 231 ESASLI METALK KPN KPRME

ZELLKLERNE ETKLER
Uur GKMEN, Halil KARAKO, Hanifi NC, Mehmet TRKER
Gazi niversitesi Teknik Eitim Fakltesi, Metal Eitimi Blm, Teknikokullar 06500 Ankara,
mturker@gazi.edu.tr;
Gazi niversitesi Teknik Eitim Fakltesi, Metal Eitimi Blm, Teknikokullar 06500 Ankara,
ugurgokmen@gazi.edu.tr
ZET
Bu almada, TM yntemi ile n alaml Alumix 231 (Al-Cu %2,5-Mg %0,5Si %14 ) tozu ierisine %1 orannda
TiH2 ve farkl oranlarda (% 3-6-9-12 ) SiC tozu ilave edilerek 3 boyutlu turbula marka kartrc ile 30 dakika kartrlmtr. Karm tozlar kalp ierisinde tek ynl basn altnda preslenerek toz metal blok numuneler haline
getirilmitir. Elde edilen blok numuneler 690C scaklkta kprtme ilemine tabi tutulmutur. Kprtme ileminden
sonra elde edilen metal matrisli kompozit kpkler atmosfer ortamnda soumaya braklmtr. retilen SiC takviyeli metal matrisli kompozit kpe takviye elemann miktarnn etkisi aratrlmtr. Elde edilen SiC takviyeli metalik
kpklerin gzenek yaplar ve dalm, lineer genileme oranlar, younluu ve gzenek duvar kalnlklar incelenmitir. Yaplan alma sonucunda parack miktarnn artna bal olarak younlukta art ve lineer genilemede
azalma gzlenmitir.
Anahtar Kelimeler : Metalik Kpkler, Alumix 231, SiC
EFFECT OF THE SiC REINFORCE ADDITION ON THE FOAMABILITY

BEHAVIOUR OF ALUMIX 231 BASED METALLIC FOAM
ABSTRACT
In this study, %1 TiH2 and various amount of SiC (3, 6, 9 and 12%) particles were added into prealloyed Alumix 231
(Al-Cu 2,5%-Mg 0,5%Si 14% ) powders and mixed in a turbula for 30 minutes. Mixed powders were compacted at
unidirectional press to produce blanks. These blanks were foamed at 690C in a furnace and then cooled to room
temperature outside the furnace. Effect of reinforcing amount on the behavior of metallic foam was investigated.
Pore morphology, pore distribution, linear expansion, density and cell thickness of the SiC reinforced foam was
investigated. It was found that high amount of reinforcing element resulted in an increase in density of the foam
however, reduced the linear expansion rate.
Keywords: Metallic Foams, Alumix 231, SiC
1.GR
Metalik kpkler, zellikle alminyum ve alminyum alaml kpkler son yllar da youn olarak ilgilenilen yaplardr. Uygulama alanlar arasnda en nemli olanlar ultra hafif olmalarndan dolay tpler ierisinde ve sandvi yaplar
arasnda dolgu malzemesi olarak kullanlmalardr [1-6].
Gzenekli metal malzemelerin yapsal kullanm alanlar arasnda otomotiv, demiryolu ve inaat endstrileri, uzay
aralar, gemi ve spor malzemeleri yapm ve biyomedikal uygulamalar; ilevsel kullanm alanlar arasnda ise
filtreleme ve ayrma, s dntrc, soutma sistemleri, elektrokimyasal uygulamalar, su artma, sv muhafaza
787

ve iletimi gibi uygulamalar sylenebilir [7]. Alminyum kpkler zellikle arpma olaylarnda yksek enerji snmleme zellii, yksek basma dayanm ve yksek rijitlik gibi mekanik zellikleri bir arada bulundurmas ile bilinirler
[8]. ok hafif olmalar nedeniyle zellikle uak, uzay arac ve gemiler gibi kritik yaplarn uygulamalarnda ekici
hale gelmilerdir [9]. Kpk malzemenin mekanik zelliklerini artrmak amacyla parack takviyeli kpk retimi
yaplmaktadr. Ergiyik ierisine seramik paracklarn ilave edilmesi, sv metalin viskozitesini ve kpn yzey
gerilmesini deitirmektedir.
Bu balamda ergiyik haldeki kpn kararllnn bu zelliklere bal olarak gelitirilebildii bilinmektedir [10].
Kpn kararln artrmak ve gzenek yapsn dzenlemek amacyla ierisine SiC, Al2O3 gibi eitli paracklar
katld bilinmektedir [11]. Yaplan almada, toz metalurjisi yntemiyle, n alaml Alumix 231 esasl deiik
oranlarda (% 3-6-9-12) SiC takviyeli kompozit kpk retimi gerekletirilmitir. lave edilen takviye elemann kpk
yapnn gzenek morfolojisine, lineer genilemeye ve younlua etkisi aratrlmtr. SEM yardmyla gzenek
parack yzey ilikisi incelenmitir.
2. MATERYAL VE METOT
Deneysel almalarda % 99,9 saflkta Alumix 231 (2,5 Cu, 0,5 Mg, 14 Si) tozu ierisine arlka % 3, 6, 9 ve 12
oranlarnda takviye elaman (SiC) ve % 1 TiH2 kprtc madde katlarak 30 dakika sreyle boyutlu turbola ierisinde kartrlmtr. Elde edilen karm tozlar kalp ierisinde tek ynl basn altnda souk izostatik preslenerek
numuneler elde edilmitir. Numuneler koruyucu gaz uygulanmadan frn ierisinde 550 Cde 4 saat bekletilmitir.
Daha sonra frn ierisinden alnan numuneler tamamen souma olmadan yaklak % 55 orannda deforme edilerek
690 C kprtme scaklnda yaklak 10 dakika sreyle kprtme ilemine tabi tutulmutur. Kprtlm metal
matrisli kompozit rnler frn ierisinden karlarak atmosfer ortamnda soumaya braklmtr. Kprtc madde
miktar (%1 TiH2) ve kprtme scakl (690C) sabit tutularak deiik oranlarda takviye eleman (% 3, 6, 9, 12 SiC)
ilave edilerek n alaml Alumix 231 esasl metalik kpkler retilmitir. retilen metal matrisli kompozit kpklerde
takviye elemann (SiC) miktarnn gzenek boyutuna, gzenek yapsna, younlua, lineer genileme oranlarna
etkileri aratrlm ve SEM yardmyla gzenek duvarlar zerinde bulunan takviye elemann durumu incelenmitir.
Kpk numunelerin lineer genileme oranlar aadaki eitlik ile hesaplanmtr;
Ls - Li
Lineer Genileme Oran = -----------Li
Kullanlan eitlikte Li kprtme ncesi, Ls kprtme sonras numune yksekliini gstermektedir [12].
retilen Alumix 231 esasl metal matrisli kompozit kpklerin younluk hesab Arimet prensibine gre yaplmtr
[12].
m
d=
V -V
y
s

Yukardaki eitlikte, d younluk, m arlk, Vy ya arlk, Vs ise su ierisindeki arl ifade etmektedir.

retilen metal matrisli kompozit kpklerde presleme ve deformasyon ynnde genileme gzlenmitir. ekil 1de
%1 orannda TiH2 ieren ve 690C scaklkta kprtme ilemine tabi tutulan numunelerde artan takviye elamann
(SiC) miktarna bal olarak younlukta meydana gelen deiimler gsterilmitir.
Elde edilen grafiklerde grld gibi en yksek younluk arlka %12 orannda SiC ieren numunelerde elde
edilmitir. 690C kprtme scaklnda % 1 TiH2 ieren metalik kpklerde en dk younluk deerleri ise arlka %3 orannda SiC ieren numunelerde elde edilmitir. Yap ierisinde %3 orannda takviye eleman bulunan
numuneler ile ierisinde takviye eleman bulunmayan numunelerin younluk deerlerinin bir birine yakn kt tespit edilmitir. Buna paralel olarak %3 orannda SiC ilavesinin Alumix 231 esasl kpklerde kprme ve younlukta
dikkate deer bir deiiklie neden olmad sylenebilir. %12 orannda takviye eleman ieren numunelerde ise
younluk 0,88 g/cm3 olarak elde edilmitir ve bu deer %12 orannda SiC ilave edilerek retilen metal matrisli kompozit kpklerin ortalamas alnarak belirlenmitir. Yaplan almalar ile retilen kompozit kpklerde elde edilen
en yksek younluk deeri 0,88 g/cm3 tr ve elde edilen bu deerin 1 g/cm3n altnda olmasndan dolay kpk
numunelerin suyun zerinde batmadan durabilecei sylenebilir. SiC parack takviyesi ile metal matrisli kompozit
kpn lineer genileme oranna paralel olarak younluunda meydana gelen azalma daha nce yaplan benzer
almalar [13] ile rtmektedir.
788

ekil 1. Alumix 231 ierisine ilave edilen SiC tozlarnn younlua etkisi
ekil 2de arlka %3, 6, 9, 12 oranlarnda takviye eleman ieren, kprtc madde (TiH2) miktar %1 olarak sabit
tutulan ve 690Cde kprtlen numunelerde parack takviyesindeki arta bal olarak lineer genileme orannda
meydana gelen deiimler gsterilmektedir. Kprme ilemi srasnda meydana gelen lineer genileme orannn
sadece ergiyik metalin viskozitesine bal olmayp ayn zamanda ayran kprtc madde miktarna da bal
olduu literatrde belirtilmitir [14]. ekil 2de grld zere sabit kprtme scaklnda ve kprtc madde
miktarnda artan takviye eleman miktarna bal olarak lineer genilemede bir azalma gzlenmitir. %3 parack
takviyeli numunelerde maksimum lineer genilemeye 690 C kprtme scaklnda %1 TiH2 orannda ulalmtr.
Ayn kprtme scakl ve kprtme sresinde ierisinde takviye eleman bulunmayan numuneler ile %3 orannda
takviye eleman ieren numunelerde llen lineer genileme oranlarnda yaklak deerler hesaplanmtr. En
dk lineer genileme oran arlka %12 orannda SiC ieren numunelerde hesaplanmtr. Artan takviye eleman miktarna bal olarak lineer genileme orannda bir azalma vardr fakat takviye eleman iermeyen, %3 ve
%6 oranlarnda parack takviyesi ieren numunelerde lineer genileme oranlar ksmen birbirlerine yakn deerler
olarak hesaplanmtr. Literatrde yaplan benzer almalarda farkl kprtme scaklklarnda SiC miktarndaki
arta bal olarak lineer genilemede azalma tespit edilmitir [15]. Takviye elemann miktarndaki arta paralel
olarak lineer genilemede meydana gelen azalmann sebebi gzenek duvarlarnn oluumu srasnda ergiyik metal
ierisinde var olan paracklarn drenaj etkisini artrd ve genlemeyi azaltt olarak belirtilmitir [15].
ekil 2. Alumix 231 ierisine ilave edilen SiC tozlarnn lineer genilemeye etkisi
ekil 3te 690C scaklkta kprtlm numunelerin gzenek yaplarna ait resimler gsterilmitir. 690C kprtme
scaklnda ve %1 TiH2 ilave edilerek elde edilen metal matrisli kompozit kpklerde ideale yakn gzenek dalm ve gzenek duvar kalnlna ulald sylenebilir. Takviye eleman iermeyen, arlka %3 ve %6 orannda
takviye eleman ieren numunelerde gzenek yaplar, gzenek dalmlar ve boyutlar ksmen benzerlik sergilemektedir. Gzenek morfolojisinde grlen benzer yaplar lineer genileme ve younluk lmleriyle elde edilen
deerler ile uyumaktadr. Artan takviye eleman miktarna paralel olarak gzenek duvarlarnda kalnlama gzenek
miktarnda azalma tespit edilmitir. Paracklar ksmen ergiyik metalin viskozitesini artrrken ksmen de metal/gaz
789

ara yzeyinde yzey etken maddesi olarak davranarak gzeneklerin ergiyik ierisinde hareket etmesine ve birbirleri ile birlemelerine engel olmaktadr [16, 17]. %9 - 12 takviye eleman (SiC) ve %1 kprtc madde katlarak
kprtlen numunelerde deiik oranlarda ve deiik boyutlarda gzenek elde edilmitir. Takviye eleman ilavesinin gzenek duvarlarn dzenleyici ve mekanik zellikleri iyiletirici etki yapt bilinmektedir [18]. SiC ilavesinin
gzenek duvarlarnda dayanm art meydana getirdii dnlmektedir. Dayanm artna bal olarak kprme
srasnda ayran hidrojen gaznn genlemeyi salamak zere gzenek duvarlarnda oluturduu basncn dk
geldii ve kprmeyi engelledii sylenebilir. Kullanlan kprtme scakl yapya ilave edilen takviye elemannn
ergime derecesinden daha dktr ve bu nedenle seramik paracklarn gzenek duvarlarnda hibir reaksiyona
girmeden kald dnlmektedir.
ekil 3. SiC miktarndaki arta bal olarak deien gzenek yaps

%1 TiH2 ve deiik oranlarda SiC takviye edilerek retilen Alumix 231 esasl kompozit kpklerin JEOL JSM 6060LV
marka SEM cihaznda ekilen SEM grntleri ekil 4de grlmektedir. SiC paracklar gzenek duvar ierisinde
yerlemi durumdadr. ekil 4a da SiC ieren Alumix 231 matrisli kompozit kpklerin gzenek yaps genel grnts verilmitir. ekil 4b ve c de gzenek duvar ve gzenek duvar zerinde bulunan SiC paracn grnts
incelenmitir. ekil 4c zerinde grlen 1 numaral noktadan EDX analizi yaplarak SiC parack olup olmad
netletirilmitir. EDX analiz deerleri ekil 5 de verilmitir. Elde edilen SEM grntlerine gre SiC ile Alumix 231
matris arasnda uyum olduu sylenebilir. SiC paracklar matris malzeme ierisine iyice girmi bir grnt sergilemektedir.
790

ekil 4. SiC ieren Alumix 231 matrisli kompozit kpklerin SEM grntleri
Gzenek yaps genel grnts b) Gzenek duvar c) Matris malzeme parack ara yzeyi ve
EDX analizi yzeyi
ekil 5. SiC ieren Almix 231 matrisli kompozit kpklerin EDX analiz deerleri
791

4. SONU
Yaplan deneysel almalar sonucunda homojen dalm ve ideal gzenek duvar kalnlklarnda Alumix 231 matrisli
kompozit kpk retimi iin %1 TiH2 orannda 690 C kprtme scaklnn uygun olduu sylenebilir. Deneysel
almalar sonrasnda yap ierisinde deiik oranlarda (%3,6,9,12 SiC) bulunan takviye elemannn metal matrisli
kompozit kpklerde, kprmeye ve buna paralel olarak da gzenek yaplarna nemli etkilerinin olduu tespit
edilmitir. Parack miktarndaki arta bal olarak gzenek duvarlarnda kalnlama, gzenek saysnda azalma
olduu ve rnlerin baz blgelerinde kprme olmad gzlenmitir. EDX analiz sonular ile gzenek duvarlar
zerinde bulunan SiC paracklar tespit edilmitir. SEM grntlerine ve EDX analiz sonularna baklarak matris
malzeme ve parack ara yzeyi arasnda bir uyum olduu sylenebilir.
KAYNAKLAR
1. Seitzberger, M., Rammerstorfer, F.G., Degischer, H.P,, Gradinger, R. Crushing of axially compressed steel
tubes filled with aluminium foam, Acta Mechanica:93,14, 1997.
2. Santosa, S.P., Wierzbicki, T., Hanssen, A.G., Langseth, M. Experimental and numerical studies of foam-filled
sections, International Journal of Impact Engineering ;24, 509-517, 2000.
3. Chen, W.G., Experimental and numerical study on bending collapse of aluminum foam-filled hat profiles, International Journal of Solids and Structures, ,38,7919, 2001.
4. Hanssen, A.G., Langseth, M., Hopperstad, O.S., Optimum design for energy absorption of square aluminium
columns with aluminium foam filler, International Journal of Mechanical Sciences, 43,153-158, 2001.
5. Song, H.W., Fan, Z.H., Yu, G., Wang, Q.C., Partition energy absorption of axially crushed aluminum foam-filled
hat sections, International Journal of Solids and Structures, 42, 2575 2583, 2005.
6. Crupi, V., Montanini, R., Aluminium foam sandwiches collapse modes under static and dynamic three-point
bending, International Journal of Impact Engineering, 34, 509-517, 2007.
7. Banhart, J., Aluminium foams for lighter vehicles, Int. J. Vehicle Design, 37: 114125 (2005).
8. Song, H., He, Q., Xie, J., Tobota, A., Fracture mechanisms and size effects of brittle metallic foams: In situ
compression tests inside SEM Composites Science and Technology, 68, 24412450, 2008.
9. Hua Qin, Q., Wang, T.J. An analytical solution for the large deflections of a slender sandwich beam with a metallic foam core under transverse loading by a flat punch Composite Structures :88, 509518, 2009
10. J. Banhart, Manufacturing routes for metallic foams, Journal of Material science: 52, 2227, (2000)
11. Esmaeelzadeh, E., Simci, A., Lehmhus, D., Effact of ceramic particle addition on the foaming behaviour,
cell structure and mechanical properties of P/M AlSi7 foam, Materials Sci&Engineering A, 424, 290-299,
(2006)
12. H. inici, M.Trker, TM Yntemi le retilen Alminyum Esasl Metalik Kpe deformasyon Miktarnn Etkilerinin Aratrlmas, 13. Uluslar aras Metalrji ve Malzeme Kongresi, 854-860, Trkiye, (2006).
13. Yu, S., Luo, Y., Liu, J., Effects of strain rate and SiC particle on the compressive property of SiCp/AlSi9Mg
composite foams, Materials Science and Engineering A 487, 394399, 2008.
14. L. Ma, Z. Song, Cellular structure control of aluminium foams during foaming process of aluminium melt,
Scripta Mater., 39,1523-1528, (1998)
15. Esmaeelzadeh, S., Simchi, A., Lehmhus, D., Effect of ceramic particle addition on the foaming behavior, cell
structure and mechanical properties of P/M AlSi7 foam Materials Science and Engineering A 424, 290299,
2006.
16. Prakash, G.O., Sang, H., Embury, J. D., Structure and properties of Al-Si foam, Mater. Sci. Eng., A 199:
195-203, (1995).
17. Gergely, V., Clyne, T.W., The Formgrip process: Foaming of reinforced metals by gas release in precursors,
Adv. Eng. Materials 2:4, 175-178, (2000).
18. Li,Y.C., Xiong, J.Y., Lin,J.G., Forrest,M., Hodgson, P.D., Wen, C.E., Mechancal
Propertes and Energy
Absorpton of Ceramc Partculate and Resn-Impregnaton Renforced Alumnum Foams ,Materals Forum,
31, 52-56, 2007.
792

VIBRATION DAMPING CHARACTERISTICS OF BORON COMPOSITES

H. Ibrahim UNAL*, Ozlem EROL*, O. Yunus GUMUS**, Berrak CETIN*, Turgay ERGIN***
*Gazi University, Chemistry Department, Smart Materials Research Lab., Ankara, Turkey, hiunal@gazi.edu.tr
**Nevsehir University, Chemistry Department, Nevsehir, Turkey
***Hacettepe University, Department of Automotive, Ankara, Turkey
ABSTRACT
Electrorheological (ER) fluids can be classified as smart materials due to their controllable and reversible rheological characteristics under external electric fields. Most ER fluids consist of polarizable solid powders dispersed in
insulating non-polar liquids. Recently, conducting polymers have gained interest in boron derivative containing
conducting composites. Conducting polymer/boron derivative composites can be fabricated with controlled levels
of conductivity and enhanced anti-sedimentation stability.
In this study, vibration damping characteristics of borax and polyindene/colemanite composites were investigated.
After characterizing these materials by various techniques, volume fraction series of dispersions were prepared in
silicone oil (SO). Anti-sedimentation stabilities of these suspensions were determined. Flow rate measurements
of these dispersions were measured at various electric field values; flow times and threshold energies were determined. Finally, vibration damping capacities of the materials were tested under external electric field, using an
automobile shock absorber and were calculated as 68% and 27% for borax/SO and polyindene/colemanite/SO
systems, respectively.
Keywords: Conducting Polymer Composite, Electrorheological Fluids, Borax, Colemanite, Vibration Damping,
Shock Absorber.
1. INTRODUCTION
Electrorheological (ER) fluids are colloidal dispersions that commonly compose of polarizable powders dispersed in
non-conducting liquids. ER fluids exhibit reversible changes (liquid-like to solid like and vice-versa) in their rheological properties as a function of the electric field strength (E). In the presence of sufficient electric field strength, the
dispersed particles are polarized and aligned in the field direction to form a solid-like network of fibrillar structures
and these structures cause to observe changes in rheological properties of dispersion.
The solid powder comprises inorganic non-metallic, organic or polymeric semi-conductive materials [1]. Borax
(Na2B4O7.5H2O) and colemanite (2CaO.3B2O3.5H2O) are important boron containing commercial borate minerals
and can be candidates for being ER material. Also, preparing their composites with conducting polymer is another
option since the interactions between organic and inorganic component of composite materials could enhance the
desired properties. Because of the rapid and reversible changes in their rheological properties with the external
applied E, ER fluids have been widely investigated for the purpose of various industrial applications such as shock
absorbers, engine mounts, clutch/brakes and vibration dampers. ER shock absorbers are characterized by a valve
containing a pair of electrodes between which the ER fluid flows [2].
The aim of this study was to investigate the vibration damping capacities of borax/SO and polyindene/colemanite
composite/SO dispersion systems. Thus, borax was kindly ground milled and polyindene was polymerized in the
presence of colemanite. The materials were dispersed in SO. Anti-sedimentation ratios of the dispersions were
determined under constant temperature. Flow rates and threshold energies of the materials were investigated
under various E. The effects of surfactant and polar additives on vibration damping capacities of the polyindene/
colemanite/SO were also examined. Results implied that all the systems perceive the applied electric field and try
to act as a vibration damper.
793

2. EXPERIMENTAL
Borax and colemanite were kindly supplied by ETI Mining Co. (Turkey) and were ground milled. All the other chemicals were Aldrich products and used as received. Indene was used after distillation.
Polyindene (PIn) was in-situ polymerized in the presence of colemanite using FeCl3 as oxidizing agent taking the
monomer to initiator ratio as 2:1 in CHCl3. The prepared PIn/colemanite was ground-milled and subjected to particle
size measurement using a Malvern Nano-ZS particle size analyzer. The obtained PIn/colemanite was subjected to
various characterization techniques, namely: FTIR, particle size, density, conductivity, TGA, XRD and SEM.
All the materials were subjected to solid pellet preparation (cylindrical in shape). Further, the apparent densities and
conductivities (by a four probe technique) of the materials were measured.
Dispersions of borax, colemanite and PIn/colemanite composite were prepared in SO at a series of volume fractions
( = 525%) and the anti-sedimentation stability of the dispersion systems were measured (T = 250.1C).
The non-ionic surfactant examined was Triton-X (t-octylphenoxypolyethoxyethanol) and the concentration of TritonX in the colemanite and PIn/colemanite dispersions was 5 wt.%. To prepare the dispersions containing Triton-X,
firstly, SO and surfactant were homogeneously mixed by using an ultrasonicator and then the materials, (colemanite
and PIn/colemanite), were added and mixed again, with the volume fraction of 25%. These surfactant containing
dispersions were coded as T-colemanite and T-PIn/colemanite. To enhance the ER activity of colemanite/SO and
PIn/colemanite/SO dispersions, glycerol was added as 10 L/mL and the resultant dispersions were coded as Gcolemanite and G-PIn/colemanite. All the prepared dispersions were allowed to equilibrate for overnight before ER
and vibration damping measurements. Flow rate measurements were carried out between two brass electrodes,
which were connected to a high-voltage dc power supply. Oscillatory tests were carried out by a Termo-Haake
RS600 parallel plate torque electrorheometer.
Vibration damping experiments were carried out on an automobile shock absorber for Borax/SO ( =15%), under
E = 0-0.3 kV/mm conditions on Therpa Hydraulic vibration damping test device. The hydraulic vibration test equipment contained a wheel (with a spring coefficient of 65400 N/m), an axle, a spring (with a coefficient of 13000 N/m),
a shock absorber, an electrically operated drum to turn the wheel, a vibrating mass (60 kg), a non-vibrating mass
(14 kg), control units and an external electric field generator (Fug Electronics). During the experiments, vibrations
occurring on the body and on the axle were recorded by a recorder, which was operated at 400 V and 16 A.
250 mL of colemanite/SO, G-colemanite/SO, T-PIn/colemanite/SO and PIn/colemanite/SO dispersion systems were
used with = 10% under the external electric field strength sweep of E = 0-170 V/mm and the experiments were
carried out using Roehrig 20VS model shock absorber test equipment. During the experiments, a modified automobile shock absorber was placed to the vibration test device and a dc external electric field generator was connected
to the inner and outer tubes of the shock absorber. The test parameters were set up using the Shock 6.3 shock
absorber test program as following: Amplitude: 25.12 mm, test temperature: 25C, maximum test speed: 0.1 ms-1,
frequency: 0.63 Hz, type of the input wave: sinusoidal.
The FTIR spectra proofed that the PIn/colemanite composite was successfully synthesized. SEM image of PIn/
colemanite composite reveals that porous structures of colemanite particles were homogeneously surrounded by
close packed PIn chains, which supports the successful PIn/colemanite composite formation. The XRD pattern of
PIn/colemanite composite showed sharp peaks at 2 = 15, 22 and 28 which indicates that colemanite was in the
composite structure. The thermal stability of PIn/colemanite composite was observed to be higher than the thermal
stabilities of colemanite and PIn [3].
The average particle size, apparent density, conductivity and anti-sedimentation ratios of the materials are given in
Table 1. The conductivity values were decided to be in a suitable range for ER measurements.
Table 1. Same physical properties of the samples.
Sample
Average particle
size (m)
Apparent
Conductivity
density (gcm-3) (Scm-1)x104
Anti-sedimentation ratios (%, at

the end of 25 days, = 25%)
Borax [4]
Colemanite
PIn/colemanite
6.35
1.2
2.2
1.51
1.69
1.02
67
73
93
1.3
3.14
2.48
794

Colloidal stability of the ER fluids against sedimentation is one of the important factors from industrial and application
points of view. The ER fluids are supposed to be homogeneously dispersed before applying external electric field
strength, and so that the stable fibrillar structures are formed under E between the upper and lower electrodes. At
the end of 25 days of observation, 93% of PIn/colemanite composite particles were determined to remain unsettled.
PIn/colemanite/SO dispersion system was significantly stable against gravitational sedimentation than colemanite/
SO and borax/SO systems. It can be concluded that in composite structure PIn chains surrounded the colemanite
particles and formed steric hindrance that holds the particles in suspended positions against agglomeration.
To observe the effect of dc electric field on the ER activity, flow rate measurements were carried out on all the
dispersions. For this purpose, dispersions were prepared at a series of particle volume fractions ( = 525%) in
SO and flow times were measured under E 0 kV/mm and E = 0 kV/mm conditions. During the flow time measurements, it was observed that electric field response time decreases with increasing volume fractions as a result of
formation of fibrillar chain-like structures between the electrodes. On the other hand, a significant fibrillar structures
between the electrodes was not observed for PIn/colemanite/SO system.
The external frequency (f) is an important factor for characterizing the dynamic viscoelastic properties of ER fluids
in vibration damping processes. Stress sweep was first carried out to determine the proper stress value to measure
the storage modulus (G) in the linear viscoelastic regime. Figure 1 shows G as a function of frequency for borax/SO
( = 20%, E = 2 kV/mm), colemanite/SO, T-colemanite/SO, PIn/colemanite/SO and T-PIn/colemanite/SO dispersion
systems ( = 25%, E = 1.5 kV/mm).
Figure 1. Change in storage modulus with frequency for all the dispersions.
It was observed that Borax/SO system showed the highest G values and G values of all dispersions except PIn/
colemanite/SO were showed slight increments in the whole frequency sweep range and owing to not providing fully
elastic solid-like structure in the dispersions, but they showed viscoelastic behavior. However, G values of PIn/colemanite/SO increased notably with increasing frequency. This suggests that fibrillar structure between the electrodes
could not occur for PIn/colemanite [5].
Figure 2. Change in damping forces with piston velocity of shock absorber.

Sample: T-PIn/colemanite/SO, = 10%.
Figure 2 represents the damping forces (Fdamping) as a function of piston velocity of the modified automobile shock
absorber for just T-PIn/colemanite/SO system under the constant conditions of T = 25C, = 10% and E = 0-170
V/mm. As the electric field increased, Fdamping of the ER damper, filled with T-PIn/colemanite/SO, also increased
thereby requiring more force to move the piston. This was mainly attributed to the increment of the shear stress of
the ER fluid with increasing applied E. The percentage increment of vibration damping of the samples was determined from the following equation:
795

(1)
Vibration damping (%) of the materials calculated to change in the following order: T-PIn-colemanite (30%)>G-colemanite (28%)>PIn-colemanite (27%)>Colemanite (14%). The addition of Triton-X or glycerol caused to increase in
the percentage of vibration damping of PIn/colemanite/SO and colemanite/SO. It was concluded that the presence
of surfactant/promoter improved the performance of ER fluid.
For Borax/SO system ( = 15%), positive body vibration amplitudes (recorded in the course of opening of the shock
absorber) were observed to be bigger than the negative body vibration amplitudes (recorded in the course of closing
of the shock absorber). Results showed that the amplitudes of body and axle, which are 10.2 and 12.6 mm, respectively, under non-electric field were reduced to 3.2 and 8.7 mm, respectively, by applying E = 300 V/mm external
electric field. Thus, the vibration damping values were calculated as 68% on the body and 31% on the axle. These
reductions on the amplitudes indicate that borax/SO system is able to perceive applied electric field strength and
significantly increase the vibration damping capacity of the automobile shock absorber [6].
ACKNOWLEDGEMENTS
The authors thank to Turkish Scientific and Technological Research Council for the financial support of this work
(Project no: 107 T 711).
REFERENCES
1. Hao, T., Electrorheological suspensions, Advances in Colloid and Interface Science, Vol. 97, pp. 1-35,
2002.
2. Wereley, N.M., Nondimensional HerschelBulkley Analysis of Magnetorheological and Electrorheological
Dampers, Journal of Intelligent Material Systems and Structures, Vol. 19, pp. 257-268, 2008.
3. Cetin, B., Unal, H.I., Erol, O., Synthesis, Characterization and Electrokinetic Properties of Polyindene/
Colemanite Conducting Composite, Clay and Clay Minerals, submitted, 2011.
4. Gumus, O.Y., Unal, H.I., Erol, O., Sari, B., Synthesis, Characterization, and Colloidal Properties of
Polythiophene/Borax Conducting Composite, Polymer Composites, Vol. 32, pp. 418-426, 2011.
5. Ramos-Tejada, M.M., Espin M.J., Perea, R., Delgado, A.V., Electrorheology of suspensions of elongated
goethite particles, Journal of Non-Newtonian Fluid Mechanics, Vol. 159. pp. 34-40, 2009.
6. Gumus, O.Y., Erol, O., Unal, H.I., Polythiophene/Borax Conducting Composite II: Electrorheology and
Industrial Applications, Polymer Composites, Vol. 32, pp. 756-765, 2011.
796

TM YNTEMYLE AlSiMg ALAIMI METALK KPK RETM N

GELTRLEN PREFORM MALZEME RETM SRECNN
KAREKTERZASYONU
Ersin BAHEC*, Yusuf ZATALBA** ve Mehmet TRKER**
* Kastamonu niv., Cide Rfat Ilgaz M.Y.O, 37600, ebahceci@kastamonu.edu.tr
** Gazi niversitesi, Teknoloji Fakltesi, Metalurji ve Malzeme Mhendislii, 06500, Ankara,
yusufoz@gazi.edu.tr, mturker@gazi.edu.tr
ZET
Bu almada, toz metalurjisi yntemiyle AlSiMg alam kapal hcreli metalik kpk imalatnda kullanlan preform
(nc) malzeme retimi ve retim srecindeki ilemlerin mikroyapya etkileri aratrlmtr. Arlka %8 Si, %0,8
Mg, %0,8 TiH2 ve kalan Al tozlar olmak zere Turbola cihaz ile 45 dakika sreyle kartrlmtr. Karm tozlar oda
scaklnda preslenmi, sinterlemi ve ardndan scak ekstrzyon ilemi uygulanmtr. Ekstrze numuneler %20,
%30, %40 ve %50 oranlarnda scak/lk haddelenerek levha numuneler retilmitir. retim srecindeki her bir ilem
sonrasnda numunelerin mikroyaplar optik ve taramal elektron mikroskop vastasyla incelenmitir. Her bir sl ve
deformasyon ilemleri sonrasnda retilen preform younluunda art gzlenmitir. Sinterleme sonras matristeki
Si dalmnn homojen olduu ancak ekstrzyon sonunda deformasyon dorultusunda Si partikllerinde ynlenme
olduu ve haddeleme sonras bu etkinin artt belirlenmitir. Ayrca, deformasyon ilemlerinin TiH2 n homojen
dalmna etkisi olmazken, Mg partikllerinin deformasyon etkisi ile kmeletii belirlenmitir.
Anahtar kelimeler: Metalik Kpk, Preform (nc) malzeme, Al Alam, Mikroyap
THE CHARACTERIZATION OF PRODUCTION PROCESS OF

PREFORMS DEVELOPED FOR THE PRODUCTION OF AlSiMg ALLOY
METALLIC FOAMS BY PM ROUTE
ABSTRACT
In this study, production of precursor material for the production of AlSiMg alloyed closed cell metallic foam by PM
techniques and the effect of production route on the properties of microstructure was investigated. Al, 8% Si, 0.8%
Mg and 0.8% TiH2 powders were mixed in a three dimensional turbula for 45 min. Mixed powders were compacted
at room temperature and sintered before hot extrusion. In order to produce sheet materials samples were hot/warm
rolled by the reduction rates of 20% to 50%. Microstructures after every production stages were investigated by
using optical and electron microscopes. A density increase has been observed after all heat treatment and deformation stages. The distribution of Si particles was found to be homogeneous after sintering whereas they exhibited
orientation towards the deformation direction after extrusion which was more severe with rolling. The rate of deformation did not affect the distribution of TiH2 whereas which result in the agglomeration of Mg particles.
Keywords: Metallic Foam, Al Alloy, Preform, Microstructure
1. GR
Kpk malzemeler retim yntemleri asndan farkllklar gstermektedir. retim ilemlerine gre kat, sv ve gaz
veya iyonize olarak snflandrlmaktadr. Sv retim yntemlerinde sv metal ierisine gaz enjektesi ile gerekle-
797

tirilmektedir. Gaz veya iyonize retim yntemlerinde elektro-biriktirme veya metal buhar biriktirme ile ok gzenekli
metalik yaplar elde edilir. Kat hal retim yntemlerinde ise tozlarn kprtc madde tozlar ile kartrlarak, sinterlenmesi ve ekstrzyon ilemi ile yar mamul elde edilir [1].
Toz Metalurjisi (TM) yntemi metal kpklerin retimi iin en yaygn kullanlan yntemlerden biridir. Bu yntem
homojen bir yap elde etmek iin gelitirilen bir yntemdir [2,3] ve bu alanda youn almalara devam edilmektedir
[2,4]. Kapal gzenekli kpk retimi yllardr TM yntemiyle gelitirilmektedir. Bu yntemde metal tozlarnn ve kprtc malzeme tozlarnn kartrlmas ve preslenmesi ile kprebilir yar mamul (preform/nc) malzeme haline
getirme ilemine dayanr. Bu ilemlerle birlikte scak presleme, ekstrzyon, toz haddeleme, vb. metotlar ile preform
retimi gerekletirilebilir. Preform malzeme ergime scaklnn zerinde bir scakla getirilerek kprtme ilemi
gerekletirilir [5, 6].
TM yntemiyle retilen kpk malzemelerde Si ilavesi nemli bir parametreyi tekil etmektedir. Kpk hcreleri ve
hcre ekilleri e eksenli yap grntsne benzer homojen ve yakn hcre boyutlu kpkler retilebilmektedir [7].
Bunun yannda % 8 Si alamnn seilmesi kprme iin gerekli olan en uygun lineer genleme ve daha dk
younluklu kpk retebilmek iin kullanlmaktadr [8]. Otomobil paralarnn ksa srede retimi iin tozlardan
metalik kpk retimi cazip hale gelmektedir. Scak ekstrzyon ile retilen preformlar istenildii gibi ekillendirilerek
veya birletirilerek kprtlebilirler [9]. Karmak ekilli paralarn uygun ekilli preformlarn hazrlanarak kprtlebilmesine imkn vermektedir.
Bu almada TM yntemiyle AlSiMg alam kapal hcreli metalik kpk elde etmek iin retilen preform malzemenin retim srecindeki ilemleri karakterize edilmitir.
2.1. Malzeme ve Metot1
% 99,9 saflkta 160 m alt Al tozu ve 10 m alt Si tozlar kullanlmtr. Mg tozlar ise % 99,95 saflkta 149 m alt
boyutunda tercih edilmitir. Arlka % 8 Si, % 0,8 Mg tozlar, % 0,8 TiH2 kprtc ajan tozu ve kalan alminyum
tozu olmak zere 3 eksenli kartrma cihaznda (Turbola) 45 dakika sre ile kartrlmtr. Karm tozlar oda scaklnda preslenerek 60 mm apnda silindirik blok numuneler retilmitir. Blok numunelerin sinterlenmesi ilemi
ardndan yaklak 8:1 ekstrzyon orannda scak ekstrzyon ilemi uygulanmtr (ekil 2.1-a). Ekstrze numune
kademeli olarak scak/lk ilem scaklklarnda %20, %30, %40 ve %50 oranlarnda haddelenerek levha biimli
numuneler retilmitir (ekil 2.1-b).
( a)
(b)
ekil 2.1. a)Ekstrze edilmi ve b) Haddelenmi numuneler
2.2. Sertlik ve younluk lmleri
Malzemelerin sertlik lmleri, vickers yntemi ile Instron-Wolpert marka Diatestor 7551 model sertlik lm cihaz
kullanlarak yaplmtr. Ayn numune iin 10 deiik noktadan llen sertlik deerlerinin ortalamas alnmtr.
Younluk lmleri Arimet yntemiyle llmtr. retilen numunelerin younluklar, havadaki arlklar, daras
alnm sudaki arlklar ile blnerek hesaplanmtr. llen younluk deerleri () ile retilen numunelerin teorik
younluunun (teorik) oranlanmasyla ((/teorik) x 100) yzde younluk deerleri bulunmutur.
1
alma konusunun ticari deeri sebebiyle scaklk, sre, basn vb. baz parametrelerin deerleri bildiri metninde belirtilmemitir.
798

teorik = %A x A + %B x B + %C x C + ..+ %N x N =
100
g/cm3
(1)
2.3. Mikroyap analizleri

Mikroyap grntlenmesinde Leica DFC 320 dijital kamera balantl Leica DM 4000 M marka optik mikroskop
kullanlmtr. Numunelerin retim aamalarnda mikro yaplar incelenmitir. Preslenmi blok numune, sinterleme
sonras, ekstrzyon sonras ve haddelemedeki deformasyon oranlarna (%20, %30, %40 ve %50) gre numunelerin mikroyaplar belirlenmitir. (ekil 3.2). Mikroyap karekterizasyonu ve grnt almlar Jeol JSM-6060 LV
marka TEM (Tarama Elektron Mikroskobu) ile salanm, elementsel mikro analizler EDS/XRF sistemi ile gerekletirilmitir.

3.1. Preform Malzeme Mikroyaps
ekil 3.1de Ekstrze edilmi AlSiMg nkarml malzemenin TEM grnts ve XRF analiz sonular verilmitir.
Ana TEM fotorafnda 1 numara ile XRF kodlamas yaplan ak gri renkli paracn arlka %78 orannda Ti
ierdii ve bu paracklarn TiH2 paracklar olduu belirlenmitir. Kmelemi blgenin byltlm fotorafnda
verilen 3 nolu koyu gri renkli paracklar ise Si paracklardr. Kmelemi blge iinde tanmlanan bir alann ise
youn olarak Mg ierdii grlmektedir.
ekil 3.1. a) Ekstrze numune SEM grnts ve XRF analizleri

ekil 3.2de sinterlenmi ve ekstrze edilmi numunelerin mikroyaplar grlmektedir. Sinterleme sonras mikroyapda Si ve Mg partikllerinin Al matris ierisinde genel olarak homojen dalml olduu sylenebilir (ekil 3.1a).
Ancak, Al tozlarna nazaran ince toz boyutunda olan Mg paracklarnn matris iinde homojen dalmyla birlikte
yer yer Si paracklar etrafnda kk kmeler meydana getirdii grlmektedir. Bu mikroyapda belirgin bir gzeneklilik mevcut deildir. Scak ekstrzyon ilemi sonras mikroyapya bakldnda Si partiklleri ve Mg kmelerinin
ekstrzyon dorultusunda ynlendii belirlenmitir.
799

ekil 3.2. a) Sinterlenmi numune, b) Ekstrze edilmi numune mikroyaps.

ekil 3.3de haddeleme sonras mikroyap resimleri grlmektedir. Ekstrzyon sonras haddeleme miktar artka
hadde ynnde Si partikllerinin ve Mg kmelemesinin de artt belirlenmitir.
ekil 3.3. %20 ve %50 haddelenmi numunelerde Si ve Mg dalmlar

Toz metalurjisi yntemiyle retilen ve ekstrze edilen numune SEM grnts ekil 3.4te verilmitir. Beyaz renkte
grnen paracklar TiH2yi gstermektedir. Baz blgelerde Mg kmelemeleri mevcuttur. Genel olarak Mg, Al
matris yap ierisinde ok kk boyutlu taneler eklinde yayld grlmektedir (Siyah renkte). Yaylma ile Mg
ilavesinin sinter kalitesi arttrma eilimi bu numunelerde de grlmtr [10]. Deformasyon ilemlerinin TiH2 n homojen dalmna etkisi olmad belirlenmitir. TiH2 hem Al matris hem de Mg, Si partikllerinin evresinde homojen
olarak dald gzlenmitir.
ekil 3.4. Ekstrze preform malzemede genel parack dalmlar

3.2. Sertlik ve younluk
Sinterleme sonras blok malzemelerin teorik younluu 2,679 g/cm3 olarak hesaplanm, Arimet yntemiyle llen younluk 2,60 g/cm3 ve % 97 oranndadr. Sinterlenen malzemeye uygulanan scak ekstrzyon sonras 2,65
g/cm3 ve % 99 a artmtr. Haddeleme sonras numunelerin younluklarndaki art maksimum 2,66 g/cm3 llmtr. ekil 3.5te ilem basamaklarna gre sertlik ve younluk deerlerini ieren grafik gsterilmitir. Ekstrzyon
ileminden sonra younluk oranlarnda nemli bir deiiklik gzlenmez iken ilem basamaklarnda srasyla sertlik
deerleri artt gzlenmitir. Ekstrzyon ileminden sonra yaplan scak/lk haddeleme ilemlerinde peklemenin
etkisiyle sertlikte bir miktar art tespit edilmitir. Sinterlenmi numune ile % 50 deforme numune arasnda yaklak
% 100luk sertlik art gzlenmitir.
800

ekil 3.5. lem trne gre younluk ve sertlikteki deiim grafii.

4. SONULAR
Kapal hcreli metalik kpk retmek iin toz metalurjisi yntemiyle gelitirilen Al, %8Si ve %0.8 TiH2 ieren nkarml malzemeye uygulanan sinterleme ve eitli deformasyon ilemleriyle retilen preform malzemenin sonularyla ilgili aadakiler sylenebilir;
Sinterleme sonrasnda ekstrzyon ile salanan deformasyon ilemleri sonunda younluk % 97den arttrlarak
% 99 younlua ulalmtr. Ekstrzyon sonras uygulanan scak/lk haddeleme ilemlerinin younlua nemli
bir etkisi olmad belirlenmitir.
Ekstrzyon ncesi sinterlenmi malzemede Si ve TiH2 paracklarnn genel olarak Al matris iinde homojen
dalm gsterdii, ancak Mg paracklarnn yer yer kk kmecikler oluturduu belirlenmitir.
Sinterlenmi malzemeye uygulanan 8:1 oranndaki scak ekstrzyon ilemi sonunda Si paraclarnn ekstrzyon dorultusunda youn olarak ynlendii, ayrca Mg kmlerinin ise, ksmen deformasyon etkisi gstererek
ekstrzyon dorultusuna paralel ynlendii belirlenmitir.
Ekstrze malzemelere scak/lk haddeleme ile salanan ve %50 varan deformasyon ilemlerinde ise, ekstrzyonla ynlenmi Si partiklleri ve Mg kmelerinin sklat grlmtr.
lem basamaklarnda srasyla sinter, ekstrzyon ve haddeleme ilemlerinden sonra sertlik art grlmtr.
Sinterlenmi numune ile % 50 deforme numune arasnda sinter numune sertliinin yaklak iki kat sertlik art
gzlenmitir.
KAYNAKLAR
1. John Banhart, Manufacture, Characterisation and Application of Cellular Metals and Metal Foams, Progress
in Materials Science, 46, pp. 559632, 2001.
2. John Banhart, Manufacturing Routes for Metallic Foams, Journal of the Minerals, pp. 22-27, 2000.
3. Chin-Jye Yu, Harald H. Eifert, John Banhart and Joachim Baumeister, Metal Foaming by A Powder Metallurgy Method: Production, Properties and Applications, Innovations in Materials Conference, vol:2, pp.
181188, 1998.
4. Mehmet TRKER, Toz Metalurjisi Yntemi ile Alminyum Kpk retimi, 5. Uluslararas leri Teknolojiler
Sempozyumu (IATS09), s.1-6, Karabk, 2009.
5. I. Duarte and J. Banhart, A Study of Aluminium Foam Formation Kinetics and Microstructure, Acta Materialia, 48, pp. 2349-2362, 2000.
6. By Frank Baumgrtner, Isabel Duarte and John Banhart, Industrialization of Powder Compact Foaming Process, Advanced Engineering Materials, 2, No:4, pp. 168-174, 2000.
7. Koza, E., Leonowicz, M., Wojciechowski, S. and Simancik, F., Compressive Strenght of Aluminium Foams,
Materials Letters, 58, pp. 132-135, 2003.
8. Uzun, A., Gmen, U. ve Trker, M., Toz Metalurjisi Yntemi le retilen Alminyum Esasl Metalik Kpkte
Si lavesinin Kprmeye Etkisi, 5. Uluslararas Ileri Teknolojiler Sempozyumu (IATS09), Karabk, s. 1-4,
2009.
9. M. Shiomi, S. Imagama, K. Osakada and R. Matsumoto, Fabrication of Aluminium Foams From Powder by
Hot Extrusion and Foaming, Journal of Materials Processing Technology, 210, pp. 12031208, 2010.
10. I.A. MacAskill, R.L. Hexemer Jr., I.W. Donaldson and D.P. Bishop, Effects of Magnesium, Tin and Nitrogen
On The Sintering Response of Aluminum Powder, Journal of Materials Processing Technology, 210, pp.
22522260, 2010.
801

MODELING AND
SIMULATION
www.turkishpm.org
802

MODELING OF HEAT TRANSFER PROCESSES IN POROUS STEELS

Penka ZLATEVA*,Diyan DIMITROV**, Marin STOYTCHEV***and Daniela CHAKYROVA*
* Technical University of Varna, Faculty of Shipbuilding,
Department of Heat Engineering, 9010, Varna, Bulgaria, pzlateva1@abv.bg
**
Technical University of Varna, Faculty of Shipbuilding,
Department of Mechanical Engineering, 9010, Varna, Bulgaria, dimitrov.diyan@gmail.com
***
Institute of Metal Science -BAS, 1000, Sofia, Bulgaria, m.stoytchev@ims.bas.bg
ABSTRACT
In the present article questions about heat transfer in sintered PM steels are discussed. Modeling of heat transfer in
porous media can help for optimizing sintering and secondary heat treatment processes. On a base of experimentally obtained heat properties (heat capacity, thermal conductivity) of steel samples different with different porosity
levels (6,11,20%), a numerical model of heat transfer was created. It seems that low porosity levels decreases
thermal diffusivity, but at high porosity levels deeper penetration of cooling media into the open pores increases it.
Keywords: Powder Metallurgy, Sintering, FEM-modeling
1. INTRODUCTION
Increasing demands of PM components required detailed knowledge of the capabilities of sintering technology, the
correct selection of the modes of ongoing processes in a wide variety of metal compositions. Knowledge of thermal
characteristics of PM products with different porosity is necessary to maximize the impact of the process [1-2].
Cooling of PM parts is set by temperature curve representing the relationship between the body temperature (model) and environment (furnace) and cooling time. Upon realization of this non-stationary temperature field of the body
significant amount of heat is released. This heat flux can be most accurately determined by modeling of unsteady
heat transfer from PM body to the furnace, reflecting its real geometry and heat properties [3,6].
2. EXPERIMENTAL
In present paper object of study is simulation modeling of cooling process of PM sintered bodies with different
porosity. For this purpose, microstructure images of iron besed sintered samples with different porosity level were
used. Sintering was carried out at 1120C in industrial conveyor belt furnace with isothermal holding time 30 min
and non-forced cooling to room temperature. The porosity of samples after sintering is 6, 11, 16%, based on the
metallographic analyses.
The metallographic analysis of the samples was made, using microscope Neofot-32, equipped with a digital
camera.
To form geometry of the model microstructure non-etched JPEG image is converted into black and white image.
Contours are obtained in the binary version of black and white image. The next step of modeling is to extract the geometry using the AutoCAD software. B&W image contains many small art and distortion effects that must be filtered.
Filtering of the image must be done very carefully because in this process most of details can be lost. The main idea
is to draw points on the border between binary 1 and 0 areas, which correspond to the contours of the pores.
803

The geometry of the pores is also made in AutoCAD. The boundaries are defined by different functions of curvature.
For example, the points are spent in the channels to form boundary curves pores. Extracting the coordinates of
pores and channels of receipt was done with the help of built into AutoCAD functions Fig.1.
Figure 1. Example of porous body geometry drawn.

Creating the finite elements network is limited by two factors. The number of elements should not be too large and
the size of the elements must be small enough to reflect the existing physical processes. Based on these limitations in FEM-software finite element network with approximate size of 3m was generated. Shape of finite element
rectangular tetrahedron was chosen.
3. RESULTS AND DISCUSION
Numerical model is built under the following conditions: Heat is given by the radiation of heat from the plate type
body, to the furnace environment. The body is heterogeneous and consists of a metal matrix and pores.
3.1 Mathematical models of transient analysis temperature flow in the plate
Transient heat transfer in plate body can be described by heat transfer equation (1) and conditions of unity to solve
it, adequate to the real thermal behavior of the body in cooling mode.

(1)
3.2 Geometry of the model

Because of the thermal and geometric symmetry, geometric model is presented in the following way. Separate a
small amount of microstructure picture after treatment in the above software is presented as a plate with the following characteristics:
- Model 1 6% porosity has dimensions of 0.552 x 0.414 x 0,001 mm;
- Model 2 11% porosity has dimensions of 0.594 x 0.446 x 0,001 mm;
- Model 3 20% porosity has dimensions of 0.571 x 0.429 x 0,001 mm.
3.3. Initial and boundary conditions
The temperature in the plate at the end of sintering process (1120C) is taken as a starting temperature of the cooling process. Initial uniform temperature distribution of 1120C was set. To all outside faces radiation with a degree
of emissivity = 0.97 was set. Radiant energy exchange between neighboring surfaces of a region or between a
region and its surroundings can produce large effects in the overall heat transfer problem. Though the radiation
effects generally enter the heat transfer problem only through the boundary conditions, the coupling is especially
strong due to nonlinear dependence of radiation on surface temperature.
Extending the Stefan-Boltzmann Law for a system of N enclosures, the energy balance for each surface in the
enclosure for a gray diffuse body is given by Siegal and Howell [5], which relates the energy losses to the surface
temperatures:
804

(2)
For a system of two surfaces radiating to each other, Equation2 can be simplified to give the heat transfer rate
between surfaces i and j as see Chapman:
(3)
where:
If Aj is much greater than Ai, Equation3 reduces to:

(4)
where:
(5)
3.4. Physical conditions

After check [3] of the thermal properties of materials for metal matrix (Fe-0.3%C) and the pores (nitrogen) are
composed the following relations: C = C (T) and K = K (T) Table 1. These dependencies are used in solving equation (1).
Table 1. Thermal properties.
3.5. Post processing results

The formulated mathematical model is solved, using Ansys 13 FEM-software. The duration of cooling is discretisated in equal (1s) time steps.
The results of simulation studies for model 1,2 and 3 are shown on Figure 2,3 and 4. Figures shows the distribution
of thermal field in the metal parts and pores in a model.
From Fig. 2 can be seen that for a time 0,3477s, plate size of around 500m is cooled to aproximatelly 89,145C.
Cooling curve is shown in the bottom of the figure.
From Fig. 3 can be seen that for a time 0,3477 s, plate with 11% porosity (mostly elongated pores) size of around
500m is cooled to aproximatelly the same temperatue as a 6% porosity sample 89,088C. Cooling curve is
shown in the bottom of the figure.
805

Figure 2.Temperature field distribution in 6% pores model. Bottom cooling curve

From Fig. 4 can be seen that for a time 0,3477s, plate with 20% porosity and size of around 500m is cooled to
aproximatelly 84,895C. Cooling curve is shown in the bottom of the figure.
The analysis of results Fig.2,3,4 shows that at the same time and temperature, simulations show varying degrees of
cooling, due to the different percentage of pores. As a rule thermal difusivity have to decrease with porosity increasing [3]. It is interestinng to mention that at higher porosity level (20%) faster cooling speed (lower
806

thermal diffusivity) was registred. The presence of open high percent open pores is a key factor here [4,7] since
cooling media can penetrate in open pores.
4. CONCLUDING REMARK
The proposed in this paper simulation model of the cooling of metal matrix and pores can be used in the design and
verification tasks associated with the cooling process of PM products in belt furnaces.
5. NOMENCLATURE
C specific heat capacity, J/(kg.K)
K - thermal conductivity, W/(m.K)
density, kg/m3
N = number of radiating surfaces
ji = Kronecker delta
i = effective emissivity (input on EMIS or MP command) of surface i
Fji = radiation view factors
Ai = area of surface i
Qi = energy loss of surface i
= Stefan-Boltzmann constant (input on STEF or R command)
Ti, Tj = absolute temperature at surface i and j, respectively
REFERENCES
2. German, R.M. Sintering Theory and Practice, Willie&Sons, NY, 1996
3. Rusev D.and etc, Heat Transfer, TU Varna, 2002
4. Bocchini G. F., A. Baggioli, B. Rivolta, G. Silva, P. Piccardo, E. Poggio, Influence Of Density And Surface/Vol-
ume Ratio On The Cooling Rate Of Sinter-Hardening Materials, Powder Metallurgy Progress, Vol.4 (2004),
No 2
5. Sundelf Erik: Modelling of Reactive Gas Transport, ISBN 91-7283-511-7 TRITA-NA-0309 Licentiate Thesis, Universitetsservice US AB, Stockholm 2003
6. Ansys Modeling and Meshing Guide Ansys Release 13.0
807

GAZ ATOMZASYONU NOZULUNUN HESAPLAMALI AKIKANLAR

DNAM (CFD) LE NMERK MODELLENMES
Mustafa GLEEN*, Rahmi NAL** ve zer AYDIN**
*
Eskiehir Osmangazi niversitesi, Mhendislik ve Mimarlk Fakltesi, Makine Mhendislii Blm,

26030, Eskiehir, mgulesen@ogu.edu.tr
**
Dumlupnar niversitesi, Mhendislik Fakltesi, Makine Mhendislii Blm, 43020, Ktahya,
runal@dpu.edu.tr, ozaydin@dpu.edu.tr
ZET
Bu almada, yakndan elemeli spersonik gaz atomizasyonu nozulu CFD simlasyonu kullanlarak Reynold
Stress Modeli ile modellenmitir. Nozulun k blgesindeki gazn davran ve metal ak borusu ucundaki etkisi
incelenmitir. zellikle metal ak borusu ucunda meydana gelen u basn deerlerini belirlemek amacyla CFD
simlasyon modelinin sonular ile deneysel sonular kyaslanmtr. CFD zmnde elde edilen gaz atomizasyonu nozulunun metal ak borusu u basn deerleri deneysel veriler ile olduka yakn bulunmutur. Ortalama
%3-5 daha byk deerler elde edilmi ve gaz basncna gre deiim erisi benzer bir davran gstermitir. Bu
sonulara gre Reynold Stress model olduka baarl bir zm ortaya koymutur.
Anahtar Kelimeler: Gaz atomizasyonu, CFD, gaz ak blgesi
NUMERICAL MODELING OF THE GAS ATOMIZATION NOZZLE BY CFD

ABSTRACT
In this study, close coupled gas atomisation nozzle was modelled by CFD using Reynold Stress Modell. Gas behaviour at the nozzle exit and effect of the gas on the melt delivery tube tip were investigated. The pressure observed
at the melt delivery tube was especially compared with the experimental melt tip pressure data. The difference
between the CFD solution and experimental data was found to be very small. About %3-5 higher tip pressure value
is observed at the CFD solution. The deviation between the numeric solution and experimental data is similar in
shape. This results show that the Reynold Stress model offer very good results for the gas atomisation nozzle.
Keywords: Gas atomization, CFD, gas flow field.
1.GR
nce metal ve alam tozu retiminde kullanlan etkili yntem yksek basnl gaz atomizasyon yntemidir. Yakndan
elemeli nozulun kullanld sv metalin gaz atomizasyonunda retilen metal tozunun homojen ve kresel olmas,
dier toz retim teknikleri ile elde edilememektedir. Bu yntem ince metal tozu retiminde, iyi ak karakteristii ve
paketleme zellii gereken uygulamalarda kullanlr. Kimyasal tekniklerle retilemeyen alam tozlar gaz atomizasyon yntemi ile kolayca retilir.
Gaz atomizasyon ynteminde ama yksek hzda genleen gazn kinetik enerjisini sv metale aktararak metali kk damlacklara ayrmaktr. Dzenli ve yksek verimli bir atomizasyon ileminin gereklemesi gaz kinetik
808

enerjisinin yksek olmas ve metal ak borusu ucunda negatif basn oluumu ile salanr. Gaz atomizasyonu
ileminde, atomizasyon gaz basnc partikl boyutu ve yzey morfolojisini belirlemede nemli bir rol oynar. Aksoy
ve ark. yaptklar almada azot gaz ile atomize edilmi kalay tozunun toz boyutu ve morfolojisi zerine knt
mesafesinin ve gaz basncnn etkisini incelemilerdir [1-4]. Artan atomizasyon gaz basnc ile ortalama toz boyut
dalmn azaldn bulmulardr. Toz karakteristiinin belirlenmesinde atomizasyon gaz basncnn fiziksel etkisini
birka aratrmac grup anlamak iin almlardr [5-10]. Ting ve ark. HPGA (yksek basnl gaz atomizasyon)
nozulda atomizasyon gaz basnc deiimi ile open wake ve closed wake durumunu aratrmtr [5]. Mi ve ark.
Hesaplamal akkanlar dinamii yazlm PHOENICS kullanm ile HPGA (yksek basnl gaz atomizasyon) gaz
ak blgesinde metal ak borusu mesafesinin ve atomizasyon gaz basncnn etkisini simle etmilerdir [6-7]. Zeoli
ve ark. sv metale maximum kinetik enerji transfer edildii ve ok dalgalarnn azaltld bir izentropik meme nozul
(IPN) tasarlamtr. IPN nin performans gaz ak dinamiini, damlack paralanma mekanizmasn ve parack
boyutunu ieren nmerik bir model kullanlarak zmlemitir. Bu modeli oluturulmasnda CFD yazlm olan FLUENT kullanmlar. Trblans model olarak Reynolds-stress modeli kullanlm. Nedeni olarak da bu modelin akta
hzl deiimlerin olmas ramen ak yakalamadaki stnl neden ile tercih etmitir [8]. Allimant ve ark. De
laval nozul ile sv metalin gaz atomizasyon yntemi ile ilenmesi balkl makalesinde De laval nozul iin gaz ak
blgesinde basn ve ergiyik debi etkisini incelemitir. Sv metal atomizasyonunda De laval nozul kullanlarak
hem deneysel hemde modelsel yaklamlar allmtr. Bu iki yaklam ile atomizasyon basncna etkisi ve toz
boyutuna etkileri karlatrmtr [9]. Deneysel olarak gzlemlenen eilimler yalnz gaz ak zerinde CFD modelleme almas ile aklanabilir olduunu tespit etmitir [10]. Bunun iin atomizasyon modeli oluturulmasnda CFD
yazlm olan FLUENT kullanarak yapmlardr. deal gaz olarak argon, trblans model olarakta k- trblans
modeli kullanmtr. Hesaplamann yaknsamasn giren ve kan debi arasndaki fark tarafndan deerlendirmitir.
Basn artmas gaz hznda bir arta yol atn, bunun ergiyii daha iyi keserek paralayp ve bylece daha ince
toz retildiini belirlemitir [9].
Bu almada, yakndan elemeli spersonik gaz atomizasyonu nozulu CFD simlasyonu kullanlarak Reynold
Stress Modeli ile modellenmitir. Nozulun k blgesindeki gazn davran ve metal ak borusu ucundaki etkisi
incelenmitir. zellikle metal ak borusu ucunda meydana gelen u basn deerlerini belirlemek amacyla iki farkl
CFD simlasyon modelinin sonular ile deneysel sonular kyaslanmtr.
2. MODELLER VE SAYISAL FORMLASYONU
CFD yazlmnn paket program FLUENT 6.3 kullanlarak atomizasyon nozulunun gaz ak simle edilmi ve
atomizasyon gaz basncnn etkileri zerine modelleme almas yaplmtr. FLUENT 6.3 program seilen denklemlerin zmnde sonlu hacim yaklamn kullanr. CFD gibi byle nmerik modelleme teknikleri ak ve s
transferi problemlerini simule etmek iin gl bir aratr. Ktlenin korunumu veya sreklilik denklemi, momentumun
korunumu veya NavierStokes transport denklemi ve enerjinin korunumu denklemi nmerik olarak zlebilir. ki
boyutlu eksenel simetrik geometriler iin sreklilik denklemi; [17]
(1)
Burada gaz younluu, x eksenel koordinat, r radyal koordinat, vx eksenel hz, and vr radyal hzdr. Sm kaynak
terimi ise ayrlm ikinci fazdan (sv damlacklarnn buharlamas nedeniyle gibi) srekli faza ilave edilen ktle
ve herhangi bir kullanc tarafndan tanmlanm kaynaktr. Denklem (1) sktrlabilir ve sktrlamaz aklar iin
kullanlan ktlenin korunumu denkleminin genel formudur.
ki boyutlu eksenel simetrik geometriler iin eksenel ve radyal momentum korunum denklemleri aada verilmitir.
(2)
ve

(3)
809

Burada;
Burada p statik basn, gerilim tens, vz swirl hz,

faz ile etkileimden ykselme gibi).
(4)
ve
Reynolds stress model (RSM) gre trblans kinetik enerji

verilmitir.
srasyla yerekimi kuvveti ve d kuvvettir (ayrk

ve trblans yitim hz
denklemleri aada
(5)
ve
(6)
= 0:82,
= 1,
= 1:44,
Burada;
and
fonksiyonu olarak llm deerler ve
= 1:92,
Yerekimi vektrle alakal lokal ak ynnn bir
kaynak terimlerdir.
Sktrlabilirlik etkilerine yksek hzlardaki gaz aklarnda ve/veya byk basn deiimlerinde karlalr. Ak
hz gazn ses hzna yaklat ya da at zaman veya sistemde basn deiimi (p=p) byk olduu zaman
basnla gaz younluunun deiimi ak hz basnc ve scakl zerinde nemli bir etkiye sahiptir. Sktrlabilir
aklar iin, ideal gaz kanunu aadaki formda yazlr;
(7)
Burada pop iletme basnc (operating conditions panelinde tanmlanr), p iletme basncna gre bal lokal statik
basn, R niversal gaz sabiti, ve Mw molekler arlktr. Scaklk T enerjinin korunum denkleminden hesaplanabilecektir.
Sutherland vizkosite kanunu ideal gazlarn kinetik kuram ve idealize edilmi bir molekller aras kuvvet potansiyeline dayanmaktadr. Bu forml iki veya katmanldr. Bu almada katmanl Sutherland kanunu kullanlmtr.
katmanl Sutherland kanunu;
(8)
Burada viskozite (kg/ms), T statik scaklk (K), 0 bir referans deer (kg/ms), T0 bir referans scaklk (K), ve S
ise gazn karakteristii olan Sutherland sabiti olarak isimlendirilen bir efektif scaklk (K). Scaklk ve basncn orta
deerlerinde hava iin, 0= 1.7894x0-5 kg/ms, T0 = 273.11 K, and S = 106.67 K [18].
3. DENEYSEL YNTEM ve SAYISAL MODEL
3.1. Deneysel alma
Atomizasyon ileminin kararl bir ekilde
gerekleebilmesi iin nozul ierisine yerletirilen
sv metal ak borusu u noktasnda meydana
gelen basn nemlidir ve bu basncn bilinmesi
gerekir. Sv metalin atomizasyonu srasnda bu
basncn lm mmkn olmadndan dolay
genellikle sadece atomizasyon gaz verilerek u
basn lmleri yaplr. Bu amala kurulmu dzenek ekil 1de gsterilmitir.
ekil 1. Spersonik geometrili nozulun
ematik gsterimi ve metal ak borusu
u basncnn lm sistemi.
810

Burada metal ak borusunun st tarafna yerletirilen bir basn alglaycsndan (pressure transmitter) alnan sinyaller sinyal alc tarafndan mbar deerine evrilerek okunmaktadr. Farkl atomizasyon basnlarnda llen
deerler kaydedilerek u basn grafikleri izilmitir.
Gaz atomizasyonu ileminde ekonomiklilik nemli bir parametredir. Bu parametre retilen toz iin tketilen gazn
debisini ifade eder. Yaplan deneylerde spersonik nozul iin farkl atomizasyon basnlarndaki gaz debisi
deerleri llmtr. lmler SIEMENS marka Strans F C Massflo Mass 2100 tipi ktlesel debi lm cihaz ile
gerekletirilmitir.
Nozul 8.5 mm2 boaz alanna, 5 mm knt mesafesine ve 260 lik nozul asna sahiptir. Atomizasyon nozul sisteminin simetrik ekle sahip olduu iin hesaplama iki boyutlu eksenel simetrik olarak zlmtr.
3.2. CFD Model Oluturulmas
Atomizasyon nozul sisteminin simetrik ekle sahip olduu iin hesaplama iki boyutlu eksenel simetrik olarak
zlmtr. Model geometrisinin oluturulmasnda daha nce toz retiminde kullanlan nozulun lleri esas
alnmtr. Nozul iki boyutlu ve eksenel simetri olmak zere GAMBIT 2.4.6 programnda izilmi ve a yaps
(meshleme) oluturulmutur(ekil 2).
ki boyutlu eksenel simetrik geometrili zm, iki boyutlu ve boyutlu geometrilere gre hassasiyet asndan
bakldnda daha avantajldr. nk grid saysnn azl zaman tasarrufu salayaca gibi, alan bana den grid
miktar dierlerine gre olduka yksektir. ekil 3 de nozulun yaknsak-raksak blgesinin grid yaps ve hesaplanan
alan gsterilmitir. Nozulun u basncn lmek iin ekil 4te gsterildii gibi nozulun ucundan itibaren bir mm ara
ile satr kullanld ve her bir hat 1,5 mm uzunluundadr. Her bir hat zerine 10 adet lm noktas konulmutur.
lm noktalarndan elde edilen tm basn verilerinin ortalamas nozul u basnc olarak kabul edilmitir.
Metal ak borusunun i ap 3 mm olduundan dolay Simlasyon basn deerleri elde etmek iin hat uzunluklar
y-ekseni ynnde 1,5 mm alnmtr. Simlasyonda elde edilen basn deerlerinin doruluunu artrmak iin
basn hatt birbirinden 1 mm aralkla yerletirilmitir. Tm noktalarn basn deerlerinin ortalamas alnarak belirlenen metal ak borusu u basn deeri, deneylerde elde edilen deerler ile kyaslanmtr.
Nozulun en dar blgesi (boaz) 0.2 mm. Ak daha iyi analiz edebilmek iin nozul blgesi ince meshlenmitir.
Simlasyon balangcnda hcre says 47196 (mesh 1) olan kaba meshleme yaplm, daha sonra rafine ederek
334917 (mesh 2) mesh den bamszln kantlamak iin ayn geometriyi hcre says 1464200 (mesh 3) olan a
yaplarnda ak simle edilmitir (ekil 5).
Buradan da anlald zere mesh 2 daha ince a yapsna sahip mesh 3 den daha avantajldr. Elde edilen modelin meshden bamszln kantlam olduumuz gibi mesh 2 ile sonu daha ksa srede ve mesh 3 e benzer
deerleri elde ettii tespit edilmitir. Bu almada incelenen tm durumlar iin, gen a yaps tercih edilmitir.
811

ekil 3. Kritik blgelerdeki ve cidarlardaki mesh yaplar.
ekil 4. CFD modellemede nozul u basn deerlerini alnmasnda kullanlan hatlarn pozisyonu.
ekil 5. Farkl mesh saysna sahip CFD modellerdeki veriler ile deneysel verilerin kyaslanmas.
812

CFD simlasyonlar basnca dayal, kararl durum ayrlm tam zc kullanlarak yaplmtr. Ak trblansl,
viskoz model olarak Reynolds stres model (RSM) kullanlarak zlmtr. Model sabitleri default deerler
uygulanmtr. Programn zc tipi seiminde seilenler ise pressure based, implicit yaklam, standart duvar
fonksiyonu ve steady (kararl) zmdr. Akkan olarak azot gaz, younluk iin ideal gaz kanunu ile sktrabilir
gaz kabul edilmi ve NIST verilerine gre gaz sabitleri Tablo 1 de verilmitir [20]. NIST verilerine gre azot gaznn
sktrabilirlik faktr 11 Atmosfer basncnda ve 300 K scaklkta 0,998 dir. Bu durumda ideal gaz kanunu bu
simlasyon kullanmak makuldr. Snr artlar ekil 2de gsterilmitir. Atomizasyon basnc 1.0, 1.3, 1.7, 2.2 ve
2.7 MPa deerler CFD modelleme esnasnda gaz giri basnc olarak kullanlmtr. Gaz giriindeki scaklk 300 K
kabul edilmitir. Gaz k CFD modelde basn k olarak belirtilmi ve atmosfer basn deeri alnmtr. Tm
duvar scaklklar 300 K kabul edilmitir.
zme balama aamasnda programn kullanc kitabndan olduka yararlanlmtr. Yksek basnl almalarda
zme balamada nerilen yollarn kullanlmas nem arz etmektedir. Aksi takdirde zme ulalamamaktadr.
Bunun iin zellikle 200 iterasyonda kararl bir yaknsama salanmas iin enerji denklemleri seilmemitir. Balang
deeri iin hz deeri programn hesaplad deerden daha dk girilmitir. Ayrca rahatlatma faktrleride (under-relaxation factor) basn iin 0.4, momentum iin 0.3, younluk iin 0.3, enerji iin 0.9 seilmitir ve dierleri
default deerleri olarak ayn kalmtr. Yaknsama da kararl bir grnt salandktan sonra (200 iterasyon sonra)
enerji denklemi almtr. zm iin 1.dereceden denklemler (first order upwind) seilmitir. RSM ayrklatrma
zmnde 2. dereceden denklemler (second order upwind) altnda simlasyonun yaknsamas olduka zordur [21]
ve yaknsama kriteri olarak ise enerji denkleminin 10-6 hata oran esas alnmtr. Ayrca giri ve k arasndaki
ktlesel debiler arasndaki farknda 10-6 orannda bir farka ulamas yaknsama kriteri olarak gz nne alnmtr.
Tablo 1 Saysal zmleme iin azot gaznn zellikleri
Fiziksel zellikler
Deer
Younluk (kg/m3)
1.138
(J/(kg.K))
1040.67
Termal iletkenlik (W/(m.K))
0.0242
Referans viskosite (kg/(m.s))
1.66310-5
Referans scaklk (K)
273.11
Efektif scaklk (K)
106.67
Molekler arl (kg/(kg.mol))
28.0134
Standart hal entropisi (J/(kg.mol.K))
191494.8
Bir problemin CFD yardmyla zlmesinde seilen modellerin uygunluunun tespiti iin CFD sonularnn deneysel verilerle kyaslanmas gerekir. CFD sonularnn deneysel verilere yaknlk derecesi ve deneysel verilerle ayn
karakteristik zelliklerine sahip olup olmad incelenir. Bu almada simlasyonun doruluunu kontrol etmek iin
naln deneysel verilerinden yararlanlmtr [1, 22, 23]. Aydn ve nal yaptklar almada saysal zmlemeleri ile deneysel verilere bakldnda nozul gaz basnlar arasndaki fark tm basnlarda ayn olduu, deneysel
verilerde nozul u basnc daha az olmakla birlikte, Realizable
model sonular ile arasndaki fark %1115 arasnda deitiini tespit etmilerdir [25]. Reynolds stres model ile deneysel verileri kyaslandnda %3-11
arasnda deiirken, %11 fark sadece 1.0 MPa basn altnda elde edilmitir. 1.3, 1.7, 2.2 ve 2.7 MPa basnlarda
deneysel verilere yaknl %3-5 arasndadr (ekil 6). Bu sonuca gre Reynolds stres model basn deerleri demodele gre daha yakn sonular vermitir. Espina ve Piomelli yaptklar
neysel veriler ile kyaslandnda
almalarnda saysal zmlemeleri ile deneysel verilere genellikle %10-20 arasnda yaknlk elde etmilerdir [24].
Bu nedenle bu simlasyonlar deneysel verilerle Espina ve Piomelli tarafndan yaplan daha nceki almalardan
daha iyi rtmektedir. Bu sonu nozul u basncnn belirlenmesinde Reynolds stres modelin kullanlabileceini
gstermektedir. ekil 7de gaz ktlesel debisinin CFD simlasyonlar ve deneysel veriler ile kyaslamas verilmitir.
Deneysel veriler ile CFD sonular arasndaki fark hemen hemen sabit olup %30 civarndadr. Bu fark nozulun y-
813

zey zelliklerinden ve gerek darboaz kesit alan ile nozulun tasarmndaki darboaz kesit alan arasndaki farktan
kaynaklanm olabilir. Yine bu konuda Anderson ve Terpstra [3] yaptklar almada teorik debi ile deneysel debi
arasnda basncn artmasyla birlikte giderek artan bir fark tespit etmiler ve teorik debi deerleri ile deneysel debi
deerleri arasnda ok byk fark bulmulardr. Anderson ve Terpstra bu farkn nedenini aklayamamlardr. Bu
almada elde edilen deerler arasnda hemen hemen sabit bir farkn olmas yaplan hesaplamann deneysel veriler ile rttn gstermektedir. Ayrca CFD almasnda gaz scakl sabit tutulmutur. Deneysel almada
ak esnasndaki gaz scakl zamanla azalmaktadr. Bu durum nozula geen gazn gerek ktlesel debisini de
etkileyebilir.
ekil 6. Nozul u basncnn CFD ve deneysel veriler ile karlatrlmas.
ekil 7. Gaz ktlesel debisinin CFD ve deneysel veriler ile karlatrlmas

Nozul blgesinde Reynolds stress zmde elde edilen gaz hzlar ekil 8de verilmitir. Gaz hz maksimum
deerine (663 m/s) 2.7 MPa gaz giri basncnda, minimum deerine (631m/sn) ise 1.0 MPa gaz giri basncnda
erimektedir. Bu sonular gaz hznn basn art ile nemli lde artmadn gstermektedir. Bu nedenle verimli
bir gaz atomizasyon ilemi iin nozul geometrisinin daha nemli olduunu gstermektedir. Bir nozulda ayn ktlesel
gaz debisinde daha yksek gaz hz elde edilebilirse nozulun verimi daha yksek olacaktr. Bundan dolay bir gaz
atomizasyon nozulunun verimi ekseriyetle nozulun geometrisine bal olduu sylenebilir.
ekil 8. Reynolds stres modelin farkl basntaki hz deerleri.
814

5. SONULAR
Bu alma kapsamnda gaz atomizasyonu nozulunun Reynold Stress model ile CFD zm yaplmtr. Elde
edilen sonular deneysel veriler ile kyaslanarak modelin doruluu incelenmitir. almann sonular aada
maddeler halinde verilmitir:
CFD zmnde elde edilen gaz atomizasyonu nozulunun metal ak borusu u basn deerleri deneysel
veriler ile olduka yakn bulunmutur. Ortalama %3-5 daha byk deerler elde edilmi ve gaz basncna gre
deiim erisi benzer bir davran gstermitir. Bu sonulara gre Reynold Stress model olduka baarl bir
zm ortaya koymutur.
Gaz debisi deerleri deneysel debi deerleri ile karlatrldnda sabit olmak zere %30 fark elde edilmitir.
Boaz akl 0,2 mm olarak teorik hesaplamalar yaplmtr. Debi deerleri arasndaki farkn nedeni nozulun
imalatndaki boyutsal sapmadan ve scaklk deiimlerinden kaynaklanabilir.
Gazn ak dorultusunda bir izgi boyunca gaz hz deerleri karlatrldnda gaz basncna gre ok
nemli fark olmad grlmtr. zellikle gazn sv metal ile buluma noktas olan blgede yksek basncn
gaz hzn ok nemli oranda arttrmad, 1.7, 2.2 ve 2.7 MPa basnlarda gaz hznn birbirine olduka yakn
olduu grlmtr.
KAYNAKLAR
1. Aksoy A, nal R. Effects of gas pressure and protrusion length of melt delivery tube on powder size and powder morphology of nitrogen gas atomized tin powders Powder Metall, 49(4): 349-354, 2006.
2. Singh D D, Dangwal S. Effects of process parameters on surface morphology of metal powders produced by free fall gas
atomizationJ Mater Sci, 41(12): 3853-3860, 2006.
3. Anderson I E, Terpstra R L. Progress toward gas atomization processing with increased uniformity and control Mater
Sci Eng A, 326(1): 101-109, 2002.
4. Srivastava V C, Ojha S N. Effect of aspiration and gas-melt configuration in close coupled nozzle on powder productivity
Powder Metall, 49(3): 213-218, 2006.
5. Ting J, Peretti M W, Eisen W B. The effect of wake-closure phenomenon on gas atomization performance, Mater Sci
Eng A, 326(1): 110-121 2002.
6. Mi J, Figliola R S, Anderson I E. A numerical simulation of gas flow field effects on high pressure gas atomization due to
operating pressure variation, Mater Sci Eng A, 208(1): 20-29, 1996.
7. Mi J, Figliola R S, Anderson I E. A numerical investigation of gas flow effects on high-pressure gas atomization due to
melt tip geometry variation, Metall Mater Trans B, 28(5): 935-941
8. Zeoli N, Gu S. Computational simulation of metal droplet break-up, cooling and solidification during gas atomisation
Comp Mater Sci, 43(2): 268-278, 2008.
9. Allimant A, Planche M P, Dembinski L, et al. Progress in gas atomization of liquid metals by means of a de Laval nozzle.
Powder Technol, 190(1-2): 79-83, 2009.
10. XinMing Z., et al. Effect of atomization gas pressure variation on gas flow field in supersonic gas atomization, Sci. China
Ser E-Tech Sci, 52 (10):3046 3053, 2009.
11. Tinoco J, Widell B, Fredriksson H, Fuchs L. Modeling the in-flight events during metal spray forming Materials Science
and Engineering A ,365: 302-310, 2004.
12. Ting J, Anderson IE, A computational fluid dynamics (CFD) investigation of the wake closure phenomenon, Materials
Science and Engineering A, 379: 264-276, 2004.
13. Zeoli N, Gu S, Kamnis S. Numerical modelling of metal droplet cooling and solidification, International Journal of Heat
and Mass Transfer 51, 4121-4131 2008.
14. Zeoli N, Gu S. Numerical modelling of droplet break-up for gas atomization, Computational Materials Science, 38,
282-292, 2006.
15. Tong M, Browne DJ. Direct numerical simulation of meltgas hydrodynamic interactions during the early stage of atomization of liquid intermetallic, Journal of Materials Processing Technology , 202: 419427 2008.
16. Tong M, Browne DJ. Modelling compressible gas flow near the nozzle of a gas atomiser using a new unified model.
Computers & Fluids, 38: 11831190, 2009.
17. Fluent 6.1 Users Guide, Fluent Inc., Centerra Resource Park, 10 Cavendish Court, Lebanon, NH 03766, USA, 2003.
18. Fluent Inc., GAMBIT Users Guide, Fluent Inc., Lebanon, 2002.
19. White F.M., Fluid Mechanics, McGraw-Hill Book Co. 2nd Ed., 1988.
20. NIST Reference Fluid Thermodynamic and Transport Properties Database (REFPROP) version 7.0, National Institute of
Standards and Technology, Boulder, CO 80305-3328, USA.
21. Gimbun, J., at all, The influence of temperature and inlet velocity on cyclone pressure drop; a CFD study Chemical
Engineering and Processing 44 (2005) 7 12, 2005.
22. Unal R. The influence of the pressure formation at the tip of the melt delivery tube on tin powder size and gas/melt ratio
in gas atomization method Journal of Materials Processing Technology, 180: 291-295, 2006.
23. Unal R. Improvements to close coupled gas atomization nozzle for fine powder production Powder Metallurgy, 50(1):
66-71, 2007.
24. Espina PI, Piomelli U. Numerical simulation of the gas flow in gas-metal atomizers. Proceedings of FEDSM98, 1998
ASME Fluids Engineering, Division Summer Meeting, June 21-25, Washington, DC, USA, 1998.
25. Aydn O., Unal R., Experimental and numerical modeling of the gas atomization nozzle for gas flow behavior, Computers and Fluids, 42, 37-43, 2011.
815

POROUS
MATERIALS
www.turkishpm.org
816

GELENEKSEL TOZ METALURJS YNTEMYLE GZENEKL

TiNi ALAIMLARIN RETM VE KARAKTERZASYONU
aydogmus@yyu.edu.tr
**
*
ZET
% 21-26 arasnda gzeneklilie sahip TiNi alamlar (Ti-50.6 at. %Ni) geleneksel toz metalurjisi yntemiyle retilmitir. Sinterleme srasnda oksitlenmeyi engellemek ve koruyucu bir atmosfer oluturmak amacyla titanyum paracklar ve magnezyum tozlar kullanlmtr. retilen gzenekli TiNi numunelerin sadece stenit fazn ierdikleri,
bunun dnda istenmeyen krlgan Ti-Ni bileikleri ya da oksit gibi herhangi bir ikincil faz iermedikleri grlmtr.
Her ne kadar geleneksel sinterleme metoduyla retilen gzenekli TiNi alamlar yetersiz gzenek miktar ve kk
gzenek boyutu (uygulanan presleme basncna bal olarak, ortalama 4-65 m) nedeniyle yapay kemik uygulamalar iin uygun olmasa da gzeneklerin birbirleriyle balantl olmas nedeniyle filtre malzemesi olarak kullanlmaya
son derece uygundur.
Anahtar kelimeler: Gzenekli TiNi Alamlar, Biyomalzemeler, Mekanik zellikler, Oksitlenme, Toz Metalurjisi.
PROCESSING OF POROUS TiNi ALLOYS VIA CONVENTIONAL POWDER

METALLURGY TECHNOLOGY AND THEIR CHARACTERIZATION
ABSTRACT
Porous TiNi alloys (Ti-50.6 at. %Ni) with porosities in the range of 21-26% were produced using the conventional
powder metallurgy technique. Titanium sponge and magnesium powders were used to prevent oxidation by providing a protective atmosphere during sintering. It has been observed that porous TiNi samples produced consisted of
only single austenite phase without any secondary phase such as brittle undesired Ti-Ni intermetallics and oxides.
Although porous TiNi alloys produced by conventional sintering have not been found to be applicable for bone replacements due to their low porosity and small pore size (4-65 m on average, depending on compaction pressure),
they are appropriate for filtering applications due to their highly interconnected pore structures.
Keywords: Porous TiNi Alloys, Biomaterials, Mechanical Properties, Oxidation, Powder Metallurgy.
1. GR
TiNi alamlar sergiledikleri stn ekil bellek ve sperelastisite zellikleri ile bilinirler. Bu zellikler TiNi alamlarnn % 8e [1] varan oranlarda elastik ekil deiimlerini tamamen geri kazanmalarna imkan vermektedir. Bu srad
termoelastik davran TiNi alamlarnn endstride pek ok kullanm alan bulmasn salamtr. TiNi alamlar
gnmze kadar yaygn bir ekilde aktatr ya da tahrik dzenei, kavrama ve balant eleman, sensr, cep
telefonu anteni, gzlk erevesi, ortodontik tel ve stent imalatnda [1-3] en ok tercih edilen malzemeler olmutur.
Biyomedikal malzeme olarak kullanlmalarn sahip olduklar yksek biyo-uyumlulua borludurlar [4].
817

ekil bellek ve sperelastisite zelliklerini gzenekli halde de ksmen koruyan TiNi alamlar son 20 ylda gzenekli olarak retilmeye balanm ve yeni uygulama alanlar nerilmitir [5]. Gzenekli TiNi alamlar, iyi korozyon
direnci gstermeleri nedeniyle zellikle kimya ve polimer endstrisinde kullanlan gzenekli filtre retiminde ve iyi
derecede biyo-uyumlulua sahip olmalar ve vcut kemiinin mekanik zelliklerine benzer zellikte mekanik davran sergilemeleri nedeniyle de diilikte ve vcut kemik deiimlerinde implant malzemesi olarak kullanlabilirler.
Bugne kadar gzenekli TiNi alam retmek iin pek ok toz metalurjisi yntemi uygulanmtr. TiNi alamnn
yksek ergime scakl, 1310 C, oksijen, karbon, azot ve hidrojene olan yksek afinitesi ve pota malzemeleri ile
reaksiyona girmesi gibi nedenlerle sv halde gzenekli metal retme yntemleri pek tercih edilmemi [6], eitli toz
metalurjisi teknikleri esas retim metodu olarak benimsenmitir. Reaktif sinterleme [7-10], geleneksel sinterleme
[11-13], sabit basnta scak presleme [14,15], elektro plazma sinterleme [16], boluk oluturucu yntem [17-22] ve
toz enjeksiyon kalplama [23,24] teknikleri sklkla kullanlmtr.
Bu yntemlerde reaktif sinterleme dnda elementel titanyum ve nikel ya da alam (TiNi) tozlar kullanlabilmektedir. Her yntemin kendine zg avantaj ve dezavantajlar bulunmakla beraber gerek elementel gerekse alamlanm toz kullanlarak sz konusu yntemlerle retilen gzenekli TiNi alamlarnda grlen ortak ve en nemli sorun
istenmeyen TiNi3, Ti4Ni2O ve Ti2Ni gibi titanyumca ya da nikelce zengin ikincil fazlara rastlanlm olmasdr. Bu
fazlar TiNi yap iinde, zellikle tane snrlarnda, byk boyutlu olarak olumakta ve malzemenin krlganlamasna
sebep olarak mekanik zelliklerini olumsuz ynde etkilemektedirler.
Bunun yan sra malzemenin ekil bellek ve sperelastisite zelliklerini azaltmakta ve malzemenin korozyon direncinde de bir de neden olmaktadrlar [25,26]. Ayrca hemen hemen tm yntemlerde zellikle elementel
titanyum ve nikel toz kullanldnda reaksiyona girmeden yapda kalan saf titanyum ve nikel fazna da ska rastlanlmaktadr. Titanyum faz malzemenin mekanik zelliklerinde bir zayflamaya neden olurken, nikel faz bilinen
toksik ve alerjik zellikleri nedeniyle malzemenin biyouyumluluunu olumsuz ynde etkilemektedir [25]. TiNi dnda
oluacak tm fazlar yapnn bileimini deitireceinden kompozisyona ok duyarl olan ekil bellek ve sperelastisite davranlar da bu deiimden etkilenecektir.
Tm bunlarn yan sra oksijen, hidrojen ve azot gibi gazlarn 200 C scakln stnde TiNi alamlarndaki yksek
znrlklerinden dolay gzenekli metal retiminde eitli zorluklarla karlalmakta ve retilen gzenekli metalik
malzemelerin mekanik zelliklerinin bu elemetlerin znmelerinden olumsuz etkilendii grlmektedir. rnein,
oksijenin TiNi iinde znmesi sonucu TiO, TiO2, Ti2O3 ve Ti3O5 gibi erime scakl ok yksek oksit bileikleri
olumaktadr. Titanyumun seici oksitlenmesi sonucu aa kan nikel atomlar da TiNi3 faznn oluumuna yol
amaktadr [1].
Bu yzden TiNi alamlarnn sinterleme srasnda oksitlenmemesi iin sinterleme atmosferindeki oksijen ksm basncnn ok dk deerlere indirilmesi (rnein 1100 C sinterleme scaklnda Ellingham Diyagramna gre 5
10-25 atm) arttr [17,18]. Ayn ekilde hidrojen elementinin de TiNi alamlar iindeki znrl yksektir. Dk
scaklk ve basnlarda TiNiH1.4 oluurken daha fazla hidrojen konsantrasyonu, yksek scaklk ve basnlarda TiH2
ve TiNi3 olumaktadr.
Hidrojen miktar 1809 ppme ulatnda ekil bellek ve sperelastisite zelliinin tamamen ortadan kalkt rapor
edilmitir [27]. Benzer ekilde azotun da TiNi alamlar iinde znmesi sonucu TiN olumaktadr. Bunlarn dnda karbon da TiNi iinde znrl az da olsa titanyum atomlar ile reaksiyona girerek TiC oluturmaktadr.
Bu almada, elementel tozlarn kullanlmas durumunda varlklar kanlmaz olan istenmeyen ikincil fazlarn oluumunu, alam TiNi tozlarn koruyucu magnezyum buhar altnda sinterleyerek engellemenin mmkn olduu
gsterilmitir. Magnezyum, Ellingham diyagramnda kalsiyumun hemen zerinde yer alan, oksijen alabilirlii (afinitesi) son derece yksek olan ok iyi bir indirgeyici elementtir. Bu yzden sinterleme scaklna stma, bekleme ve
soutma aamalarnda (sv ve gaz haldeyken) TiNi alamlarnn olas oksitlenmesini tamamen engelleyebilmektedir. Buna ilaveten retilen tek fazl TiNi alamlarnn yapsal ve mekanik zellikleri ortaya konulmutur.
2. DENEYSEL YNTEM
2.1. Kullanlan tozlar
retim ynteminde daha nceki almalarmzda [6,11,17,18] detayl olarak analiz edilmi, alamlanm nikelce
zengin, stenitik, kresel TiNi tozlar (Ti-50.6 at. %Ni, % 99.9 saflkta, Nanoval GmbH & Co. KG) kullanlmtr. Gaussian (log-normal) dalm gsteren TiNi alam tozunun ortalama ap 21 m iken koruyucu atmosfer yaratmak
818

iin kullanlan kresel Mg tozunun (% 99.82 saflkta, Tangshan Weihao Magnesium Powder Co. LTD) ap ortalama
450 m olarak belirlenmitir.
2.2. retim Yntemi
TiNi tozu sktrma ncesi balayc olarak kullanlan % 5 polivinil alkol (PVA) zeltisi (% 2.5 PVA + su) ile homojen
bir karm elde etmek zere 30 dakika sreyle kartrlmtr. Elde edilen karm, souk hidrolik preste, sertletirilmi elikden yaplm basma kalplar iinde, n deneylerle belirlenmi olan 770 MPa optimum basn altnda ift
ynl olarak baslmtr.
Presleme sonras kalplardan karlan yaklak 10 mm apnda ve 12 mm yksekliindeki numuneler 1100 C
scaklkta, sngerimsi titanyum paracklarla temizlenmi koruyucu argon atmosferi altnda 1 saat sreyle sinterlenmilerdir. Sinterleme ilemi ncesi potaya TiNi kompaktn arlnn % 12si miktarnda magnezyum konulmutur.
Oda scaklndan 1100 Cye stma hz 10 C/dak olarak sabit tutulmutur. 1090 Cye ulaldnda, 650 Cde
eriyerek sv hale geen magnezyumun tamam buharlaarak pota iinde TiNi iin indirgeyici bir atmosfer oluturmaktadr. Bu sebeple argon gei hz frn ierisinde bir miktar i basn oluturmaya yetecek kadar yavalatlmtr.
Oksitlenmeye kar ek bir nlem olarak sngerimsi titanyum paracklar TiNi kompakt zerine temas etmeyecek
ekilde yerletirilmitir. Sinterleme sonrasnda pota frnn souk blgesine ekilerek yaklak 60-75 C/dak bir hzda
numunelerin oda scaklna soutulmalar salanmtr.
Younluk ve gzenek miktar Arimet yntemi kullanlarak llmtr. Gzenek boyutlar Quantachrome PoreMaster 60 cival gzenek ler cihaz kullanlarak llmtr. TiNi tozda ve retilen gzenekli TiNi alamnda
bulunan fazlar belirlemek iin Rigaku D/Max 2200/PC model X-In Difraktometresi (XRD) kullanlmtr. yap
incelemeleri Noran System 6 enerji dispersiv spektrometresine sahip Jeol JSM 6400 taramal elektron mikroskobu
(SEM) kullanlarak gerekletirilmitir.
Tek eksenli basma testleri 10X10 mmlik silindirik numuneler kullanlarak 30 kN kapasiteli Instron 3367 mekanik test
cihaz yardmyla oda scaklnda (25 C) 0.1 mm/dak basma hzyla gerekletirilmitir. Elastik modul deerleri
gerilim-gerinim diyagramnn dorusal ksmndan hesaplanrken stenit-martensit dnm gerilimi % 0.2-offset
metodu ile belirlenmitir.
3.1. Younluk ve Gzeneklilik
Ya younluk ve gzenekliliin presleme basnc ile deiimi ekil 1de gsterilmitir. TiNi tozlarn grnr younluu 4.195 g/cm3 olarak llmtr ve buna karlk gelen gzeneklilik miktar % 34.96dr. Beklendii gibi uygulanan
basncn artrlmas younlukta bir art ve gzeneklilikde bir azalmaya yol amtr ve elde edilen maksimum ya
younluk, 1150 MPa maksimum basn altnda yaplan sktrmasktrma sonras % 22lik bir gzenek oranna
karlk gelen 5.07 g/cm3 olmutur.
ekil 1den TiNi tozlarn sktrma davrannn dier alam tozlarnkine benzer olduu aktr. Sktrma ilemi
tozlarn yeniden dzenlenmesi ile balar. Bu aamada tozlarn yzey alan, yzey morfolojisi ve yzey przll
tarafndan kontrol edilen partikller aras srtnme etkin olan mekanizmadr.
Bu almada kullanlan TiNi tozlar (ortalama 21 m) ok kk olduundan, yzey alanlar son derece byktr.
Geni yzey alan genel olarak daha yksek srtnme ve daha dk paketlenme, hem de yetersiz dzenlenme
anlamna gelir. Basncn uygulanmasna devam edilmesiyle tozlarn yeniden dzenlenmesini takiben, toz temas
blgelerinde lokal deformasyon gerekleir. Basncn daha fazla artrlmasyla plastik deformasyon geiren her
paracn bal hacminde bir art gerekleir ve gzeneklerin miktarnda azalma meydana gelirken yeni temaslarn oluumu artar ve nihayet btn kompakt homojen deformasyona maruz kalr. Plastik deformasyon ile birlikte
deformasyon sertlemesi kanlmaz olur ve bunun sonucunda yksek younluk dzeyleri daha yksek d enerji
gerektirir.
819

ekil 1. Sinterleme ncesi younluk ve gzenekliliin

sktrma basnc ile deiimi.
ekil 2. Farkl basnlarda baslm TiNi kompaktlara

ait XRD diyagramlar.
TiNi tozlarn baslabilirliinin, geleneksel tozlarnkine gre daha dk olduu tespit edilmitir. Dayankl, atlak
iermeyen kompakt retimi basma srasnda gzlenen sperelastik davran nedeniyle ok daha zordur. stenitik
iyapya sahip olan balang TiNi alam tozlar sktrma esnasnda uygulanan basnla birlikte % 7-8 kadarlk deformasyonu martensitik dnm ile gerekletirmektedir. Daha fazla deformasyon uygulandnda tozlar
klasik dislokasyon hareketi yoluyla plastik ekil deitirmektedirler. Bilindii zere sperelastik davran gsteren
malzemelerde ykn boaltlmasyla birlikte malzeme ters dnm (martensitstenit) nedeniyle ilk ekline geri
dnmektedir. Fakat yapda dislokasyonlar da oluturulduu zaman bu ekil geri kazanm ksmi olmaktadr. ekil
2deki XRD patternlerinden farkl sktrma basnlar ile preslenen TiNi kompaktlarn bu ilem sonras hangi fazlar
ierdikleri grlmektedir. Dk sktrma basnlar uygulandnda, oluan martensit faznn basncn sfrlanmasyla birlikte tamamen stenite geri dnt gzlenmitir. te yandan daha yksek presleme basnlar kullanldnda, rnein 575 MPa, iyapda meydana gelen dislokasyonlar gerilimle oluturulan martensitlerin kararl
hale gelmesine yol amtr. Dislokasyonlar normalde hareketli olan stenit/martensit ara yzeylerinin hareketini
engelleyerek ters dnmn gereklemesini ve dolaysyla ekil geri kazanmn ksmen engellerler. ekil geri
kazanm artan basnla birlikte daha da azalr. Normal artlar altnda istenmeyen bir fenomen olan martensit stabilizasyonu sperelastik TiNi tozlarnn baslabilmesi iin gerekli bir koul haline dnr. Aslnda presleme basnc
10 mm apnda ve 3 mm yksekliinde disk eklindeki numunelerin retiminde kritik bir parametre deildir. Ancak,
basma deneyleri iin gereken ve 10 mm ap ve 12 mm boyunda numunelerin sadece 770 MPa civarnda bir basn
ile retilebilecei tespit edilmitir. 1150 MPa gibi daha yksek basnlarda ise her ne kadar ya mukavemeti daha
yksek ve gzenek miktar daha az numuneler retilebilse de, bu kompaktlarn kalp ierisinden karlmas inko
stearat gibi bir yalayc kullanlmasna ramen ok daha zor olmutur. Kald ki bu almada ama zaten dk
gzenekli malzeme retmek deildir.
ekil 3 presleme basncnn sinterleme sonras younluk ve gzeneklilik zerindeki etkisini gstermektedir. Sinterleme ilemi sonucu gzeneklilikte % 0.8-3.7 aralnda bir d meydana gelmitir. Sinterleme sonucu oluan
aptaki bzlme miktar retilen tm numunelerde % 2den daha dk iken numune boylarnda yaklak % 2lik bir
ime (swelling) gzlenmitir. Fakat bu ime, elementel tozlar kullanlarak sinterlenen TiNi alamlarnda gzlenen
klasik ime deildir. Daha ziyade sinterleme ncesi stma srasnda ekil bellek etkisi mekanizmas ile geri kazanlan elastik gerinimlerden kaynaklanan bir imedir.
Farkl basnlarda preslendikten sonra sinterlenmi TiNi alamlarna ait gzeneklilik dalm ekil 4de verilmektedir. Gzenek byklnn artan sktrma basnc ile azald grlebilir. Ortalama gzenek boyutu (% 50 kmla-
ekil 3. Sinterleme sonras younluk ve gzenekliliin

sktrma basnc ile ilikisi.
ekil 4. Sinterlenmi TiNi alamlarnda sktrma

basncna bal olarak gzenek dalmnn deiimi.
820

tife karlk gelen), en dk basn iin, 190 MPa, 65 m iken maksimum basn olan 1.150 MPa iin yaklak 4 m
olarak tespit edilmitir. Gzlenen en byk gzenek boyutu 200 m civarndadr. Biyomedikal uygulamalar kemik
dokunun implant malzemesi iinde geliimi iin 100-600 m arasnda deien gzenek boyutlar gerektirmektedir
[3]. Bu nedenle, gzenek boyutlar 100 mdan byk olan gzenek ierii nemli bir parametredir. 190 MPalk bir
presleme basnc toplam porozitenin % 40nn boyutlarnn 100 mdan daha byk olduu gvencesini verirken bu
oran 380 ve 575 MPa iin % 20 seviyelerine dmtr. Daha yksek basnlarda ise sadece % 5-6 civarndadr.
Ancak, bu tr byk gzenek boyutlar (100 m ve daha yksek), SEM analizi srasnda gzlenmemitir.
Geleneksel sinterleme yntemiyle retilen gzenekli TiNi alamlarnda belirli bir gzenek eklinin olmad ekil
5den aka grlmektedir. Genel olarak, gzenekli bir malzeme veya kpkte gzenekli numunenin d yzeyine
bal gzenekler ak gzenekler, d yzeye bal olmayan gzeneklerse kapal ya da izole gzenekler olarak
snflandrlabilir. Geleneksel toz metalurjisi yntemiyle retilen gzenekli TiNi alamlarnda gzeneklerin byk bir
ounluunun balang tozlarn dk paketlenme, dk sktrma basnc ve basnsz ksmi sinterleme sonucu
birbirine bal ve ak tip olduu bulunmutur. Yine de bir miktar izole veya kapal gzenek de ekil 5den grld
zere SEM incelemeleri srasnda gzlenmitir. Bu gzeneklerin byk bir ksm tozlarn atomizasyonu srasnda
olumutur. Ancak sinterleme esnasnda da baz kapal gzeneklerin olumu olmas muhtemeldir. Ak gzenek
oran, retilen btn numunelerde % 90dan daha fazladr.
ekil 5. % 23 gzenekli TiNi alamnn SEM grnts.

Genel gzeneklilik (yani toplam porozite), ak gzenek oran ve gzenek boyutu zellikle kemik implantasyonu
gibi biyomedikal uygulamalar iin ok nemli faktrlerdir. Yksek bir ak gzeneklilik oran ile yeterli gzenek
miktar ve gzenek boyutu implant malzemesi iinde doal kemik bymesini garanti eder. Yapay kemik deiimi
uygulamalar iin gzenek miktar % 30-90 aralnda olmaldr [5]. Kemik bymesi ve vcut svlarnn tanm
iin gzenekler ak tipte ve birbirleriyle balantl olmaldr. Bu gereksinimlerin nda klasik souk presleme ve
sinterleme yntemi ile retilen gzenekli TiNi alamlarnn yapay kemik implant olarak kullanlmalar uygun deildir.
te yandan, birbirine yksek oranda bal gzenek yaplar (mkemmel geirgenlik) nedeniyle pek ok uygulamada
filtre olarak kullanlmalar mmkndr.
3.2. Makro ve Mikroyap
ekil 6da verilen SEM grnts sinterlenmi gzenekli TiNi alamnn makro grnmn gstermektedir. 5 m
boyutlarna varan beyaz renkli magnezyum oksitler (MgO) aka grlmektedir. Bu oksitlerin TiNi kompakta dorudan temas eden magnezyumun ortamdaki oksijenle reaksiyona girmesi sonucu olutuu anlalmaktadr. Buna
karlk, balangta magnezyum tozu ile dorudan temas halinde olmayan yzeylerde magnezyum ya da MgOe
hemen hemen rastlanlmamtr.
(a)
(b)
ekil 6. Sinterleme srasnda TiNi kompakt yzeyinde oluan beyaz renkli MgOlar gsteren SEM grntleri,
(a) kk bytme, (b) yksek bytme.
821

Magnezyum 650 Cde erir ve artan scaklkla buhar basnc sv haldeyken byk lde artmaya balar. Scaklk art ayn zamanda magnezyumun oksidasyon reaksiyonunu da hzlandrr. Sv magnezyum TiNi kompakt
yzeyini slatr ve TiNi tozlarn oksitlerini indirgerken pota iinde bulunan frn atmosferindeki kalnt oksijen ile de
reaksiyona girer. Sonu olarak, sinterleme ncesi magnezyum tozu ile dorudan temas blgelerinde youn olarak
MgO paracklar oluturur ve bu oksitler kompakt zerinde yapr kalr. Ayn zamanda sv magnezyum ekil 6
(b)de belirgin bir ekilde grld zere bir dereceye kadar kompakt yzeyini andrmaktadr. Balangta direk
temasn olmad blgelerde MgOnun olmama ya da ok ok az olmasnn nedeni bu blgelerin sadece magnezyum buharna maruz kalmalarndandr. Bu blgelerde erozyon izine de rastlanlmamtr. blgelerin ise tamamen
magnezyum ve MgO paracklardan muaf olduu tespit edilmitir.
Sv magnezyum ile TiNi kompakt erozyonunu nlemek ve yzey zerinde kalan MgO paracklarn en aza indirmek iin kompakt sinterleme ncesi uzun MgO pelet zerine yerletirilmitir ve magnezyum tozu bu peletin zerine
ve yanlarna ilave edilmitir. Bylece kompaktn hibir blmnn magnezyum tozu ile temas halinde olmamas
garanti altna alnmtr. Bu tasarm kalnt MgO paracklarn minimize etmitir. ekil 7 gelitirilmi tasarm kullanlarak retilmi bir numuneyi gstermektedir.
ekil 7. Sinterlenmi ve nerdeyse hi kalnt MgO iermeyen TiNi alamnn makro grnts.
Farkl basnlarda preslenmi ve daha sonra ayn artlarda sinterlenmi gzenekli TiNi numunelere ait XRD desenleri ekil 8de gsterilmitir. Grld zere ne istenmeyen ikincil Ti-Ni intermetalikler ne de oksit, karbr gibi
bileikler tespit edilememitir. Btn numunelerde i yap sadece B2 stenit fazndan olumaktadr. Daha nce
de belirtildii zere 1100 C sinterleme scaklnda TiNi alamnn oksitlenmesini nlemek iin ksmi oksijen basncnn 5 10-25 atmden daha dk bir deerde olmas gerekir. Ayn scaklkta, oksijen giderici olarak kullanlan
titanyum 510-27 ve magnezyum 10-34 atmlik ksmi oksijen basnc seviyelerine inmeyi olanakl klmaktadr. Her ne
kadar bu teorik deerlere ulalmas ok mmkn olmasa da pratikte salanan oksijen ksmi basnc TiNi alam
oksitleyecek ve ikincil faz oluturacak seviyelere ulamamtr. Bu konuda daha detayl aklamalar [6 ve 8] numaral referanslarda bulunabilir.
ekil 8. Farkl basnlarda baslm TiNi kompaktlarn sinterleme sonras XRD patternleri.
822

3.3. Mekanik zellikler

% 23 gzenee sahip TiNi alamna ait basma gerilim-gerinim erisi ekil 9da verilmitir. Bu eriden elde edilen
mekanik zellikler de izelge 1de verilmitir. Dngsel yklemeyle birlikte dayan artarken geri kazanlamayan
gerinim miktarnda zellikle ilk dng sonrasnda nemli bir azalma sz konusudur, elastik modl ise ayn kalmaktadr. lk dngde % 6ya yakn bir gerinim uygulandktan sonra geri kazanlamayan gerinim miktar % 1.7 civarnda
gereklemitir. Gzenekli TiNi alamlarnda hacimli olanlardakinin (sabit gerilimde dnm) tersine dorusal
sperelastisite davran gzlenmitir. Bu davrann ve geri kazanlamayan gerinimlerin iki nedeni vardr: test scaklnn (25 C) stenit biti scaklndan (41 C) dk olmas ve ekilsiz, homojen olmayan gzenek yapsnn
yaratt lokal gerilmelerdir.
Geleneksel sinterleme metoduyla retilen gzenekli TiNi alamlarnn yetersiz olan gzenek boyutu ve gzenek
miktar nedeniyle kemik deiimi uygulamalar iin uygun olmad belirlenmesine ramen, mekanik zellikleri bakmndan hibir sorun tespit edilmemitir. Bir implant malzemesinden beklenen yksek mukavemet, dk elastik
modl ve gerinim kazanma yeteneini baaryla yerine getirmektedirler. Bu anlamda kolayca, derece derece deien gzenekli implant uygulamalar iin gereken metalik malzemelerin retiminde kullanlabilir. rnein, implantn
youn ekirdek ksm olarak sert doku nakil malzemesi retiminde kullanlabilir. Yksek gzenekli d yzeyler doku
bymesine izin verirken i ksmda yer alan daha dk gzenekli ksm gerekli dayanc salayacaktr. Kk
gzenekler ayn zamanda vcut svlarnn tanmna imkan verirken dk elastik modl sayesinde de gerilim
perdeleme etkisi minimize edilebilecektir.
ekil 9. % 23 gzenekli TiNi alamnn gerilim-gerinim erisi.

izelge 1. % 23 gzenekli TiNi alamnn mekanik zellikleri.
Young modl, E
(GPa)
13.2
Martensit oluum gerilimi,

(MPa)
140
% 2 gerinimde basma gerilimi, (MPa)
cr
lk dng
kinci dng
nc dng
135
186
188
4. SONULAR
zellikle filtre malzemesi olarak kullanlmaya uygun TiNi malzemeler alam tozu kullanlarak magnezyum buhar
altnda sinterleme suretiyle % 21-26 aralnda gzenekli olarak retilmilerdir. Magnezyumun TiNi alamn sinterleme esnasnda oksitlenme v.b. eitli kirlenmelerden ve buna bal istenmeyen ikincil Ti-Ni faz oluumundan
koruduu grlmtr. retilen gzenekli malzemelerin gzenek miktar ve boyutu asndan yetersiz iken mekanik zellikler asndan olduka baarl olduu bulunmutur. Gzenekli TiNi alamlarnn dorusal sperelastisite
davran sergiledikleri ve dngsel ykleme-boaltma ile byk miktarda gerinimleri tamamen geri kazanabildii
belirlenmitir.
TEEKKR
823

KAYNAKLAR
1. Otsuka, K., Wayman, C.M., Shape Memory Materials, Cambridge University Press, Cambridge, UK, 1998.
2. Pelton, A.R., Stoeckel, D., Duerig, T.W., Medical Uses of Nitinol, Materials Science Forum, Vol. 327-328,
pp. 63-70, 2000.
3. Itin, V., Gyunter, V., Shabalovskaya, S., Sachdeva, R., Mechanical Properties and Shape Memory of Porous
Nitinol, Materials Characterization, Vol. 32, pp. 179-187, 1994.
5. Bansiddhi, A., Sargeant, T.D., Stupp, S.I., Dunand, D.C., Porous NiTi for Bone Implants: A Review, Acta
Biomaterialia, Vol. 4, pp. 773-782, 2008.
stanbul, 2010.
7. Li, B.Y., Rong, L.J., Li, Y.Y., Gjunter, V.E., Synthesis of Porous Ni-Ti Shape-Memory Alloys by Self-Propagating High-Temperature Synthesis: Reaction Mechanism and Anisotropy in Pore Structure, Acta Materialia,
Vol. 48, pp. 3895-3904, 2000.
8. Yuan, B., Zhang, X.P., Chung, C.Y., Zeng, M.Q., Zhu, M., A Comparative Study of the Porous TiNi ShapeMemory Alloys Fabricated by Three Different Processes, Metallurgical and Materials Transactions, Vol.
37A, pp. 755-761, 2006.
9. Kaya, M., Orhan, N., Kurt, B., Khan, T.I., The Effect of Solution Treatment under Loading on the Microstructure and Phase Transformation Behavior of Porous NiTi Shape Memory Alloy Fabricated by SHS, Journal of
10. Tosun, G., Ozler, L., Kaya, M., Orhan, N., A Study on Microstructure and Porosity of NiTi Alloy Implants Produced by SHS, Journal of Alloys and Compounds, Vol. 487, pp. 605-611, 2009.
Research, Vol. 13, pp. 2847-2851, 1998.
16. Zhao, Y., Taya, M., Kang, Y.S., Kawasaki, A., Compression Behavior of Porous NiTi Shape Memory Alloy,
Acta Materialia, Vol. 53, pp. 337-343, 2005.
17. Aydomu, T., Bor, ., Processing of Porous TiNi Alloys Using Magnesium as Space Holder, Journal of
press, DOI: 10.1007/s11661-011-0714-z.
19. Bansiddhi, A., Dunand, D.C., Shape-Memory NiTi Foams Produced by Solid-State Replication with NaF,
Intermetallics, Vol. 15, pp. 1612-1622, 2007.
23. Grummon, D.S., Shaw, J.A., Gremillet, A., Low-Density Open-Cell Foams in the NiTi System, Applied Physics Letters, Vol. 82, pp. 2727-2729, 2003.
26. Dutta, R.S., Madangopal, K., Gadiyar, H.S. Banerjee, S., Biocompatibility of NiTi Shape Memory Alloy, Br.
Corros. J. Vol. 28, pp. 217-221, 1993.
27. Pelton, A., Trepanier, C., Gong, X.Y., Wick, A., Chen, K.C., Structural and Diffusional Effects of Hydrogen in
TiNi, SMST 2003, Organizer: SMST, pp. 33-42 Monterey, CA, 2004.
824

POWDER
PRODUCTION
www.turkishpm.org
825

AA 2014 ALMNYUM ALAIM TOZLARINDA MA VE SPEX YNTEMLER

KULLANILARAK KARBON LAVES ve ZELLKLERNN ARATIRILMASI
Sinan AKSZ, A. Tamer ZDEMR, B. BOSTAN
sinanaksoz@hotmail.com, tozdemir@gazi.edu.tr , bostan@gazi.edu.tr
ZET
Bu almada argon atmosferinde ve 790 C alma scaklnda gaz atomizasyon yntemi kullanlarak retilen AA
2014 alam tozlar kullanlmtr. Elde edilen tozlar daha sonra dikey atritrde ierisine karbon tozlar ilave edilerek
tme ilemine tabi tutulmutur. tme ileminde spex ile tlen tozlar ile atritrdeki tozlar arasnda karlatrma yaplmtr. Atritrde yaplan tme ileminde yalayc olarak kullanlan inko stearatrn etkisi aratrlmtr.
tme sresinin toz boyutuna olan etkisi tespit edilmeye allmtr. Yaplan deneysel almalar neticesinde
spex ile tmede 45 dakika gibi ksa srelerde nihai rn elde edilebilirken atritrde bunu elde edebilmek iin 7
saat zerindeki srelere ihtiya duyulabilmektedir ve yalayc kullanlmadan yaplan tme ileminde gereklemesi gereken evrelerin olumad belirlenmitir.
Anahtar Kelimeler: AA2014 Alminyum Alam, Mekanik Alamlama, Metal Matris Kompozit .
RESEARCH ON CARBON ADDITING IN AA2014 ALUMINIUM ALLOY AND

FEATURES OF THE PRODUCTS AFTER MECHANICAL MILLING AND SPEX
ABSTRACT
In this study, fine AA 2014 alloy powders manufactured by the method of gas atomization were used. Processing
was accomplished under argon gas atmospheric conditions at 7900C. Then, some powders were mixed with graphite and attrition milled in a horizontal attritor where, rest of the powders was processed by using spex. There after,
products of these different processes were compared in details. Thus, together with the effect of the addition of zinc
stearate as a lubricant, the effect of processing time on mean powder sizes was investigated. It was found that,
processing with spex was fast and the desired composite powder could only be achieved after 45 minutes. Where
as, for the same product, the required attrition time was about 7 hours. It was concluded that, lubrication during
processing was essential and without it, quality of milling was insufficient.
Key words: AA 2014, Mechancal Alloying, Metal Matrix Composite.
1.GR
Mekanik Alamlama (MA) yntemi bir hazne ierisindeki tozlara yksek enerjili bilyalar ile tekrarl olarak devam
eden kaynaklanma, krlma ve yeniden kaynaklanmann meydana getirildii bir kat hal reaksiyonudur. lk olarak
nikel ve elik bazl sper alamlarda uak endstrisi uygulamalarnda kullanlmak iin oksit dalmyla glendirilerek retilmitir. SPEX ileminde ise bir kerede 10 ile 20 g arasnda toz ilave edilebilen hazneye sahip olup
ounlukla laboratuar artlarnda kullanlan bir cihazdr. MA sonras mikro yap gaz atomizasyon yntemi ile retilen tozlardan daha iyidir ve tane boyutu oranlar hzl katlatrma teknikleri kullanlarak elde edilen yntemlerle
ayndr. lk aamada MA ilemi oksit dalm ile glendirme ilemleri ve Ni bazl sper alamlar iin gelitirilse de
bu gnlerde alminyum ve bakr alamlarnn uygulamalarnda ve zellikle intermetalik yaplarda kullanlmaktadr
826

[1-2]. TM yntemi ile retilen paralar gnmzde yaygn olarak kullanlmakta ve kullanm alanlar da giderek
artmaktadr [3].
Mekanik retim sonras boyut aral tme esnasnda bilyelerin oluturduu enerji, bilye toz aarlk oran ve
tme ilemi esnasnda oluan toplam scaklk ile belirlenebilir. Yaplan aratrmalarda SPEX ile yaplan tme
ilemi ile dier dk enerjili tme ilemlerine gre daha hzl bir tme gereklemektedir. Yaplan deneysel
almalarda SPEX ile 20 nm gibi dk tane boyutlarna ksa srelerde ulalabilirken dier yntemlerde bu boyuta
ulamak iin uzun srelere ihtiya duyulmakta baz retim yntemlerinde ulalamamaktadr (ekil 1). Pulverisette
isimli SPEX ile 32 saat tme sresinde 90 d/d hzda 40 nm, 180d/d hzda 31 nmve 360 d/d hzda ise 20 nm tane
boyutuna ulalabilmektedir [4]. Suryanarayana ve arkadalarnn yapt alma ile ticari olarak kullanlan MA
ileminin kullanm ve kullanm alanlar giderek artmaktadr [5].
ekil 1. Demir tozlar iin farkl tme trlerinde zamana bal olarak ortalama toz boyutu [4].
tme sonras tozlar birok taneden meydana gelecek ve tane boyutunun azalmas ile Hall Petch eitliine gre
(=0 + kd1/2)mekanik zelliklerde bir artma meydana gelecektir [6]. ekil 2 incelendiinde tme sresine bal
olarak numunelerin sertliklerinin giderek artt gzlemlenmektedir. Bu sertlik artna da yukardaki ekil 1 incelendiinde tme sresinin artmas ile tanelerin boyutunun artmasna neden olmakta ve tane boyutundaki azalma ise
malzemede mukavemetlemeye neden olmaktadr.
ekil 2. tme sresine bal olarak saf ve glendirilmi Al alamnn sertlik grafikleri [6].
827

2.1. tme lemi
Kullanlan AA 2014 tozlar, Dey tip gaz atomizasyon nitesinde 15 bar basn altnda yksek saflktaki inert tip
argon gaz ile retilmitir. Tozlar atomizasyon nitesinde retildikten sonra elek analizi ile boyut dalm gerekletirilmi ve 100 m altndaki tozlar alnarak boyut dalm cihaz ile ortalama boyutu 95 m olarak tespit edilmitir.
Boyutlandrma ilemi esnasnda, yaklak 5 kere ilem tekrarlanm ve btn sonular ortalama 95 m deerinde
kmtr.
Daha nce yaplan almalarda herhangi bir yalayc kullanlmad taktirde (Saf Al ierisine % 2 C) 2 saatte
istenilen toz boyutuna ulalmtr [7]. Bu almada da nceki almaya paralel olarak yalaycsz olarak AA
2014 ierisine %2 C ve %2 C + % 0,5 orannda yalayc (inko stearat) ilave edilerek MA ilemine yalaycnn
ve karbonun etkisi incelenmitir. Ayrca MA ile SPEX arasnda karlatrmalar yaplarak, her iki nitenin tme
srelerinin tane yaplarna etkileri tespit edilmeye allmtr. tme sresinin; toz boyutuna, ekline ve sertlie
olan etkileri belirlenmeye allmtr. Bu kapsamda MA ilemine tabi tutulan tozlarn tme sresine bal olarak
sertlikleri ve mikro yaplar incelenmitir. MA ilemi sonrasnda karbonun sistem ierisinde karbr oluturma eilimi tespit edilmeye allmtr. Bu amala XRD analizleri yaplarak Al4C3 iin gerekli piklerin oluup olumad
belirlenmeye allmtr. tme ilemleri sonrasnda numunelerin SEM ve XRF incelemeleri yaplarak meydana
gelen deiimler ve kirlenme oluumlar tespit edilmeye allmtr.
Tozlarn karakterizasyonu ve grntlenmesi esnasnda bir ok deneysel ekipmandan yararlanlmtr. Bu cihazlar
sralamak gerekirse G.. Mhendislik Fakltesindeki Malvern Mastersizer E toz boyutu analiz cihaz, Atom Enerjisindeki Bruker D8 XRD analiz cihaz ile Cuk =1.5406 ve 2/dakika tarama hznda deneyler yaplmtr. Mikro
yap incelemeleri G.. Teknoloji Fakltesi Metal Eitimi Blmndeki Joel JSM-5600 taramal elektron mikroskobunda, sertlik lmleri ise, Shimadzu Mikro Sertlik cihaznda 100g yk kullanlarak gerekletirilmitir.
Tozlarn boyut analizleri esnasnda yaplan boyutlandrmalarda yaklak 5 adet boyutlandrmann da ayn boyut
aralnda kmas, tozlarn retiminin uygun artlarda gerekletirildiini gstermektedir. Tozlarn SEM ile yaplan
boyutlandrlmas ve mikro yap incelemelerinde kresel ve kresele yakn bir mikro-yapya sahip olduu gzlemlenmektedir (ekil 3).
ekil 3. MA ileminde kullanlan tozlar

Sistemde kullanlan AA2014 tozlarna yalayc olarak kullanlan grafitin MA sresine bal olarak etkileri incelendiinde, normal artlarda tanelerde plakalama olmas beklenirken tozlar direk olarak krlp birlemektedir. Kullanlan
grafitin AA 2014 tozlar iin yalayclk grevi stlenmedii tespit edilmi ve yalayc olarak alam tozlar iin
inko stearat kullanmna geilmitir. 6064 malzemesinde ise yalayc olarak grafit kullanlm ve yksek tme
srelerine ulalmtr. Yalaycnn kullanld artlarda ise tozlar MA srecinde izlemesi gereken nce tabaklama
ve sonrasnda yksek sertlik ve peklemeyle birlikte krlma gzlenmitir [1, 8]. Krlma sonras ise tozlar tekrar
mekanik birleme sonras nihai yapsn oluturmaktadr. Yalayc ilavesi yaplmadan almalarda en fazla 240
dakika MA sresine ulalrken (ekil 4 a) ve bu sre yalayc kullanlan sistemlerde ise krlmann yeni balad
noktalara tekabl etmektedir (ekil 4 b). MA ileminin tamamland sre ise 420 dakika olarak belirlenmitir (ekil 4
c). 420 dakika allan Atritr kitlenmeye ve sorunlar oluturmaya balamaktadr. Bu sebeplerden dolay MA sresi
olarak, en fazla 420 dakika kullanlmtr.
828

ekil 4. MA a) Yalayc kullanlmadan 240 dak. b) Yalayc kullanlarak 240 dak

c) Yalayc kullanlarak 420 dak.
Yaklak 45 dak. sren SPEX ile tme almalarnda elde edilen toz yapsna (ekil 5) , MA ileminde yalayc
da kullanlarak ancak 420 dakikada ulalabilmitir. Bu sonu ise SPEX ile yaplan tme performansnn MAya
gre daha iyi olduu gstermektedir. Ancak MA ileminde yksek oranlarda toz malzeme kullanlabilirken, SPEX ile
tme ileminde 10 gram gibi ok dk deerlerde toz tlebilmektedir [9].
ekil 5. SPEX ile 45 dak. tme

a)
X 100 b) X 200
Karbon ilavesi ile yaplan MA ilemindeki tozlarda XRD incelemeleri sonras karbr yapsna rastlanlamamtr
(ekil 6). XRF incelemelerinde de, karbon miktarnn tme sresine bal olarak deimemesi XRD verilerini
dorular niteliktedir. Bylece MA sresinin karbr oluumuna etkisinin olmad belirlenmitir. Bu konu hakk
nda yaplan dier almalarda da benzer sonular elde edilmitir [7,10-13].
ekil 6. 7 saat MA ilemi gren tozlarn XRD analizi.

MA sresinin artmasyla birlikte doal olarak tozlarn sertliklerinde de bir art meydana gelmektedir (ekil 7). Buradaki sertlik art azalan tane boyutlarndan (Hall Petch bants) ve uygulanan deformasyon neticesinde deformasyon sertlemesinden kaynaklanmaktadr. Tane boyutlarnn klmesi ile meydana gelen sertlik art ile birlikte
tanelerin presleme basnlarnda da benzer artlar meydana gelmektedir. [6,14].
829

ekil 7. Farkl srelerde MA ilemine tabi tutulmu tozlarn sertlik sonular

KAYNAKLAR REFERENCES
1. Suryanarayana C., Mechanical alloying and milling, Progress in Materials Science, 46: 1-184 (2001).
2. Ruiz-Navas E.M., Fogagnolo J.B., Velasco F., Ruiz-Prieto J.M., Froyen L., One step production of aluminium
matrix composite powders by mechanical alloying Composites: Part A 37 :21142120 (2006)
4. Claudio L. De Castro, Brian S. Mitchell., Nanoparticles from Mechanical Attrition, Department of Chemical
Engineering, Tulane University,New Orleans, Louisiana, USA, syf.6.
5. Suryanarayana C., Ivanov E., Boldyrev V.V., The science and technology of mechanical alloying, Materials
Science and Engineering A304306 : 151158, (2001).
6. Razavi Tousi S.S.*, Yazdani Rad R., Salahi E., Mobasherpour I., Razavi M. , Production of Al20 wt.% Al2O3
composite powder using high energy milling , Powder Technology, 192 (2009) 346351.
8. Son H.T., Kim T.S., Suryanarayana C., Chun B.S., Homogenous Dispersion of Graphite in a 6061 Aluminium
Alloy by Ball Milling, Materials Science & Engineering, 163-169, (2002).
9. Suryanarayana C, Mechanical Alloying, Pergamon Materials Series, Volume 2, Pages 49-85, (1999).
10. Arslan G., Kara F., Turan S., Quantitative X-ray Diffraction Analysis of Reactive Infiltrated Boron CarbideAluminium Composites Journal of the European Ceramic Society 23, 12431255, (2003).
11. Wu, N. Q., Wu, J. M., Wang, G.X., Li, Z. Z., Amorphozation in the Al-C System by Mechanical Alloying, J. of
All. And Comp. 260 (1997) 121-126.
(2006) 107-122.
14. Sivasankaran, S., Sivaprasad K., Narayanasamy R., Vijay Kumar Iyer, An investigation on flowability and
compressibility of AA 6061100x-x wt.% TiO2 micro and nanocomposite powder prepared by blending and
mechanical alloying, Powder Technology 201 (2010) 7082.
830

BOR OKSTTEN ELEMENTEL BOR TOZU RETM

PARAMETRELERNN ARATIRILMASI
Bahadr GNEY ve brahim USLAN
Gazi niversitesi, Makina Mhendislii Blm, Maltepe, Ankara,
bahadirguney@gmail.com, iuslan@gazi.edu.tr
ZET
Bu almada elementel bor tozu oda scaklnda, mekanik tme tekniiyle retilmitir. Bu amala
magnezyum (Mg) ve bor oksit (B2O3) tozlar spekste farkl parametreler kullanlarak tlmtr.
Tepkimenin gereklemesi ile elementel bor (B) ve magnezyum oksit (MgO) rn olarak elde edilmitir.
Farkl parametrelerde tlm olan numuneler XRDde analiz edilmi ve elde edilen pik deerleri
patern deerleri ile karlatrlarak yorumlanmtr. Elementel bor tozu tayini yapmak iin iki numune
ICP- OESde analiz edilerek 100 mglk numunede 11,7 mg elementel bor tozu tespit edilmitir. alma
neticesinde magnezyum ve bor oksitin mekanik tlmesi ile bor oksit iindeki bor indirgenerek %
77lere varan oranlarda elementel bor tozu retilmitir.
Anahtar Kelimeler: Bor Oksit, Elementel Bor, tme, Speks.
INVESTIGATION OF PRODUCTION PARAMETERS OF ELEMENTAL
BORON FROM BORON OXIDE
ABSTRACT
In this study, elemental boron powder was produced by mechanical milling technique at room temperature. With this purpose, magnesium (Mg) and boron oxide (B2O3) powders were milled in a spex by
using different parameters. Elemental boron (B) and magnesium oxide (MgO) were obtained as a product after the reaction. The milled samples by different parameters were analyzed using XRD unit and
interpreted by comparing values of peak and pattern.
By analyzing of the samples using ICP-OES unit
11,7 mg of elemental boron powder was determined in the sample which is 100 mg. As a result of this
study, magnesium and boron oxide were milled mechanically and with this process, boron which was in
the boron oxide was reduced and finally obtained with the yield of 77%.
Keywords: Boron oxide, elemental boron, milling, spex.
1.GR
Bor madenleri iindeki B2O3 oranna gre deerlendirilir ve ticari deer kazanr. lkemizde Emet, Bigadi ve Kesdelekde bulunan kolemanit (Ca2B6O11.5H2O), %50,8 oran ile en yksek B2O3 ieriine
sahip bor minerallerinden biridir. Yksek saflkta B2O3, borik asitin iki aamada dehidrasyonu yntemiyle retilmektedir [1-4].
Mekanik enerji sayesinde kimyasal reaksiyonlarn ve faz deiimlerinin gerekletii mekanik- kimyasal
sentez yntemi ile indirgeme reaksiyonlar, oksitleme reaksiyonlar ve elementel toz retimi gerekle-
831

tirilebilmektedir. Literatrde bunlarla ilgili almalar mevcuttur [5-17]. Mekanik-kimyasal sentez uygulamalar genellikle atritr ve speks tipi tclerde yaplmaktadr [11]. Atritrler ve speksler, mekanik
tme ve mekanik alamlama almalarnda kullanlan yksek enerjili ve verimli tclerdir. Koruyucu gaz atmosferinde de allabilen atritrlerde iinde tmenin yapld kap sabittir/dnmez.
Atritrlerin verimliliinde en etkin parametre kartrc kollarn hzdr. Spekste ise, iinde tmenin/
mekanik alamlamann gerekletii reaktr dnme ve titreim hareketleri birlikte yapldndan alamlama etkinlii daha yksektir.
Spekste mekanik tme yaparak; Bolarin ve arkadalar [6], Mn2O3 ve La2O3 bileik tozlarndan lantanyum magnatit (LaMnO3) bileiini, Garcia ve arkadalar [7] de elementel Co ve Ni tozlarndan Ni-Co
alamn elde etmilerdir. Ricceri ve Matteazzi [12] ise Mg ve B2O3 tozlarn spekste terek elementel bor tozunu rettiklerini bildirmilerdir. Bununla ilgili deerlendirme, tartma blmnde verilmitir.
2. DENEYSEL ALIMA
2.1. Malzeme
Deneylerde kullanlan Mg tozlar piyasadan, B2O3 ise Eti Maden letmeleri Bandrma Bor Oksit
Fabrikasndan temin edilmitir. Mg tozlar, Gazi niversitesi Fizik Blmnde bulunan XRD cihaznda
analiz edilerek dorulanmtr. Amorf yapdaki bor oksitin XRD analizinden ise sonu alnamamtr.
2.2. Speks Uygulamalar
Speks uygulamalar Gazi niversitesi Kimya Mhendislii Blm Laboratuvarnda bulunan Spex
8000M cihaz ile yaplmtr. Speks almalarnda kullanlan parametreler izelge 1de verilmitir. tme ilemlerinde drt adet paslanmaz elik bilya kullanlmtr. Bu bilyalardan bir tanesi 16 mm apnda
dier ise 4,8 mm apndadr.
Bu bilyalarn toplam arl 17,51 gramdr. Speks uygulamasnda tepkimeye girecek toz miktarnn
arlka %48,83nn Mg, %51,17sinin ise B2O3 tozlar olduu hesaplanmtr. Bu deerlere gre,
izelge 1de verilen toz/bilya oranlar iin Mg ve B2O3 miktarlar bulunmutur. Spekste tmenin gerekleecei reaktr iine Mg, B2O3 ve bilyalar kontroll atmosfer nitesinde (glove-box) koyulmu ve
reaktr kapa skca kapatlp hava girii engellenmitir. Daha sonra reaktr speks cihazna yerletirilip
tme ilemi yaplmtr.
2.2. XRD, ICP-OES ve SEM Analizleri
tme sonras elde edilen toz karmlarn tm
Eti Maden letmeleri Ar-Ge Laboratuvarnda bulunan Rigaku D-max 2200 model XRD cihaznda
analiz edilmitir. Ayrca elementel bor analizi iin
ODT Merkez Laboratuvarnda bulunan Perkin Elmer Optima 4300DV ICP-OES (Endktif Elemi
Plazma Optik Emisyon Spektrometresi) cihazndan
yararlanlmtr. Bu cihazla, yetmi civarnda kimyasal elementin eser, minr ve major konsantrasyon
dzeylerinde ve ayn anda analizi mmkndr. ICPOES analizleri 5 ve 9 nolu deney numuneleri iin
gerekletirilmitir. Bu analizler iin 0,1 g rnek alnp kral suyu (3 hacim HCI ve 1 hacim HNO3) iinde
zlmtr.
nce stlan zelti daha sonra 100 mlye saf su ile
seyreltilmitir. Oluan zeltiden 1 ml alnp 50 mlye
saf su ile tamamlanmtr. Analiz sonucu cihazdan
okunan deerden 0,1 glk toz karm iindeki elementel bor miktar hesaplanmtr. Mg ve B2O3 tozlar ile 5 ve 9 nolu deney numunelerinin taramal
elektron mikroskop almalar ise Gazi niversitesi Metal Eitimi Blmnde bulunan JEOL JSM 6060
LV model SEM cihaznda gerekletirilmitir.
832

3. DENEYSEL BULGULARLAR VE TARTIMA

Deneysel almalarda Mg ve B2O3 tozlar speks tipi deirmende tlm ve denklem (1)de verilen
reaksiyon ile elementel bor tozunun retilmesi amalanmtr:
B2O3 + 3Mg 2B + 3MgO
(1)
Deneylerde kullanlan Mg ve B2O3 tozlarnn SEM grntleri ekil 1de verilmitir.
(a)
(b)
ekil 1. (a) Mg, (b) B2O3 tozlarnn SEM grntleri
1/27 toz/bilya oran ve 20 dakika sreyle yaplan tme almalarndan elde edilen toz numunelerinin
XRD analizinden elde edilen grafikteki zirve deerleri XRD cihazndaki desenlerle karlatrlm ve
grafikteki zirvelerin tamamnn magnezyuma ait olduu, hedeflenen tepkimenin bu deney parametreleri
iin gereklemedii grlmtr (ekil 2).
Karm oran 1/27 alnarak yaplan tme ileminden beklenen sonu alnamamas zerine yeni parametreler belirlenmitir. Yaplacak uygulamalarda bilya says sabit tutulurken, farkl karm oranlar
(toz/bilya) ve sreler kullanlmtr (Deney 2-4). Olas farkllklar grebilmek iin birbirine uzak karm
oranlar alnmtr. 1/48 karm orannda 90 dak. sreyle yaplan Deney 2 iin hem Mg hem de MgO
pikleri grlm
ekil 2. Deney 1 iin XRD analizi. Toz/bilya oran: 1/27, sre: 20 dak.
833

(ekil 3); reaksiyonun gereklemeye balad fakat srenin tozlarn tamamnn tepkimeye girmesine
yetecek kadar uzun olmad anlalmtr. MgOe ait desen deerlerinde yer alan 42,917de oluan
%100lk pik grafikte net olarak grlmektedir. Ayrca grafikte yer alan ikinci en yksek iddetli pik ise
hem magnezyumun 36,620deki pikine uyarken, hem de MgOe ait 36,937deki pike uymaktadr. Dolaysyla bu pikin tam olarak hangisine ait olduu bilinmemektedir. Fakat magnezyumun %100lk pikine
uymas, ona ait olma olasln artrmaktadr. Ayn karm orannda 180 dak. sreyle yaplan Deney
3 iin tepkime tamamen gereklemitir (ekil 4). Burada magnezyuma ait pikler yok olarak, yerine
MgO pikleri olumutur. Grafikte bir de demire ait bir pik ortaya kmtr. Bu pikin uzun sreli tmeye
bal arpmalar neticesinde, bilyalardan veya reaktr eperlerinden kaynakland dnlmektedir.
Bir nemli nokta ise, her iki reaksiyon sonucunda olumas beklenen bir dier rn olan elementel bor
grlmemitir.
1/8 karm orannda 300 dak. sreyle yaplan Deney 4e ait numunelerin analizinden elde edilen grafik
(ekil 5) incelendiinde, oluan piklerin magnezyuma ait olduu grlmektedir. Ayrca 42-44 deerleri
arasnda MgOe ait olabilecek kk bir pik grlmektedir. Dier iki almaya gre uzun sren bir tme olmasna ramen beklenen reaksiyon gereklememitir. Bu da toz/bilya karm orannn tepkimenin gereklemesinde ok etkin bir rol olduunu gstermektedir.
834

1/48 karm oran iin 90 dakikada balayan tepkimenin 180 dakikada tamamland grldnden,
bu karm oran sabit tutulup, zaman aral daraltlarak tepkimenin yaklak olarak ne zaman tamamland yeni deneylerle belirlenmeye allmtr (Deney 5-6). Ayrca yeni karm oran (1/36) ve srelerle (120, 150, 180 dak.) farkl uygulamalar yaplmtr (Deney 7-9). Deney 5-9un hepsinde reaksiyonun tamamen gerekletii Mg pikinin olumad, sadece MgOe ait piklerin olutuu grlmektedir.
Bunlara ait rnek bir XRD kts Deney 7 iin ekil 6de verilmitir. Buradan hem bir 1/36lk hem de
1/48lik karm oranlarnda yaklak
120 dakikalk tme sresinin reaksiyonun gereklemesi iin yeterli olduu anlalmtr. Yaplan bu
be uygulamann sonularnn ortak zelliinden biri de, hepsinde demire ait pik grlrken, beklenen
rn olan elementel bora ait herhangi bir pik grlmemitir.
Deney 5 ve Deney 9 numuneleri iin ICP-OES cihaznda yaplan elementel bor tayini almalarndan
elde edilen dalga boyu-konsantrasyon erisi ekil 7de verilmitir. Cihazdan okunan deerlere bal
yaplan hesaplamalardan 0,1 glk toz karm iinde, Deney 5 iin 11,35 mg, Deney 9 iin ise 11,7 mg
elementel bor tozu bulunduu tespit elikidir.
835

ekil 7. ICP-OES dalga boyu-konsantrasyon erisi. Deney 5: 1/48, 120 dak., Deney 9: 1/36, 180 dak.
ekil 8. Ricceri ve Matteazziye ait makalede verilen XRD grafikleri [12]. a) tme ncesi B2O3 ve Mg
karm, b) Karm oran 1/27, sre 10 dak. olan karm (reaksiyon tamamlanm), c) bdeki parametrelerle tlm ve kimyasal ayrtrlm, d) Karm oran 1/8, sre 300 dak. olan karm (kimyasal
ayrtrlm). Not: Mg (x), MgO (o), B (+).
edilmitir. Stokiyometrik hesaplara gre bu miktarn 15,17 mg olmas gerekmektedir. Speks uygulamasyla elementel bor tozu retimi iin buna gre bir karlatrma yapldnda; Deney 5 iin %75lik,
Deney 9 iin ise %77lik bir baar elde edildii grlmtr.
Bu almada elde edilen sonular Ricceri ve Matteazzinin almasyla [12] karlatrldnda, dikkat ekici farkllklar ortaya kmtr. Ricceri ve Matteazzi [12], 8 adet 8 mmbapnda bilya kullanm
ve optimum artlar 1/27 karm orannda 9 dakika olarak bulmular; tme ncesi ve sonras XRD
grafiklerini sunmulardr (ekil 8). Buradaki grafikler incelendiinde, ilgili makale ieriiyle elikiler tespit edilmitir. ekil 8.adaki grafiin B2O3 ve Mg iin olduu belirtilmi, ancak * ile gsterilen piklerin
neyi temsil ettii belirtilmemitir. Bu pikler, desenlerle karlatrldnda hibir eye uymamtr. Fakat
piklerin dizilii ve tipik grntsnn magnezyuma benzemesi nedeniyle, bu grafik kaydrldnda magnezyuma ait piklere uyduu grlmtr. ekil 8.bdeki pikler Mg olarak tanmlanm, fakat Mg desenleri
incelendiinde bu piklerin magnezyuma ait olmad grlmtr. Ayrca reaksiyonun tamamland belirtilen bu grafikte, olumas gereken MgO ve elementel B pikleri yerine Mg piklerinin grlmesi nemli
bir elikidir. XRD analizi ncesi kimyasal ayrtrma ile Mg, Fe ve tepkimeye girmeyen Mg tozlarnn
ortamdan uzaklatrld, ortamda sadece elementel bor tozu kald ifade edilen ekil 8.cde verilen
grafik iin; tm piklerin MgO olmas da ayr bir
Ayrca literatrdeki MgOe ait desenlerde sadece on noktada pik oluurken, ekil 8.cde birok noktada
pik olumaktadr. Benzer ekilde ekil 8.dde de, kimyasal ayrtrmaya karn hem MgO, hem de elementel bor pikleri iaretlenmitir. Ricceri ve Matteazzi [12] XRD analizlerini Co K kullanarak yapmlardr. Bir element veya bileie ait XRD grafiinde ilk olumas gereken pik noktas %100lk noktadr. Co
K iin elementel bora ait %100lk zirve yaklak 20,3te olumaldr. Fakat ekil 8.dde grld gibi,
grafik 20den balamakta ve MgO ve elementel B pikleri, desenlere uymamaktadr. Bir dier husus da,
ekil 8.dde olduu gibi eer XRDde elementel B analizi mmknse, buna ait piklerin ekil 8.cde niin
grlmediidir. XRD analizlerindeki bu hatal yorumlardan dolay, bu alma kapsamndaki sonularn
Ricceri ve Matteazzinin verileriyle [12] uyum gstermedii kanaatine varlmtr.
4. SONULAR
Drt bilyann kullanld spekste tme uygulamalarnda, 1/8 karm oran ile 300 dakika tme
sresiyle bile mekanik-kimyasal sentezleme gereklememi iken, 1/48 karm oran iin 90 dakikalk
bir tme sresiyle sentezlemenin balad tespit edilmitir.
836

Reaksiyonun en ksa zamanda gereklemesi ve yksek oranlarda elementel bor tozu elde etmek iin
magnezyum ve bor oksit tozlarnn toz/bilya karm orannn 1/36 veya 1/48 alnarak en az 120 dakika
sreyle spekste tlmesi gerektii belirlenmitir. Bu tme ilemleri sonunda bor oksitin indirgenerek %77ye varan miktarlarda elementel bor elde edilmitir. Bu miktar artrmak iin bilya says ve boyutunun deitirilmesinin veya reaksiyon hzn artrmak iin katalizr kullanlabilecei dnlmektedir.
almalar sonunda elementel borun XRDde tespit edilemedii grlmtr. Borun teyiti ve miktar olarak analizi ICP-OESde yaplabilmitir. Bunun dnda elementel bor tespiti iin kimyasal tayin yntemleri
aratrlabilir.
tme ilemi ile elementel bor tozu retiminde hem kullanlan hemde elde edilen rnlerin miktarlar
dktr. Endstriyel olarak yksek miktarlarda elementel bor tozu retmek iin atritr, silindirik deirmen veya byk hacimli kaba sahip speks kullanlm aratrlmaldr.
Ricceri ve Matteazzinin almasnda [12] verilen XRD analizlerine ait grafiklerin yorumlarnda elikiler
sz konusudur.
KAYNAKLAR
1. Ulusal Bor Aratrma Enstits (BOREN), www.boren.gov.tr/borhk.htm.
2. DPT 8. Be Yllk Kalknma Plan Madencilik zel htisas Komisyonu Raporu,Endstriyel Hammaddeler Alt Komisyonu, Kimya Sanayi Hammaddeleri, DPT:2608-K:619 2: 5-40, 2001.
3. alk A., Trkiyenin Bor Madenleri Ve zellikleri, Mhendis Ve MakineDergisi, Say 508, Mays
2002.
4. Ylmaz A., Her Derde Deva Hazinemiz Bor, Bilim ve Teknik Dergisi, say 414,38-48, Mays 2002.
5. Gennari F.C., Castro F.J., Gamboa J.J.A., Synthesis of Mg2FeH6 by Reactive Mechanical Alloying:
Formation and Decomposition Properties, Journal ofAlloys and Compounds, 339, 261267, 2002.
6. Bolarin A.M., Sanchez F., Ponce A., Martinez E.E., Mechanosynthesis ofLanthanum Manganite,
Materials Science and Engineering A, 454455, 6974, 2007.
7. Garcia-Contreras M.A., Fernandez-Valverde S.M., Vargas-Garcia J.R., Oxygen Reduction Reaction
On CobaltNickel Alloys Prepared By Mechanical Alloying,Journal of Alloys and Compounds, 434435,
522524, 2007.
8. Choi C.J., Preparation Of Ultrafine Tic-Ni Cermet Powders By Mechanical Alloying, Journal of Materials Processing Technology, 104, 127-132, 2000.
9. Valderruten J.F., Perez Alcazar G.A., Greneche J.M., Study Of FeNi Alloys Produced By Mechanical Alloying, Physica B, 384, 316318, 2006.
10. Birajdar B., Gruner W., Herrmann M., Perner O., MgB2 Bulk And Tapes Prepared By Mechanical
Alloying: Influence Of The Boron Precursor Powder, Supercond. Sci. Technol., 19, 512520, 2006.
11. Suryanarayana C., Mechanical Alloying and Milling, Marcel Dekker, New York, 359, 2004.
12. Ricceri R., Matteazzi P., Mechanochemical Synthesis Of Elemental Boron, International Journal of
Powder Metallurgy, 39(3), 48-52, 2003.
13. Boldyrev V., Boldyreva E., Mechanochemical of Interfaces, Materials ScienceForum, 88-90, 711714, 1992.
14. Tokumitsu K., Mechanochemical Reaction Between Metals and Hydrocarbons-Formation of Metal
Hybrides, Materials Science Forum, 88-90, 715-722, 1992.
15. Hida M., et al., Mechanochemical Reaction in Various Systems Involving Ionic and Hydrogen Bond
Crystals, Materials Science Forum, 88-90, 729-736, 1992.
16. Popovich A.A, et al., Mechanochemical Technology of Synthesis of Refractory Compounds and
Alloys Based Upon Them, Materials Science Forum, 88-90, 737-744, 1992.
17. Gney, B., Bor Oksitten Elementel Bor Tozu retim Parametrelerinin Aratrlmas, Yksek Lisans
Tezi, Gazi niv. Fen Bil. Enst., Ankara, 2007.
837

Fe2O3N ZOTERMAL NDRGENMES AKABNDE SAF CH4 LE

REAKSYONUYLA Fe3C TOZ SENTEZ
enol ETNKAYA, erafettin EROLU
stanbul niversitesi, Mhendislik Fakltesi, Metalurji ve Malzeme Mh. Blm Avclar Kamps,
34320 Avclar / stanbul
senol-c@istanbul.edu.tr seref@istanbul.edu.tr
ZET
Tek fazl Fe3C tozu, 800 Kde H2 atmosferinde Fe2O3in izotermal indirgenmesini takiben indirgenmi rnn saf CH4
ile reaksiyonu yoluyla sentezlenmitir. lk olarak Fe2O3in H2 atmosferinde farkl srelerdeki indirgenme davran incelenmitir. Daha sonra farkl indirgeme sresi (2.5 dk, 5 dk ve 10 dk) akabinde saf CH4 gaz ile deiik srelerde
karbrizasyon reaksiyonlar gerekletirilmitir. Arlk deiim lmleri ve XRD analizleri, tek faz Fe3C tozunun
yksek oranda indirgenmi ( 5 dk) tozun saf CH4 (15 dk) ile reaksiyonu sonucu elde edildiini gstermitir. Sentezlenen rnlerde morfoloji almalar SEM kullanlarak yaplmtr. Sentezlenen Fe3C tozunun partikl ve kristal
boyutlar srasyla 0.30.9 m ve 40130 nm olarak llmtr.
Anahtar Kelimeler: Fe3C toz sentezi, kat-gaz reaksiyonu, X-n difraksiyonu, morfoloji.
SYNTHESIS OF Fe3C POWDER BY ISOTHERMAL REDUCTION OF

Fe2O3 AND SUBSEQUENT REACTION WITH PURE CH4
ABSTRACT
Single phase Fe3C powder was synthesized by isothermal reduction of Fe2O3 in H2 atmosphere followed by reaction
of reduced product with pure CH4 at 800 K. Firstly, reduction behavior of Fe2O3 was investigated in H2 atmosphere at
various times. Then, carburization reactions were subsequently carried out after three different reduction times (2.5
min, 5 min and 10 min). Weight change measurements and XRD analysis showed that single phase Fe3C powder
was obtained by reaction of highly reduced ( 5 min) powder with pure CH4 ( 15 min). Morphological analysis
on the products was carried out by SEM. The particle and crystallite sizes of the synthesized Fe3C powder were
measured to be 0.30.9 m and 40130 nm, respectively.
Keywords: Fe3C powder synthesis, solid-gas reaction, X-ray diffraction, morphology.
1. GR
Fe3C (demir karbr / sementit), elik ve demir alamlarnn mekanik zelliklerini gelitirmesi ve CO2/H2 gazlarndan
hidrokarbon retiminde katalizr olarak kullanlmas nedeniyle byk bir teknolojik neme sahiptir. Genellikle elik
matriks ierisinde bulunduundan tek faz olarak elde edilmesi olduka gtr. Manyetik zellik gsterdii iin Fe3C
tozlarnn manyetik uygulamalar da vardr. Son zamanlarda nanoboyutlu Fe3C, karbon fiber, nanotp ve nanopartikllerin sentezinde katalizr olarak tercih edilmektedir [1].
imdiye kadar Fe3C sentezi iin pek ok yntem rapor edilmitir. Nikitenko ve dierleri [2], Fe-Fe3C nanokristal
partikllerini sonokimyasal metotla retmilerdir. Nelson ve Wagner [3], alkali redksiyon; Morjan ve dierleri [1],
838

lazer piroliz; Lee ve dierleri [4] ise kimyasal buhar biriktirme (CVD) yntemleriyle nanokristal Fe3C tozu sentezlemilerdir. Tm bu sentez teknikleri yksek scaklk, pahal hammadde veya karmak tehizat gerektirmektedir. Reaktan olarak nanopartikl Fe ve hidrokarbon gazlar kullanldnda [5, 6] ise Fe3C nispeten daha dk scaklklarda
olumaktadr. Bu ynteme ait baz detaylar aada verilmektedir.
Arabczyk ve dierleri [5], az miktarda K2O, Al2O3 ve CaO gibi oksitler ieren Fe3O4i H2 ieren atmosferde 853 Ke
stma srasnda nce Fee redklemilerdir. Daha sonra nanokristal Fe katalist tozunun CH4, CH4/N2 veya CH4/H2
gazlar ile 773853 K aralnda karbrizasyon kinetiini incelemiler ve Fe3C oluum artlarn aratrmlardr.
Sentezlenen rnlerin Fe3Cn yannda karbrlenmemi Fe ve serbest C ierdiini rapor etmilerdir. Karbrizasyon
prosesinin paralanm CH4 gaznn demir yzeyindeki adsorbsiyonu ile kontrol edildiini vurgulamlardr.
Narkiewcz ve dierleri [6], yukarda bahsedilen yntemle [5] sentezlenen Fe3Cde ayrntl karakterizasyon almalar yapmlardr. Aratrmaclar, sentezlenen rnlerin ortalama kristal (tane) boyutlarnn 4167 nm arasnda
olduunu ve nihai rnlerin arlka % 7.816.8 arasnda serbest C ierdiini rapor etmilerdir.
Bu almada ise Fe3C sentezi, Fe2O3 tozlarnn 800 Kde H2 atmosferinde izotermal indirgenmesi akabinde saf CH4
gaz ile reaksiyonu sonucu gerekletirilmitir. Sentezlenen rnlerin karakterizasyonu iin arlk deiim grafikleri
ile XRD ve SEM teknikleri kullanlmtr.
Deney dzenei temel olarak Ar (% 99,999), H2 (% 99,99) ve CH4 (% 99,5) gazlarn ieren gaz silindirlerinden, bu
gazlarn ak hzlarn hassas bir ekilde belirlemek iin ak lerlerden (Dwyer) ve ierisinde sentez reaksiyonlarnn gerekletirilecei kuvars tp (i ap: 20 mm) bulunan frn sisteminden (Strhlein) olumaktadr.
Sentez almalar iin gerekletirilen her bir deneyde ~10-3 mol (~0,1597 g) Fe2O3 tozu (SigmaAldrich) kullanlmtr. Tm deneyler ncesinde, oksit tozunun bnyesinde bulanabilecek olan nemin giderilmesi amacyla ~373
Kdeki etvde 10 dakikalk bekletme yaplm ve tartmlar 10-4 g hassasiyete sahip analitik terazide (Sartorius
BP110S) gerekletirilmitir. Tartlan Fe2O3 tozu almina kaykk ierisinde tp frnn merkezine yerletirilmitir.
Yaklak 25 K/dk stma hzyla 800 Ke klncaya kadar 85 cm3/dk ak hznda Ar gaz sisteme beslenerek stma
yaplmtr. Frn istenilen scakla ulatktan sonra oksit tozunun H2 gazyla (110 cm3/dk) deiik sreler iin indirgenmesi incelenmitir. Daha sonra farkl indirgeme srelerinin (2.5, 5 ve 10 dk) akabinde 40 cm3/dk ak hzndaki
saf CH4 gaz ile deiik srelerde deneyler gerekletirilmitir. Tm deneylerde frn oda scaklna soutuluncaya
kadar 85 cm3/dk ak hznda Ar gaz sistemden geirilmi ve akabinde sentezlenen rnlerin arlklar tespit edilmitir.
Sentezlenen rnlerinin faz analizleri, Rigaku D/Max2200/PC marka XInlar Difraksiyon (XRD) cihaznda; morfoloji incelemeleri ise, Jeol 5600 ve Jeol 6335 marka Taramal Elektron Mikroskoplarnda (SEM) gerekletirilmitir.
Reaksiyon rnlerinin kristal byklkleri ise, (1) nolu eitlikte verilen Scherrer forml kullanlarak hesaplanmtr.

(1)
Eitlik (1)de gsterilen , Cu K radyasyonunun dalga boyunu (0,15418 nm); , difraksiyon asn; t, kristal boyutunu ve , yar ykseklikteki pik geniliini (FWHM) ifade etmektedir. FWHM deerleri belirlenirken ~0,2lik cihazdan kaynaklanan pik genilemesi de dikkate alnmtr.
3.1. Fe2O3in H2 Atmosferinde zotermal ndirgenmesi
3.1.1. Fe2O3in ndirgenme Kinetii
ekil 1de 800 Kde Fe2O3in H2 atmosferinde indirgenmesi srasnda reaksiyon sresinin oksit tozundaki arlk
deiimine etkisi grlmektedir. ekildeki yatay kesikli izgiler, Fe2O3ten Fe3O4, FeO ve Fe dnmleri iin hesaplanm teorik arlk deiimlerini ifade etmektedir. Arlk deiimi grafiinden, 800 Kde 10 dk iinde % 100e
yakn bir indirgemenin gerekletii anlalmaktadr.
839

ekil 1. H2 atmosferinde reaksiyon sresinin Fe2O3in arlk deiimine etkisi (T = 800 K)

3.1.2. XRD Analiz Bulgular
ekil 2de balang tozuna (Fe2O3) ve indirgeme almalar sonras elde edilen reaksiyon rnlerine ait X-nlar
difraksiyon paternleri grlmektedir. XRD paternleri, 2.5 dklk indirgeme sresinin yeterli olmadn ve oluan Fein
yannda yapda hala demir oksitler (Fe2O3, Fe3O4 ve FeO) bulunduunu; 5 ve 10 dklk indirgeme sonras ise rnlerin sadece Fe ierdiini gstermektedir. Bu bulgular, arlk deiimleri ile kalitatif olarak uyumaktadr.
ekil 2. Balang tozunun (Fe2O3) ve bu tozun 800 Kde H2 atmosferinde deiik srelerdeki indirgenme
almalarna ait X-nlar difraksiyon paternleri
840

Kristal boyutlar, yar ykseklikteki pik geniliklerinden (1) nolu eitlik kullanlarak belirlenmitir. Balang malzemesi olan Fe2O3 tozunun kristal boyutunun ~75 nm, 2.5, 5 ve 10 dklk indirgeme sonras elde edilen rnlerin
kristal boyutlarnn ise >200 nm olduu hesaplanmtr.
3.1.3. Morfoloji ncelemeleri
Fe2O3 tozunun ve 800 Kde H2 atmosferinde indirgenmi rnlerin SEM grntleri ekil 3te verilmektedir. Fe2O3
tozu, kk kresel partikllerden (ap: 2080 nm); rnler ise kaba partikllerden olumaktadr. Reaksiyon sresi
2.5 dk olan rn morfolojisinin 5 ve 10 dklk numunelere kyasla farkl olduu (daha kk partikl boyutuna sahip
partiklleri de bnyesinde bulundurduu) SEM grntlerinden grlmektedir. XRD sonularna gre bu rnde
hala oksitler bulunduundan, morfolojideki kk partikllerin demir oksitler olduu anlalmaktadr. 5 ve 10 dklk
indirgeme sonras rn morfolojilerin birbirine benzedii ve partikl boyutlarnn
0.20.8 m arasnda deitii
belirlenmitir. Ayrca, indirgeme srasnda oluan ve birbirleri ile temas halindeki demir tozlarnn sinterletii grlmektedir.
ekil 3. (a) Fe2O3 tozu ve 800 Kde H2 atmosferinde (b) 2.5 dk, (c) 5 dk, (d) 10 dk indirgeme sonras elde edilen
reaksiyon rnlerinin SEM grntleri
3.2. H2 Atmosferinde Elde Edilmi rnlerin Saf CH4 Gazyla zotermal Reaksiyonu
3.2.1. Farkl Oranlarda ndirgenmi rnlerin Karbrizasyon Kinetii
Karbr sentezi almalar srasnda sinterlemeyi dk tutabilmek iin farkl indirgenme oranlarna sahip tozlarda
karbrizasyon almalar yaplmtr. ekil 4te 800 Kde karbrizasyon sresinin arlk deiimine etkisi grlmektedir. Arlk deiimlerinden, tam indirgeme sonras (10 dklk indirgeme sonras) yaplan karbrizasyon almalarnda, 15 dklk reaksiyon sresinin Fe3C oluumu iin yeterli olduu grlmektedir. 5 dk indirgenmi numuneye
ait eriden, CH4 gaznn balangta yapda kalan az miktardaki oksitleri indirgedii ve 15 dkda karbrizasyonun
tamamland anlalmaktadr. Daha dk indirgeme orannda (2.5 dklk indirgeme sonras) ise tek faz Fe3C sentezinin allan artlarda mmkn olmad grlmektedir.
841

ekil 4. 800 Kde 2.5, 5 ve 10 dk indirgenmi numunelerde karbrizasyon sresinin arlk deiimine etkisi
3.2.2. XRD Analiz Sonular
ekil 5te farkl indirgenme oranlar iin yaplan karbrizasyon almalar sonras elde edilen rnlere ait X-nlar
difraksiyon paternleri verilmektedir. XRD paternlerinden, 2.5 dklk indirgeme sonras yaplan karbrizasyon almalar neticesinde CH4 gaznn hem indirgeme hem de karbrleme iin yeterli olmad anlalmtr. Bu rnde
30 dk CH4 gaz ile reaksiyon sonrasnda dahi fazlarn deimedii (Fe, Fe2O3, Fe3O4 ve FeO) ilgili paternden
grlmektedir. Ancak, arlk deiimleri az miktarda arlk kazanm olduunu gstermektedir. Arlktaki art,
muhtemelen Fe3C oluumu nedeniyle olmaktadr. Bu faz, miktarnn az veya kristalleme derecesinin dk olmas
nedeniyle XRD ile saptanamamtr. H2 atmosferinde 5 ve 10 dk indirgenmi tozlarn 15 ve
30 dklk CH4 gaz
ile reaksiyonuyla elde edilen rnlerin esas itibaryla Fe3Cden olutuu ilgili paternlerden grlmektedir. Ayrca,
sentezlenen Fe3C tozlarnn kristal boyutlarnn 40130 nm arasnda olduu XRD paternlerindeki pik geniliklerinden tespit edilmitir.
842

ekil 5. Fe2O3in (a) 2.5 dk, (b) 5 dk ve (c) 10 dk H2 atmosferinde indirgenmesi sonras saf CH4 gaz (40 cm3/dk)
ile yaplan karbrizasyon almalarna ait rnlerin XRD paternleri
3.2.3. Morfoloji ncelemeleri
ekil 6da farkl indirgenme oranlar iin yaplan 15 ve 30 dklk karbrizasyon almalar sonras elde edilen rnlere ait SEM grntleri verilmitir.
843

ekil 6. Karbrizasyon almalar sonras elde edilen rnlere ait SEM grntleri.
H2 atmosferinde indirgeme sresi: (a), (b) 2,5 dk; (c), (d) 5 dk ve (e), (f) 10 dk
Saf CH4 gazyla reaksiyon sresi : (a), (c) ve (e) 15 dk; (b), (d) ve (f) 30 dk
SEM grtlerinden 2.5 dk indirgenmi numunenin karbrizasyonu sonras rn morfolojisinde belirgin bir deiim
olmad (kk demir oksit partiklleri hala mevcut) grlmektedir. 5 ve 10 dklk H2 atmosferinde indirgeme akabinde saf CH4 gazyla yaplan karbrizasyon almalar sonrasnda elde edilen Fe3Cn morfolojilerinin indirgenmi
rn morfolojileri (ekil 3) ile benzerlik gsterdii saptanmtr. SEM grntlerinden karbrizasyon sonras elde
edilen reaksiyon rn partikl boyutlarnn 0.30.9 m arasnda deitii belirlenmitir.
3.3. Deneysel Sonularn Literatrle Karlatrlmas
Literatrde [5, 6] nanokristal Fein 773853 Kde saf CH4 gaz ile reaksiyonu sonucu elde edilen rnlerin Fe3C, Fe
ve C [5] veya Fe3C ve C [6] ierdii rapor edilmitir. Bu almalarda [5, 6] rnlerde serbest karbon grlmesi, balang Fe3O4 tozunda bulunan K2O, Al2O3 ve CaO gibi yapsal oksitlerle ilikilidir. Bu oksitler, H2 atmosferinde indirgeme srasnda sinterlemeyi byk oranda engelleyerek nanoboyutlu Fe olumasn salamaktadr. Nanoboyutlu
partikller karbrizasyon srasnda katalitik etki gstermekte ve CH4n daha fazla paralanmasn salamaktadr.
Dolaysyla literatrde [5, 6] rapor edilen nihai rnlerde serbest C bulunmaktadr. Mevcut almada ise Fe partikllerinin indirgenme srasnda sinterlemesi nedeniyle CH4n katalitik olarak paralanmas mmkn grlmemitir.
4. SONULAR
Fe2O3in Ar atmosferinde stldktan sonra 800 Kde H2 gazyla izotermal indirgenmesi (5 dk) sonucu 0.20.8 m
aralnda deien partikl boyutuna ve >200 nm kristal boyutuna sahip Fe tozu elde edilmitir. Bu ilemin akabinde
yaplan saf CH4 gaz ile reaksiyonlar (15 dk) sonras partikl boyutu 0.30.9 m, kristal boyutu 40130 nm arasnda deien Fe3C tozlar sentezlenmitir. Arlk deiim lmleri ve XRD analizleri, sentezlenen Fe3C tozlarnn
olduka saf olduunu ve serbest C iermediini de gstermemitir.
TEEKKR
Bu alma, stanbul niversitesi Bilimsel Aratrma Projeleri Koordinasyon Birimince desteklenmitir. Proje numaras: 1453.
KAYNAKLAR
1. Morjan, I., Alexandrescu, R., Scarisoreanu, M., Fleaca, C., Dumitrache, F., Soare, I., Popovici, E., Gavril, L., Vasile, E., Ciupina, V., Popa, N.C., Controlled Manufacturing of Nanoparticles by the Laser Pyrolysis: Application
to Cementite Iron Carbide, Applied Surface Science, Vol. 255, pp. 96389642, 2009.
844

2. Nikitenko, S.I., Koltypin, Y., Felner, L., Yeshurun, I., Shames, A.I., Jiang, J.Z., Markovich, V., Gorodetsky, G.,
Gedanken, A., Tailoring the Properties of Fe-Fe3C Nanocrystalline Particles Prepared by Sonochemistry,
Journal of Physical Chemistry B, Vol. 108, pp. 76207626, 2004.
3. Nelson, J.A., Wagner, M.J., High Surface Area Nanoparticulate Transition Metal Carbides Prepared by Alkalide
Reduction, Chemistry of Materials, Vol. 14,
pp. 44604463, 2002.
4. Lee, D.W., Yu, J.H., Km, B.K., Jang, T.S., Fabrication of Ferromagnetic Iron Carbide Nanoparticles by a Chemical Vapor Condensation Process, Journal of Alloys and Compounds, Vol. 449, pp. 6064, 2008.
5. Arabczyk W., Konicki W., Narkiewicz U., Jasinska I., Kalucki K., Kinetics of the Iron Carbide Formation in
the Reaction of Methane with Nanocrystalline Iron Catalyst, Applied Catalysis A: General, Vol. 266, pp.
135145, 2004.
6. Narkiewcz, U., Guskos, N., Arabezyk, W., Typek, J., Bodzion, T., Konicki, W., Gasiorek, G., Kucharewcz, I.,
Anagnostakis, E.A., XRD, TEM and Magnetic Resonance Studies of Iron Carbide Nanoparticle Agglomerates
in a Carbon Matrix, Carbon, Vol. 42, pp. 11271132, 2004.
845

KMYASAL BUHAR BRKTRME YNTEMYLE Fe2O3 TOZU

VE METAN KULLANILARAK KARBON NANOTP BYTLMES
Melek CUMBUL ALTAY, erafettin EROLU
stanbul niversitesi, Mhendislik Fakltesi, Metalurji ve Malzeme Mhendislii
Blm, 34320, Avclar, stanbul, mcumbul@istanbul.edu.tr, seref@istanbul.edu.tr
ZET
Karbon nanotpler, <100> ynne sahip silisyum altlk zerinde Fe2O3 tozu ve metan gaz kullanlarak
kimyasal buhar biriktirme tekniiyle bytlmtr. C nanotp sentezinde iki yol kullanlmtr. Birinci
yolda, 1200 byme scaklnda C nanotp altlk zerinde sentezlenmitir. kinci yolda ise bytme,
n stlm CH4 frnn scak zonundan (1200 K) geirildikten sonra daha dk scaklklarda (10501150 K) gerekletirilmitir. Tp apnn artan scaklk ve sreyle artt gzlenmitir. Ayrca HR-TEM
grntleri, birbirine ve tp eksenine paralel olarak bym ok sayda grafit tabakalarndan oluan
tpleri gstermitir. Fe2O3-CH4 sistemi iin yaplan termodinamik analiz, artan CH4 miktaryla Fe
oksitFeFe3CFe3C+C dnmlerinin olabileceini ortaya koymutur.
Anahtar Kelimeler: Karbon nanotp, Kimyasal buhar biriktirme, Fe2O3, Metan
GROWTH OF CARBON NANOTUBE BY CHEMICAL VAPOR

DEPOSITION USING Fe2O3 POWDER AND METHANE
ABSTRACT
Carbon nanotubes were grown on a silicon substrate with a <100> orientation by chemical vapor deposition technique using Fe2O3 powder and methane gas. Two routes were used for C nanotube synthesis
experiments. In the first route, C nanotube was synthesized on the substrate at a growth temperature
of 1200 K. In the second route, growth was carried out at lower temperatures (1050-1150 K) after preheating CH4 gas by flowing it through the hot zone of the furnace (1200 K). It was observed that tube
diameter increased with increasing time and temperature. Also, HR-TEM images showed that the tubes
consisted of multi graphite layers grown parallel to each other and to the tube axis. Thermodynamic
analyses carried out in the system of Fe2O3-CH4 revealed that Fe oxideFeFe3CFe3C+C transformations take place with increasing CH4 amount.
Keywords: Carbon nanotube, Chemical vapor deposition, Fe2O3, Methane
1. GR
Nano yapl karbon malzemeler bilim dnyasnda olaanst elektronik, termal, mekanik, optik ve kimyasal zellikleri nedeniyle nem arz etmekte ve dikkat ekmektedir. Nanoyapl karbon malzemeler,
kimyasal sensr, alan emisyon malzemeleri, katalizr tayc, elektronik ve enerji depolama alanlarnda
potensiyel kullanm alanlarna sahiptir [1,2]. Karbon nano tpler (KNT) temel olarak ark dearj, lazer
kazma ve kimyasal buhar biriktirme (KBB) yntemleriyle sentezlenmektedir [3]. KBB, ok daha dk
scaklklarda karbon nano tp bymesine olanak salamasndan dolay daha ekonomik bir yntemdir. Bu yntemde, karbon ieren gazlarn, yksek scaklktaki altlk yzeyinde bulunan metal katalizr
partikllerle etkileimiyle gerekleen yzey reaksiyonlar (heterojen biriktirme reaksiyonlar) ile birlikte
846

karmak gaz faz reaksiyonlar (homojen piroliz reaksiyonlar) sonucu altlk zerinde kat karbon biriktirilmektedir [4]. Metal katalizr olarak Fe, Co ve Ni gibi gei elementleri KNT lerin bymesinde
nemli rol oynamaktadr. C kayna olarak genellikle seyreltilmi hidrokarbon (CH4, C2H2, C2H4) ve
CO gazlar kullanlmaktadr [5,6].
KNT morfolojilerinin sentez srasnda katalizr boyutu ve ekliyle ilikili olduu rapor edilmitir [6]. Farkl
bileim ve formlarda katalizrler ile C ieren deiik gaz bileimlerinin karbon nanotp sentezine etkileri
zerine aratrmalar devam etmektedir. Demir esasl katalizr kullanlarak deiik gaz ve karmlar
altnda karbon bymesine etkileri incelenmitir [7-12]. Mccaldin ve dierleri, Fe(NO3)3 tan elde edilen
Fe2O3 katalizr, C2H4/H2 gaz karmlar kullanarak 773- 1073 K scaklk aralnda 2 saat srede hem
nano fiber yapda hem de nano tp yapda karbon sentezlediklerini rapor etmilerdir. Ayrca, % 20 C2H4
- % 80 H2 gaz karmnda 773 K de elde ettikleri balk kl yapsnn artan reaksiyon scaklyla ok
cidarl nano tp morfolojisine dntn belirlemilerdir [7]. Schnitzler ve Zarbin, KNT sentezi hava
atmosferinde ferrosenin ssal bozunmasyla gzenekli silika cam zerinde ince film eklinde Fe2O3 katalizr hammaddesini biriktirmilerdir. Benzen ieren gaz karmn katalizr zerinden geirmek suretiyle 1173 K de 30 dak lk reaksiyon sresinde, 50-250 nm apnda ok cidarl KNT ler elde etmilerdir
[8]. Kong ve dierleri, n ilemlerle hazrlam olduklar almina ve silika nano partikl destekli Fe2O3
katalizr tozuyla 1273 K de CH4 gaz kullanarak tek duvarl KNT ler sentezlemiler ve nano tp byme
mekanizmasnn kk byme mekanizmasna gre gerekletiini rapor etmilerdir [12].
Katalizr tozu olarak n ilem grmemi Fe2O3 ve saf metan gaz kullanlarak KBB yntemiyle KNT
sentezi konusunda literatrde bir almaya rastlanmadndan mevcut alma yrtlmtr. Bu almada Si altlk zerinde saf metan gaz ile n stmal ve n stmasz artlarda scaklk ve byme
sresine bal olarak KNT sentez almalar gerekletirilerek optimum sentez koullar belirlenmitir.
Ayrca sentez prosesinin daha iyi anlalmasna ve C oluum artlarnn ngrlmesine yardmc olmas
iin termodinamik analiz yaplm, Fe2O3-CH4 sistemi iin muhtemel genel reaksiyon belirlenmitir.
2. MALZEME VE YNTEM
Mevcut almada kullanlan deney dzenei (ekil 1) esas olarak SiC stc elementli scak cidarl frn,
kuvars tp (20 mm apnda) ve gaz ak lerlerden olumaktadr. Deneysel almada katalizr olarak
<50 nm boyutlarnda Fe2O3 tozu kullanlmtr. Katalizr partikller, etanol/katalizr sspansiyonuna
daldrlmak suretiyle ultrason yardmyla <100> ynne sahip Si altlk zerinde datlmtr. Sentez
almas iin karbon kayna olarak metan (%99,5), reaksiyon ncesi ve sonrasnda inert atmosfer
salamak amacyla yksek safiyette argon (%99,999) kullanlmtr.
ekil 1. Kimyasal buhar biriktirme reaktrnn ematik grnm.

Bu almada, n stlmam ve n stlm metan gaz kullanlarak iki seri sentez almalar gerekletirilmitir. lk seride, n stmasz almada, altlk 1200 K frn merkez scaklna yerletirilmitir.
kinci seri, n stmal deneylerde, 1200 K de frn merkezinden metan gaz geirilerek reaktr tpnn
k tarafna yerletirilmi olan daha dk scaklklardaki altlk zerinde karbon bytme yaplmtr.
Bu deneylerde altlk (reaksiyon) scaklk aral 1050-1150 K olarak seilmitir. Her iki seride sabit
CH4 gaz ak hznda (13,4 cm3/dak) scakla ve sreye (15-60 dak) bal olarak karbon bytme
deneyleri yaplmtr. C sentez almalar iin TMerkez/TBytme/CH4 gaz ak hz/sre eklinde ksaltmalar kullanlarak optimum deneysel artlar ifade edilmitir.
847

Deneysel almalar sonucunda elde edilen rnlerin morfolojileri Taramal Elektron Mikroskobu (SEM
Jeol 5600, FEG-SEM Jeol 6335F) ve Yksek znrlkl Geirim Elektron Mikroskobunda (HR-TEM
Jeol 2100) incelenmitir. Termodinamik hesaplamalar Fe2O3-CH4 sisteminde serbest enerji minimizasyon yntemiyle [13] 1000- 1300 K scaklk aralnda yaplmtr. Hesaplamalarda 40 gaz faz (r. CH4,
CH3, C2H6) ve 6 kat faz (C, Fe, Fe3C, FeO, Fe2O3 ve Fe3O4) bileenleri gz nne alnmtr.
3. BULGULAR
3.1. n stlmam metan gaz ile sentez almas
n stlmam metan gaz kullanlarak 1200 K de 30 dakika bytme sresinde elde edilen numuneye
ait ekil 2 (a-c) de verilen HR-TEM resimleri rn morfolojisinin tps yapda olduunu gstermektedir.
ekil 2 (a) dan baz tplerin ularnn ak (ekilde A ile gsterilmi), bazlarnn ise kapal (B) olduu
anlalmaktadr. Ayrca, katalizrn, tp ierisinde belirli bir yere kademeli olarak ilerledii (C) ve yer
yer tp ierisindeki partikller arasnda boluk olduu grlmektedir. Koyu renkli keli alanlar (D) sinterlenme sonucu kabalam partiklleri temsil etmektedir. ekil 2 (b) de baz tplerde boumlar (E)
grlmektedir. ekil 2 (c), ucu kapal bir tpn HRTEM grntsn sergilemektedir. Grnt, tpn tek
cidarl deil ok cidarl olduunu (birden fazla grafit katman ierdiini) aka ortaya koymaktadr.
ekil 2. . n stlmam metan gaz kullanlarak 1200 K de 30 dak bytme sonrasnda

elde edilen rnn HR-TEM grntleri.
ekil 3 (a-c), 1200 K frn merkez scaklnda, 15, 30 ve 60 dak bytme srelerinde sentezlenen
numunelerin altlk zerindeki SEM grntlerini gstermektedir. ekilden grld zere rn morfolojileri i ie giren yumak eklinde uzun (r. 20 m) nanotplerden olumaktadr. Bu yaplarn aplar sreye bal olarak artmaktadr (ekil 3 c). Ortalama tp aplarnn 15 ve 30 dak lk bytme srelerinde
100 nm nin altnda, 60 dak sonra ise ~250 nm civarnda olduu tespit edilmitir.
ekil 3. n stlmam metan gaz kullanlarak 1200 K de a) 15 dak, b) 30 dak, c) 60 dak da elde
edilen rnlerin SEM grntleri ve d) rnlerin tp ap boyutuna bytme sresinin etkisi.
848

3.2. n stlm metan gaz ile sentez almas

1200 K deki frn merkezinden geirilen CH4 n frnn daha dk scaklk blgelerine (1050, 1100 ve
1150 K) yerletirilmi olan altlk zerindeki katalizrle reaksiyona girmesi sonucu elde edilen rnlerin
FEG-SEM resimleri ekil 4 (a-) de verilmitir. n stlmam metan gaz kullanlarak elde edilen rnlerde gzlenen morfolojilere benzer oluumlarn n stlm artlarda da ortaya kt tespit edilmitir.
Ayrca yer yer dall fiberler morfolojide yer almaktadr (rnein ekil 4 () da A ile iaretlenmi alan).
ekil 5 te deiik sreler iin bytme scaklnn rn ap boyutuna etkisi grafik halinde verilmitir.
ekil 4. n stlm (1200 K) metan gaz kullanlarak 1050 K (a-c), 1100 K (d-f), 1150
K (g-) bytme scaklnda 15 dak (a,d,g), 30 dak (b,e,h) ve 60 dak (c,f,) bytme
sonras elde edilen numunelere ait FEG-SEM grntleri.
ekil 5. n stlm (1200 K) metan gaz kullanarak deiik bytme sreleri iin
bytme scaklklarnn tp ap boyutuna etkisi.
849

Grafikten grld zere, artan bytme scakl ve srelerinde tp aplarnda art gereklemitir.
allan scaklklarda 15 ve 30 dak sre sonunda tp aplar 100 nm nin altndadr. Bu srelerde
sentezlenen rnlerin artan bytme scaklna bal olarak tp aplarndaki art hemen hemen ayn
seviyededir. Ancak, aptaki byme 60 dak iin daha fazla olup 1050 K bytme scaklnda ortalama
tp ap ~ 70 nm iken 1150 K de ise ~ 200 nm dir.
3.3. Termodinamik analiz
Fe2O3-CH4 sistemi iin yaplan termodinamik hesaplamalar sonucunda elde edilen denge kat hal diyagram, denge durumunda oluan rnlerin (kat ve gaz) miktarlar scaklk (1000-1300 K) ve C mol
kesrine (nC/(nFe+nC) bal olarak ifade ekil 6(a-c) de grafikler halinde verilmektedir
ekil 6. a) Scaklk ve C mol kesrine bal olarak denge kat hal diyagram,
b) C mol kesrinin kat rn % mol miktarlarna etkisi, c) rnlerin ksm basnlarnn C mol
kesri ile deiimi.
ekil 6 a da verilmi olan denge kat hal diyagramndan grld zere, tm scaklklar iin, yaklak 0,25 C mol kesrine kadar artan CH4 ile srasyla Fe2O3+Fe3O4, Fe3O4, Fe3O4+FeO ve FeO
bulunmaktadr. Bu faz alanlarndan sonra 1005-1300 K scaklk aralnda artan CH4 miktaryla birlikte
FeO+Fe, Fe, Fe+Fe3C, Fe3C ve Fe3C+C faz alanlar grlmektedir. Ayrca, 1000 K de dier scaklklarda bulunan faz alanlarna ek olarak FeO+Fe3C ikili faz ile FeO+Fe3C+Fe l faz alanlar olumaktadr. ekil 6 b, denge durumunda sistemde oluan kat rn % mol miktarlarna C mol kesrinin etkisini
gstermektedir. Grafikten, CH4 miktar arttka ikili veya l faz blgelerinde ortaya kan yeni fazlarn
miktar artt, mevcut olann miktarnn ise azald grlmektedir.
Tek faz blgelerinde ise ilgili bileenin miktar % 100 olmaktadr. rnein, Fe3C+C blgesinde Fe3C faz
miktar azalrken, ortaya kan C un miktar artmaktadr. Scakln mol miktarlarna etkisi yaklak 0,74
C mol kesrine kadar grlmektedir. Ancak, bu deerden sonra esas itibaryla etkisi olmamaktadr. ekil
850

6 c verilen grafik ise Fe2O3-CH4 sisteminde 1000-1300 K aralnda bulunan 10-5 atm den byk olan
rnlerin ksmi basnlarnn C mol kesri ile deiimini gstermektedir. Bu grafikten elde edilen nemli
sonular sistem iin yle zetlenebilir: H2O, CO2, H2, CO ve CH4 gaz faznn bileenleridir. C mol kesri
arttka, H2O ve CO2 in ksmi basnlar azalmakta, buna karlk H2 ve CH4 ksmi basnlar ykselmektedir. Yaklak 0,15 C mol kesri civarnda CO ve H2 e ait ksm basn erileri CO2 ve H2O erilerini
kesmektedir. Daha yksek C mol kesirlerinde H2 ve CO ksm basnlar dier iki gaz bileenine kyasla
daha fazladr. Sabit C mol miktar iin scaklk arttka, CO2, H2O ve CH4 ksm basnlar azalmaktadr.
Ayrca, dk ksmi basnlara sahip tali gaz bileenleri de (C2H4, H2CO, CH3, Fe(OH)2, H, HCO, HO)
sistemde bulunmaktadr.
Oluan rnlerin miktarlar gz nne alnarak olas kimyasal reaksiyonlar Fe2O3-CH4 sistemi iin belirlenmitir. Fe2O3+Fe3O4 faz alannda gaz faznda CO2 ve H2O ana gaz bileeni olarak yer almakta ve
artan CH4 miktaryla Fe3O4 miktar artmakta ve Fe2O3 miktar azalmaktadr. Buna gre Fe2O3+CH4
sisteminde Fe3O4, CO2 ve H2O oluumu iin ana reaksiyon Denklem 1 ile ifade edilebilir.
6Fe2O3(k) + 1/2CH4 4Fe3O4(k) + H2O+ 1/2CO2 (1000-1300 K iin Gr<0)
(1)
Artan CH4 ile Fe3O4 ten FeO e dnm iin muhtemel ana reaksiyon Denklem 2 de verilmitir.
2Fe3O4(k) + 1/2CH4 6FeO(k)+ H2O + 1/2CO2 (1000-1300 K iin Gr<0)
(2)
FeO+Fe faz alannda CO miktar CO2 ten daha yksek olduu ekil 11 den grlmektedir. Dolaysyla
FeO ten Fe e dnm reaksiyonu Denklem 3 ile gsterilebilir.
3FeO(k) + CH4 3Fe(k) + 2H2O + CO (1100-1300K iin Gr<0)
(3)
Ayrca, Fe ieren faz alanlarnda, artan CH4 miktar ile CO ve H2 nin ksmi basnlar artmakta, buna
karlk CO2 ve H2O in ksmi basnlar dmektedir (ekil 5.5). Bu durum CH4 n Denklem 3 te ortaya
kan H2O ve CO2 in CH4 ile gaz faznda reaksiyona girebileceine iaret etmektedir (Denklem 4-5).
CH4 + H2O CO + 3H2 (1000-1300 K iin Gr<0)
(4)
CH4 + CO2 2CO + 2H2 (1100-1300 K iin Gr<0)
(5)
Ayrca, metann paralanmas (Denklem 6) sonucu oluan kat C un, CO2 ile reaksiyona girerek (Boudouard reaksiyonu, Denklem 7) CO oluumuna katkda
bulunaca dnlmektedir.
CH4 C(k) + 2H2 (1000-1300 K iin Gr<0)
(6)
CO2 + C(k) 2CO (1000-1300 K iin Gr<0)
(7)
Fe3C ise yksek metan miktarlarnda Denklem 8 de verilmi olan reaksiyon uyarnca olumaktadr:
3Fe+C(k) Fe3C (1000-1300 K iin Gr<0)
(8)
Oluan C un stokiometrik orandan fazla olduu durumda ise Fe3C yannda serbest C da olumaktadr.
Fe2O3-CH4 sisteminde Fe3C+C oluumu iin nemli genel reaksiyon Denklem 9 ile ifade edilebilir.
3Fe2O3(k) + 12CH4 2Fe3C(k) + C(k) + 9CO + 24H2 (1000-1300 K, Gr<0)
(9)
4. TARTIMA
Karbon nanotp bymesi metan gaznn katalizr partikl zerinde muhtemelen uygun kristallografik
yzeylerde paralanmas sonucu C oluumu, C atomlarnn partikl iinde yaynm ve nanopartikln
belirli yzeylerinde birikerek bymesi eklinde aklanmaktadr [14]. Si altlk zerinde katalizrlerin
bulunmad blgelerde C birikiminin gzlemlenmemesi KNT yaplarn katalizr etkisiyle CH4 n paralanmas sonucu bydn ortaya koymaktadr. KNTlerin sentezi iin katalizr seimi yannda CH4
gaznn paralanma derecesi veya sentez scakl nemli bir rol oynamaktadr. Bu nedenle CH4 gaz-
851

nn paralanma derecesini artrmak iin gaz 1200 K de n stma ilemine tabi tutulduktan sonra daha
dk scaklklarda (1050-1150 K) altlk zerinde C bytme ilemleri yaplmtr. n stlm CH4 gaz
kullanlarak gerekletirilen almalarda, rn morfolojisinin n stlmam artlardaki morfolojiyle ayn
olduu belirlenmitir. Artan sentezleme srelerinde ise elde edilen rnlerin morfolojik zellikleri deimemi, sadece nceden oluan tp zerinde pirokarbon birikmesi nedeniyle tp aplarnda zamana
bal olarak art meydana gelmitir. Ancak, bu artlarda (n stlm), n stlmam artlara gre daha
dk ortalama aplara sahip tpler sentezlenmitir. Bu durum nispeten dk bytme scaklndan
kaynaklanmaktadr. HR-TEM analizi, sentezlenen tplerin ok cidarl olduunu sergilemitir. Cidar says katalizr partiklnn boyutlaryla ilikilendirilmektedir [15]. Mevcut almada kullanlan Fe2O3
tozunun ortalama partikl boyutunun ~38 nm olmas nedeniyle ok cidarl nanotpler elde edilmitir.
Metal katalizr - altk etkileimlerinin, byme mekanizmasnda nemli rol oynad rapor edilmitir [6].
Katalizr-altlk etkileimi gl olduunda karbon nano tp, katalizr partikl tabanda kalacak ekilde
(kk byme modeli) bymektedir. Altlk - katalizr etkileimi zayf olduunda ise katalizr partikl,
oluan karbon tp tarafndan altlktan koparlarak tpn ucunda bymeyi tevik etmektedir (u byme
modeli) [15]. Mevcut almada elde edilen morfoloji grntlerinden bahsi geen tp byme modellerinden genel olarak karbon nanotplerin kk modeline gre byd dnlmektedir.
Fe2O3-CH4 sisteminde 1000-1300 K scaklk aralnda atmosferik basn altnda yaplan termodinamik hesaplar, Fe2O3 in saf CH4 atmosferi altnda Fe e indirgendiini ve artan CH4 miktaryla serbest
C un da olutuunu gstermektedir. Termodinamik analiz, CH4 miktar arttka kat fazdaki kimyasal
deiimlerin Fe2O3 Fe3O4 FeO Fe Fe3C Fe3C+C, ekilde olduunu ngrmektedir.
Deneysel almalar, serbest C un olduu alan iinde kalacak ekilde (diyagramlarda sa alt blgede)
gerekletirilmi olup allan scaklklarda katalitik etkiyle metann paralandn deneysel almalarda teyit etmitir.
5. SONU
Fe2O3 tozu kullanlarak ok cidarl C tpler deiik srelerde sentezlenmitir. Deneysel bulgular, scaklk ve sre arttka tp apnn bydn1 gstermitir. Nano tp sentezi iin optim3um -artlarn
1200 K/1200 K/13,4 cm3.dak- /15-330 da1k, 1200 K/1050- 1150 K/13,4 cm .dak 1/15-30 dak ve 1200
K/1050 K/13,4 cm .dak- /60 dak olduu tespit edilmitir. HR-TEM analizi, sentezlenen tplerin ekseni
boyunca birbirine paralel grafit tabakalardan olutuunu sergilemitir. Nanotplerin muhtemel byme
mekanizmalarnn elde edilen HR-TEM ve SEM grntlerinden genel olarak kk byme mekanizmasna gre gerekletii sonucuna varlmtr. Fe2O3-CH4 sisteminde yaplan termodinamik analiz,
artan CH4 miktaryla Fe oksitFeFe3CFe3C+C dnmlerinin olduunu gstermektedir. Ayrca,
denge halindeki kat ve gaz fazlardaki CH4 miktarna bal olarak ortaya kan bileim deiimlerinden
Fe2O3-CH4 sistemindeki muhtemel genel reaksiyon 3Fe2O3(k) + 12CH4 2Fe3C(k) + C(k) + 9CO +
24H2 olarak belirlenmitir.
TEEKKR
Bu alma, ..Aratrma Projeleri Birimi tarafndan 1459 numaras ile desteklenen proje ile M. C. Altay
n doktora tezinin bir blmdr.
KAYNAKLAR
1. Mamalis, A. G., Vogtlnder, L. O. G., Markopoulos, A., Nanotechnology and Nanostructured Materials: Trends in Carbon Nanotubes, Precision Engineering, 28, 16-30, 2004.
2. Paradise, M., Goswami, T., Carbon Nanotubes - Production and Industrial Applications, Materials
& Design, 28, 1477-1489, 2007.
3. Kuchibhatla, S. V. N. T., Karakoti, A. S., Bera, D., Seal, S., One Dimensional Nanostructured Materials, Progress in Materials Science, 52, 699-913, 2007.
4. Delhas, P., Fibers and Composites, Taylor & Francis, London, U.K., 2003.
5. Yang, P., The Chemistry of Nanostructured Materials, World scientific publishing, New Jersey,
U.S.A., 2003.
6. Dupuis, A. - C., The Catalyst in the CCVD of Carbon Nanotubes - A Review, Progress in Materials
Science, 50, 8, 929-961, 2005.
7. Mccaldin, S., Bououdina, M., Grant, D.M., Walker, G.S., The Effect of Processing Conditions on Carbon Nanostructures Formed on An Iron-Based Catalyst, Carbon, 44, 2273-2280, 2006.
852

8. Schnitzler, M. C., Zarbin, A. J. G., Utilization of Iron Oxide Film Obtained by CVD Process as Catalyst
to Carbon Nanotubes Growth, Journal of Solid State Chemistry, 182, 2867-2872, 2009.
9. Singjai, P., Thongtem, T., Kumfu, S., Thongtem, S., Synthesis of CNTs via Ethanol Decomposition
Over Ball-Milled Fe2O3 Coated Copper Sheets, Inorganic Materials, 43, 2, 143-147, 2007.
10. Homma, Y., Kobayashi Y., Ogino, T., Takagi, D., Ito, R., Joon Jung, Y., Ajayan, P., M., Role of Transition Metal Catalysts in Single-Walled Carbon Nanotube Growth in Chemical Vapor Deposition, The
Journal of Physical Chemistry B, 107, 12161- 12164, 2003.
11. Narkiewicz, U., Podsladyy, M., Jedrzejewski, R. J, Pelech, I., Catalytic Decomposition of Hydrocarbons on Cobalt, Nickel and Iron Catalysts to Obtain Carbon Nanomaterials, Applied Catalysis A:
General, 384 , 27-35, 2010.
12. Kong, J., Cassell, A. M., Dai, H., Chemical Vapor Deposition Of Methane for Single-Walled Carbon
Nanotubes, Chemical Physics Letters, 292, 567-574, 1998.
13. Erolu, S., Bakan, H., Chemical Vapor Reaction, Mo2C Powder Synthesis, Thermodynamic Analysis, Key Engineering Materials, 264-268, 121-124, 2004.
14. Yoon, S., Lim, S., Hong, S., Qiao, W., Whitehurst, D. D., Mochida, I., An, B., Yokogawa, K., A Conceptual Model for the Structure of Catalytically Grown Carbon Nano-Fibers, Carbon, 43, 1828-1838,
2005
15. Ando, Y., Zhao, X., Sugai, T., Kumar, M., Growing Carbon Nanotubes, Materials Today, 7, 10,
22-29, 2004.
853

SINTERING and
SINTERING
ATMOSPHERES
www.turkishpm.org
854

INVESTIGATION OF POWDER INJECTION MOLDING STEATITE:

RHEOLOGY, DEBINDING AND SINTERING PARAMETERS
Levent URTEKN *, brahim USLAN ** and Bedri TU **
* Dumlupinar University, Department of Mechanical Engineering,Kutahya, TURKEY,
lurtekin@dpu.edu.tr
**
Gazi University, Faculty of Technology, Department of Materials Technology, 06500, Ankara, Turkey,
iuslan@gazi.edu.tr , btunc@gazi.edu.tr
ABSTRACT
Steatite ceramics have been produced by dry pressing, extrusion, slip casting, wet pressing and injection moulding methods. In this study, steatite samples were produced by powder injection moulding (PIM) using a feedstock
based on a polyethylene glycol (PEG), polypropylene (PP) and stearic acid (SA) formulation. Rheological experiments are performed using a capillary rheometer on mixtures with 50-60 vol.% powder. A volume fraction of 58
vol.% shows the best properties and is used for injection moulding. Two procedures were used for debinding the
injection moulded samples, solvent and thermal methods. The solvent debinding is carried out at 60 0C in water.
Thermal debinding parameters are deduced from thermogavimetric (TGA) analysis. Sintering is performed at 12001300 0C for 2-4 hours in air. The theoretical densities of 98-99% are realized. Furthermore, the porosity associated
with density changes was observed by electron microscopy.
Keywords: Powder Injection Molding, Rheolghy, Debinding
1. INTRODUCTION
There are many shaping method of ceramics such as slip casting, dry pressing, wet pressing, hot pressing, isostatic
pressing and injection molding. Powder injection molding is a method in which production of inorganic powder engineering components is performed using injection molding equipments and debinding processes. If the used powder
is metallic, it is known as metal injection molding (MIM). On the other hand, if it is ceramic, it is named ceramic injection molding (CIM) [1]. The application area of this method is fairly large. For examples, these areas are complex
shape, machine parts, small clock parts, robot arms, medicine equipment parts, tooth prosthesis, office equipments,
laboratory parts, engine parts of air space vehicle, printing circuits, automotive parts, hand equipments, cutting
tools, electric and electronic parts, gun parts, high temperature ceramics can be given as examples of PIM application [2-3]. In 1999 the estimated market value of PIM system was found to be 664 million US dollars [4]. In 2003
value of PIM process market was 1 billion US dollars. It is estimated that PIM market will be 2 billion dollars until
2010 [5]. Today PIM process finds large application areas in USA, European countries, Israel, China and Indian.
Lately, PIM has been used in micro processing like as 400 nm alumina grains and 5 m big parts. These dimensions of PIM processing are useful for micro electromechanical systems (MEMs) and micro systems technologies
(MST). Both have a market value in the world with 68 billion US dollars [6]. Steatite is a natural mineral. Its formula
is (Mg(Si4O10)(OH)2), magnesium silicate. Steatite ceramics can be produced by dry pressing, extrusion, casting
and semi wet pressing. Steatite, which has very good mechanical and electrical properties, can show high densities
when it is sintered. By these properties, steatite can be used as a good electric insulator in the electrical equipment
industry. Steatite has applications such as socket, control units, insulating bed, low voltage power protection and
plates. [7-8].
Karatas et al. [9] studied on rheology of prepared feedstock produced using steatite powder and polyethylene
based binders. Loebbecke et al. [10] this work focuses on the flow behaviour of alumina feedstocks with high solids
855

content, based on two different binder systems and two different alumina powders. By varying particle size, organic
binder system, and solids content, the rheological properties of the feedstocks were modified significantly. Vielma at
al [11]; in this experimental work, injection molding of alumina parts was performed with a developed binder system
based on high density polyethylene (HDPE), paraffin wax (PW) and stearic acid.
Rheological character was determined by torque rheometer and performed with alumina by 50-60 % in volume. The
flow type was pseudo-plastic and optimum flow occurred at 58 % alumina powder load by volume. 99 % therotica1
density was obtained by sintering at 600 0C for 2 hours.
Soykan [12]; used 80-90 wt % talc, 10 wt % clay and 5-10 wt % flux mixture by adding TiN and barium carbonate to
this mixture. Clay provided mass formation, barium carbonate affected liquid flow during sintering. Sotomayor at al
[13] have studied rheological properties of binding system consisting of HDPE and paraffin wax, and stainless steel
powders produced with gas atomization method by using capillary rheometer.
The effects of powder loading and different powder distributions on rheological parameters were studied. In a study
by Ahn at al. [14], they have examined the combination of different binding systems under four main bases, First of
these is the rheological action of stainless steel with binders, the second is the feeding stock characteristics which
can be listed as shear speed, viscosity and injection pressure. The third is the relationship of powder-binder and the
fourth basis is carrying out the control of speed and powder-binder mixture depending on the shear speed.
In this study capillary rheometer trials were carried out for binding mixture that contains 50-60 % steatite powder
by volume for a temperature range of 170-220 0C. The homogeneity of the mixture and optimum powder loading
were determined empirically. After performing injection molding debinding was carried out by two means solvent
and thermal.
Selecting a multi-system binder, i.e. preferring binding system which consists of PEG/PP/SA, was due to avoiding
deformations that may occur during debinding. Debinding speed and temperature were determined by TGA. Sintering was carried out 99% theoretical density was obtained for optimum sintering temperature of 1300 0C at 4 hours
of waiting period. The rest of the paper is organized as follows: in Section 2, we will present experimental model
under study. In Section 3, we gave the experimental results. The conclusions of the research are summarized in
Section 4.
2. EXPERIMENTAL METHOD
Material: The used steatite powder was provided from Kale Chemical Co. Its composition is given in Table 1. Steatite C221; optimum dielectrically property according to European Electro Technical Standard Institution (CENELEC)
norm as CEI 672-1. Sockets, insulating beds and low voltage power fuse are some usage areas of steatite. Table
2 shows some of their physical and mechanical properties. The particle size distribution is as follows: d10=0.74,
d50=3,96 and d90=15.92m.
Table 1. Composition of Steatite, wt.%
SiO
60
MgO
30
Al2O3
2.5
CaO
1
Fe2O3
1.5
Na2O3 + K2O
0.5
tempering losses
4.5
Table 2. Properties of Steatite

porosity (%)
density, g/cm3
hardness, Mohs
modulus of elasticity, MPa
tensile strength, MPa
*
bending strength, MPa
compression strength, MPa
0
2.7
7-8
110
50-51
124-140
900
Feedstock: The evaluation of the feedstock rheological properties is based on the viscosity and its shear sensitivity
and temperature sensitivity [3]. Water based binder of composition (wt.%) 65% PEG 8000, 30% polypropylene (PP)
and 5% stearic acid (SA) were used to prepare feedstocks. Density of the binder mixture was 1.084 g/cm3.
856

Rheology: Rheological evaluation serves as a quality control tool in a PIM operation. Maximum useful viscosity for
the mixture is 103 Pa.s at the molding temperature. [3].The rheological properties of the feedstocks were analysed
capillary rheometer. Then rheological properties of feedstock were measured at four temperatures from 170 C to
220 C.
Molding: The feedstock was molded Arburg Allrounder 220S injection molding machine in the PM Laboratory of
Gazi University. The molding parameters are shown in Table 3. Tensile and bending samples were produced under
the PIM parameters.
Molding
pressure, bar
Bending
samples
Tensile
samples
Table 3. PIM operation parameters

Feedstock
Holding
Barrel temperature,
flow rate,
pressure, bar
C
cm3/s
Mold
temperature,
C
Green
density
(%)
1000-1250
600
35-185-190-195-200
15
20
70
1350
600
35-190-195-200-205
17-25
20
72
Debinding: Debinding was performed into two ways. For PEG8000, distilled water was used as a solvent PP and
SA were debound using thermal method during the sintering. Moulded parts were immersed into distilled water at
60C for 24h. The samples were oven dried at 50C for 5h and weighed.
Thermal analysis methods are widely used in the ceramic industry for research and quality control purposes. Thermal behavior and removal of the binders from the PIM feedstocks prepared were studied by TGA analysis. Heating
rate was 1 C/min until 400 C and holding time was 30 min. at this temperature for thermal debinding (pre-sintering). Heating up rate was same to 550 C, but the holding time was changed as 60 minutes at this temperature. Fig.
1 gives TGA analysis of the feedstock.
Fig. 1. Thermo-gravimetric analysis (TGA) of the feedstock

Sintering: Sintering process was carried out for different temperatures between 1200-1300 C and different holding
times between 2-4 hours. Heating rate to sintering temperature and cooling rate to room temperature were same as
5 C/min. Fig. 2 shows thermal debinding and sintering procedures.
857

Fig. 2. Pre-sintering and sintering processes

3. EXPERIMENTAL RESULTS
Powder additions to the binder raise the viscosity. Viscosity got over 103 Pa.s rapidly after 58 vol. % steatite loading
and critical solid loading was 60 vol. % as seen in Fig. 3. At 160-170 C, the viscosity values were over 103 Pa.s for
all feedstocks. The viscosity must be evaluated over the range of temperatures and shear rates expected during
molding.
Fig. 3. (a) Viscosity versus temperature (b) viscosity versus shear rate (pressure :1.36 MPa)
The melt volume index (MVI), defined as the extruded volume over 10 min., also illustrates that the critical solid
loading is 60 vol. % steatite. The mixture is not flowing above this loading ratio. Spiral and direct flow was observed
at 55-58 vol. % steatite loading. Loaded mass kept constant, the addition of steatite powder to the binder formulations caused a decrease at the MFV values, as a result, increased the temperature required to achieve a good
capillary flow.
Burning was observed in feedstocks after 230 0C (Fig 3.a). Shear rate increased when decreasing viscosity (Fig
3.b). This is known as pseudo plastic behavior. 102-105s-1 intervals are desired values for feedstocks. Viscosity
increased when the solid loading was increased. Viscosity was 800 Pa.s at 58 vol % solid loading. Capillary rheo-
858

logical tests were not achieved for 60 vol % solid loading because of high viscosity (Fig. 4.a) Melt volume index was
also higher at high temperatures than lower ones (Fig. 4.b).
Fig. 4. (a) Viscosity versus steatite loading (b) the melt volume index versus steatite loading
(pressure: 1.36 MPa )
About 90% of binder was successfully extracted by solvent debinding. Debinding rations of PEG in water by solvent
debinding process were approximately 90.7 %, 91.7 % and 92.17 % for bending, graded and tensile samples. The
remaining amount of binder (skeleton binder, PP, and lubricant, SA) was also burned by thermal debinding process
(pre-sintering). Fig. 5 shows debinding ratios in water by time for three different samples.
Fig. 5. Weight loss of steatite compact immersed in water for various extractive times
Densities of the bending and tensile samples were the lowest at 1200 C and increased when the temperature
was increased (Fig. 6). Increasing has continued obviously until 1275 C for different holding times. Any significant
change has not observed at temperatures above 1275 C for 4h. Theoretical densities were 97 % and 98 % under
sintering conditions of 1250 C for 4h and 1275 C for 2h respectively. Maximum density values of the samples were
obtained at 1300 C for 4h. After waiting for 4h at 1300 C, the porosities were found close and density was found
maximum. Similar results were obtained for tensile samples.
859

Fig. 6. Theorical densities of (a) three point and (b) tensile samples versus holding time at different sintering
temperatures
For 1300 C for 4 h, maximum linear shrinkages of tensile and bending samples were 18.17 % and 18.18 %, respectively (Fig. 7).
Fig. 7. Linear shrinkages of (a) three point (b) tensile samples versus sintering time for different holding times
Images obtained by SEM analyses are illustrated in Fig. 9. Sintered samples have open porosity at 1200 C (Fig.
8.a). If sintering temperature was increased to 1300 C, most of porosities were close and samples were near full
density (Fig. 8.b).
b) surface contact (1300 0C)

a) interconnected porosity (1200 0C)
Fig. 8. Pore structure in sintering samples (SEM and Optic images)
860

Graded and bending samples of green part, debinding and sintering are shown in Fig. 9.a and Figure 9.b, respectively. Figure 9.c shows sintered tensile sample.
Fig. 9. Green, debinding and sintered samples

4. CONCLUSIONS
Critical steatite solid loading with the PEG-based binder is 60 vol. %. Temperature ranges 170 to 200 C are

suitable for molding of PEG-based feedstocks with steatite solid loadings 50, 55, 56 and 58 vol. %. The rheological behavior of feedstock flow was found to be pseudo-plastic. In this behavior by increasing shear rate
viscosity is decreasing. This behavior is known the desired property.

90.7 % PEG for bending sample, 91.7% PEG for stepped sample and 92.17% PEG for tensile sample were
removed easily from system. When debinding, the possibility of distortion was decreased. The removal of
binder was different for each sample. The reason of this behavior was related with the dimensions and package
efficiency of samples.

At 400 0C, all binder was completely debinding for PEG/PP/SA with TGA method. Thermal debinding rate was
kept very small such as 1 0C/min. The maximum shrinkage was found to be 18.18%. After injection molding
green density was found 70-72%. The highest density (99 %) values were obtained by sintering this steatite
powder at 1300 C.
ACKNOWLEDGEMENTS
The authors are grateful to Prof. Dr. Suleyman SARITAS. The authors acknowledge the support of Gazi University
(DPT Projects No: 2001K120590 and 2003K120470) labs for facilitating the experimental studies.
REFERENCES
1. R.M. German, (in Turkish) editors: S. Sartas, et al., Powder Mettalurgy, First Press, 2007, Uyum Agency,
Ankara.
2. C. Karatas, Rheology for feedstocks used powder injection moulding, 1997, Ph.D. Thesis, Gazi University,
Ankara.
3. R.M. German, A. Bose, Injection Molding of Metals and Ceramics, 1997, Metal Powder Industries Federation,
New Jersey.
861

4. P.A. Hauck, Powder Injection Molding: Current and long term outlook, Int. J. Powder Metallurgy, 2000, vol.
36, no. 3, pp. 29-30.
5. C. Karatas and S. Sartas, Powder Injection Molding: A high technology manufacturing process, Journal of
The Faculty Engineering And Architecture of Gazi University, 1998, vol.13, no. 2, pp. 193.
6. R. Zauner, Micro Powder Injection Moulding, Microelectronic Engineering, 2006, vol. 83, pp. 1442-1444.
7. L. Urtekin Investigation of the effect of molding and sintering parameters on properties of powder injection
molded steatite ceramics, 2008, Ph.D. Thesis, Gazi University, Ankara.
8. L. Urtekin, I. Uslan, and B. Tuc Investigation of Properties of Powder Injection-Molded Steatites, Journal of
Materials Engineering and Performance, DOI: 10.1007/s11665-011-9901-8.
9. C. Karatas, A. Kocer, H.I. Unal, S.Sartas, Rheological Properties of Feedstocks Prepared with Steatite Powder and Polyethylene-Based Thermoplastic Binders, J. Materials Processing Technology, 2004, vol. 152, no.
1, pp. 77-83.
10. B. Loebbecke, R. Knitter, J. Hauelt, Rheological properties of alumina feedstocks for the low-pressure injection moulding process Journal of the European Ceramic Society, 2009, vol. 29, no. 9, pp 1595-1602.
11. P. T. Vielma, A. Cervera, B. Levenfeld, A. Vrez, Production of alumina parts by powder injection molding with
a binder system based on high densitypolyethylene, Journal of the European Ceramic Society, 2008,vol. 28,
no. 4, pp 763-771.
12. H.S. Soykan, Low-temperature fabrication of steatite ceramics with boron oxide addition, Ceramics International, 2007, vol. 33, pp. 911-914.
13. M.E. Sotomayor, A. Vrez, B. Levenfeld, Influence of powder particle size distribution on rheological properties
of 316L powder injection moulding feedstocks Powder Technology, 2010, vol. 200, no. 1-2, pp. 30-36.
14. S
Ahn,
S.
J.
Park,
S.
Lee,
S.
V.
Atre,
R.
M.
German
Effect
of
powders
and
binders
on
material
properties
and
molding
parameters
in
iron
and
stainless
steel
powder
injection
molding
process
Powder Technology, 2009, vol. 193, no. 2, pp 162-169
15. B.C. Mutsuddy and R.G. Ford, Ceramic Injection Molding, 1995, U.S.A.
862

SNTERLEME SICAKLII VE SRESNN YKSEK ORANDA GZENEK

EREN DEMR ESASLI KOMPAKTLARIN BASMA MUKAVEMETNE ETKS
* stanbul niversitesi Metalurji ve Malzeme Mhendislii Blm, Avclar, stanbul.
ZET
Bu almada; toz metalurjisindeki boluk yapc teknii kullanlarak yksek oranda gzenek ieren demir esasl
kompaktlar retilmitir. Boluk yapc malzeme olarak 0,71-1,00 mm partikl boyut aralna sahip dzensiz ekilli
karbamit, n alaml Distaloy AB demir tozuyla kaplanm ve 200 MPa basn altnda tek ynl preslenerek ap
12 mm ykseklii yaklak 18 mm olan ham kompaktlar elde edilmitir. Ham kompaktlar ierisindeki karbamitin
%95i oda scaklnda suda zndrlerek uzaklatrlmtr. Ham kompaktlar hidrojen atmosferi altnda 1150
C ile 1200 C de 60 dakika ve 1200 C de 120 dakika sinterlenmilerdir. 60 dakika sinterleme sresi iin sinterleme scaklnn 1150 Cden 1200 Cye karlmas kompaktlarn maksimum basma mukavemetini %41 orannda
arttrmtr. Fakat 1200 Cde 120 dakika sinterlemenin yksek oranda gzenek ieren demir esasl kompaktlarn
basma mukavemeti zerine az bir etkisi olmutur. Bulgular sinterlenmi kompaktlardaki gzeneklerin kresel ap
ve kresellik deerleri altnda tartlmtr.
Anahtar kelimeler: Gzenekli malzemeler, boluk yapc, sinterleme, basma mukavemeti, kresellik, kresel ap.
EFFECT OF SINTERING TEMPERATURE AND TIME ON THE

COMPRESSIVE STRENGTH OF HIGHLY POROUS IRON BASED
COMPACTS
ABSTRACT
In this study; highly porous iron based compacts were manufactured using the space holder technique in powder
metallurgy. Carbamide which had a particle size distribution in the range 0.71-1.00 mm with an irregular shape were
covered with prealloyed Distaloy AB iron powder and pressed uniaxially at 200 MPa to obtain cylindrical compacts
having a diameter of 12 mm and height of about 18 mm. About 95% of the carbamide was removed from the compacts by water leaching at room temperature. The compacts were sintered at 1150 C and 1200 C for 60 minutes
and at 1200 C for 120 minutes under hydrogen atmosphere. For 60 minute sintering time, raising the sintering
temperature from 1150 C to 1200 C increased the compressive strength values of the compacts about 41%. But,
sintering at 1200 C for 120 minutes made a small contribution to compressive strength values of the compacts. The
findings were discussed in light of spherical diameter and sphericity values of the pores.
Keywords: Porous materials, space holder, sintering, compressive strength, sphericity, spherical diameter.
1. GR
Srekli gelien ve deien teknolojinin bir sonucu olarak kullanlan malzeme trlerinde ve zelliklerinde de ilerlemeler kaydedilmektedir. Gzenekli malzemelerin ortaya k hem hafif hem de mukavemetli malzemelere duyulan
ihtiyacn artmasna dayanmaktadr. Yeni bir mhendislik malzeme snf olan kpks metaller; dk younlua,
bklmeye kar dirence, yksek enerji snmleme kabiliyetine, sesi emme zelliine, dk s ve elektrik iletkenliine sahiptirler. Enerji tketiminin azalmasna olanak veren hafif yaplar ayn zamanda evreye duyarl yeni bir malzeme grubu olarak da dikkat ekmektedir [1-3]. Kpks metaller; sv hal kpklendirmesi, gaz hapsetme, amur
863

kpklendirme, metalik bo kre kullanarak kpklendirme, dkm, ktrme- kaplama, gaz-tektik dnm ve
toz metalurjisi yntemleri ile retilmektedir. Boluk yapc kullanlarak toz metalurjisi yntemiyle gzenekli malzeme
retimi; gzenek zelliklerinin, malzeme eklinin ve mekanik zelliklerinin kontrolnde dier yntemlere gre salad birok stnlkten dolay son yllarda kullanlan bir yntem olarak karmza kmaktadr. Kullanlacak boluk
yapc, malzemenin ierisinde kalnt brakmadan kolayca atlabilmeli ve metalle reaksiyona girmemelidir. Karbamit,
hem termal hem de suda zndrlerek yapdan uzaklatrlabildiinden; alminyum, titanyum, paslanmaz elik,
nikel ve bunlarn alamlarndan metalik kpk retiminde son yllarda baarl olarak kullanlmaktadr [4-6].
Sinterleme scakl ne kadar yksek olursa ham kompakt ierisindeki toz partikllerin de arzu edilen derece bir
balanma elde etmek iin gereken sre o kadar ksa olur. malat asndan ksa sinterleme sreleri daha ok tercih
edilir. Ancak yksek sinterleme scaklklar sinter frn bakm maliyetleri asndan ekonomik deildir. Demir esasl
alamlar iin en yaygn sinterleme koullar 1120-1150 Cdir. Uygulamaya bal olarak sinterleme sresi 15-60
dakika arasnda deiir [7]. Ancak toz metalurjisi yntemiyle yksek oranda gzenek ieren malzeme retiminde
dk presleme basncndan kaynaklanan ksmi sinterleme yksek sinterleme scakl ve sresiyle iyiletirilebilir
[8-12].
Ak gzenek yaps malzemenin dayanmn drmesine karn yksek oranda s tanmn mmkn klan zelliinden dolay yksek g reten cihazlarda etkili bir soutucu mekanizma olarak, yksek hzda ve titreim frekansnda alan makine paralarnda akustik sourma salamak amacyla ve kimyasal reaktrlerde katalizr tayc
olarak kullanm alan bulmaktadr. Mo ile n alamlandrlm demir tozlarndan retilen gzenekli malzemeler;
yksek scakla ve sl oklara kar dayanma sahip olmasndan dolay s kalkan olarak s yaltm ve soutma
sistemlerinde, yanma motorlarnn yksek scakla maruz kalan k yerlerinde kullanm potansiyeline sahiptir
[1-3, 13].
Literatrde; Distaloy AB tozundan hareketle boluk oluturucu kullanlarak toz metalurjisi yntemiyle kpks metal
retimine ynelik bir alma bulunmamaktadr. Bu almada, toz metalurjisi yntemiyle Distaloy AB tozundan yksek oranda gzenek ieren numuneler retilerek; farkl sinterleme scakl ve sresinin basma davran zerine
etkisi gzeneklerin kresel ap ve kresellik deerleri altnda tartlmtr.
2. MALZEME VE YNTEM
Deneylerde; Hgans firmas tarafndan atomizasyon yntemi ile retilmi ortalama tane boyutu 112 m olan dzensiz ekilli n alaml Distaloy AB demir tozu kullanlmtr. Ham mukavemeti arttrmak amacyla balayc olarak
kullanlan parafin Merck firmasndan temin edilmi olup 46-48 C arasnda erime scaklna sahiptir. Boluk yapc
olarak; +710-1000 m boyut aralna sahip dzensiz ekilli teknik safiyette karbamit kullanlmtr. Karbamitin
younluu; 1,34 g/cm3, erime scakl 133 C ve 20 C scaklktaki suda znrl 108 g/mLdir. Deneysel almada kullanlan n alaml demir tozunun kimyasal bileimi Tablo 1de verilmektedir.
Tablo 1 : n alaml demir tozunun kimyasal bileimi [14].
ekil 1-(a)da atomizasyon yntemiyle retilmi n alaml Distaloy AB tozunun ekil 1-(b)de dzensiz ekilli karbamitin Taramal Elektron Mikroskobu (SEM) grntleri verilmitir.
ekil 1 : Deneysel almada kullanlan (a) Distaloy AB tozunun ve (b) karbamitin SEM grnts
864

Toz metalurjisi yntemi ile kpks metal retiminin temel ilem admlar; metal tozunun balayc ile kartrlmas,
karbamit yzeyinin metal tozuyla kaplanmas, presleme, ham numunelerden karbamitin uzaklatrlmas ve sinterlemedir.
Ham numunelerin mukavemetinin arttrlmas amacyla balayc olarak a.%3 orannda hazrlanan parafin zeltisi, n alaml demir tozuna hac.%2 orannda katlarak oda scaklnda 30 dakika kartrlmtr. Karma;
hac.%80 orannda karbamit ilave edilip turbula tipi kartrcda 1 saat sre ile kartrma sonucu, karbamit paracklar demir tozlar ile kaplanmlardr.
Demir tozlaryla kaplanm karbamitin elik bir kalp ierisinde 200 MPa basn altnda tek ynl preslenmesiyle 12
mm apnda ve yaklak 18 mm yksekliinde silindirik numuneler elde edilmitir. Ham numunelerdeki karbamitin
yaklak %98i saf su banyosunda 3 saatte gider3ilmitir. retilen ham numunelerin younluklar ktle/hacim ilikisinden 2,20 g/cm olarak belirlenmitir.
Numuneler ierisinde kalan az miktardaki karbamit ile balayc olarak kullanlan parafinin termal olarak giderilmesi
ve sinterleme ilemi seramik bir boruya sahip Lenton marka frnda yaplmtr.
Numuneler; ortamdan N2 gaz geirilerek nce 5 C/dak. stma hzyla 400 Cye stlm ve bu scaklkta 30 dakika
tutulmu daha sonra ortamdan yksek safiyette H2 gaz geirilerek 10 C/dak. stma hzyla; 1150 C ile 1200 C
de 60 dakika ve 1200 C de 120 dakika sinterlenmilerdir.
Sinterlenmi numunelerin younluklar, ak ve kapal gzenek oranlar Arimed Yntemine gre belirlenmitir.
Ak ve kapal gzenek oranlarn belirlemek iin numuneler 150 Cde kaynayan parafin ierisinde 1,5 saat bekletilerek parafinin gzeneklere emdirilmesi salandktan sonra numunelerin arlk lmleri gerekletirilmitir.
Numunelerin grnt analizleri Jeol JSM-5600 Taramal Elektron Mikroskobunda yaplmtr. Sinterlenmi numunelerdeki gzeneklerin kresel ap ve kresellik dalmlar; Clemex Vision PE-4.0 grnt analiz program kullanlarak SEM resimleri zerinde belirlenmitir.
Basma testleri, boy/ap oran 1,5 olan numuneler zerinde, ZWICK marka Z 050 PROLINE model mekanik test
cihaznda oda scaklnda 0,5 mm/dak. basma hzyla gerekletirilmitir. Gerilme-%ekil deiim grafikleri ve
hesaplamalar, Test-Xpert programnn V11-02 versiyonu kullanlarak elde edilmitir.
3. SONULAR VE DEERLENDRME
2,20 g/cm3 ham younluktaki numunelerin; 1150 Cde 60 dakika, 1200 Cde 60 dakika ve 1200 Cde 120 dakika
sinterlenmesi sonucu hacimsel ekmeleri srasyla; %6,41, %6,62 ve %6,68 olarak gereklemitir. Artan sinterleme scakl ve sresi tm numunelerde hacimsel ekmeyi arttrmtr. Sinterleme scaklnn hacimsel ekme zerine etkisinin sinterleme sresinden daha fazla olduu belirlenmitir. Sinterlenmi numunelerin Arimed Yntemine
gre belirlenen younluklar, toplam, ak ve kapal gzenek oranlar sinterleme scakl ve srelerine gre Tablo
2de verilmitir.
Tablo 2 : Arimed Yntemine gre belirlenen younluk, toplam, ak ve kapal gzenek oranlar
Sinterlenmi numunelerin toplam gzenek oran hedeflenen gzenek oranndan (hac.%80) dk kmtr. Artan
sinterleme scakl ve sresi ile kapal gzenek oran bir miktar artmtr. Azalan sinterleme scakl ksmi sinterlemeden dolay ak gzenek orann bir miktar arttrmtr.
ekil 2-(a)da 1150 Cde 60 dakika, (b)de 1200 Cde 60 dakika ve (c)de 1200 Cde 120 dakika sinterlenen numunelerin SEM fotoraflar verilmitir.
865

ekil 2 : (a) 1150 Cde 60 dakika, (b) 1200 Cde 60 dakika ve (c) 1200 Cde 120 dakika sinterlenen
numunelerin SEM grntleri
ekil 2de verilen SEM fotoraflarnda belirgin bir ekilde kpks yapnn olutuu grlmektedir. Gzenekler
birbirlerinden hcre duvarlaryla ayrlmlardr. Yaplarda atlak oluumlarna rastlanmam ancak mikro gzenekler bulunmaktadr. Gzenek morfolojisinin karmak olmas kullanlan karbamitin dzensiz ekilli olmasndan ileri
gelmektedir.
ekil 3de; farkl scaklk ve srelerde sinterlenmi numunelerdeki gzeneklerin kresel ap ve kresellik dalmlar
verilmitir.
ekil 3 : (a) ve (b) 1150 Cde 60 dakika, (c) ve (d) 1200 Cde 60 dakika ve (e) ve (f) 1200 Cde 120 dakika
sinterleme sonras numunelerdeki gzeneklerin kresel ap ve kresellik dalmlar
Kresel ap ve kresellik dalmlar; numunelerin farkl scaklk ve srede sinterlenmesine gre deiiklik gstermektedir. Sinterleme scaklnn 1150 Cden 1200 Cye ykselmesi ile gzeneklerin maksimum ve ortalama
kresel aplar srasyla; 1026,2 mden 991,2 mye ve 608,7 mden 586,5 mye azalm, kresellii 0,54den
0,56ya artmtr. Ancak artan sinterleme sresiyle ortalama gzenek boyutlar ve kresellik deerlerinde kayda deer farkllklar olmamtr. 1150 Cde 60 dakika sinterleme ile retilen numunelerdeki gzeneklerin %50si 400-800
m boyut aralna sahipken, 1200 Cde 60 ve 120 dakika sinterleme ile retilen numunelerdeki gzeneklerin yaklak %60 400-800 m boyut aralna sahiptir. Boluk yapc olarak kullanlan karbamitin balangta maksimum
ve ortalama kresel aplar ve kresellik deerleri srasyla; 996,7 m, 812,6 m ve 0,66dr. Balangta kullanlan
karbamite gre tm numunelerde sinterleme sonras gzeneklerin oratalama kresel aplar ve kresellikleri azalmtr. Bu durum, sinterlemeden dolay gzenek duvarlarnda ekmenin baskn olmasndan kaynaklanmaktadr.
Maksimum gzenek boyutunun kullanlan karbamitin boyutundan byk olmas gzeneklerin birbirleriyle balant
kurmasndan kaynaklanmaktadr.
ekil 4de farkl sinterleme scakl ve sresinde sinterlenmi numunelerin gerilme- %ekil deiim erileri verilmitir.
866

ekil 4 : Farkl sinterleme scakl ve sresinde sinterlenmi ve yaklak %70 gzenek

ieren numunelere ait basma erileri
Bu eriler kpks metallerin tipik basma davrann yanstmaktadr. Her bir eri elastik bir blgeye, uzun bir plato
blgesine ve gerilmenin hzla artt younlama blgesine sahiptir. Elastik blgeden sonra numunelerde meydana
gelen youn gzenek duvar krlmas nedeniyle; gerilmede ani dler gereklemitir. 1150 Cde 60 dakika,
1200 Cde 60 dakika ve 1200 Cde 120 dakika sinterleme sonras numunelerin maksimum basma mukavemeti
srasyla; 17 MPa, 24 MPa ve 25 MPa olarak belirlenmitir. Artan sinterleme scakl maksimum basma mukavemetini bir miktar arttrm ancak artan sinterleme sresi maksimum basma mukavemetinde az bir arta neden
olmutur. 60 dakika sinterleme sresi iin sinterleme scaklnn 1150 Cden 1200 Cye karlmas kompaktlarn
maksimum basma mukavemetini %41 orannda arttrrken; 1200 C sinterleme scaklnda sinterleme sresinin 60
dakikadan 120 dakikaya karlmas kompaktlarn maksimum basma mukavemetini %4 orannda arttrmtr. 1150
Cde 60 dakika, 1200 Cde 60 dakika ve 1200 Cde 120 dakika sinterleme sonras numunelerin elastisite modlleri srasyla; 0,47 GPa, 0,68 GPa ve 0,71 GPa olarak belirlenmitir. Artan sinterleme scakl ve sresiyle elastisite
modlleri bir miktar artmtr. Sinterleme scakl ve sresinin artmasnn younlamann balad ekil deiimi
zerine belirgin bir etkisi olmamtr. Aly yapt almada [13], ticari isimleri Distaloy SA ve Astaloy Mo olan n
alaml demir tozlarna amur kpklendirme prosesi uygulam ve rettii3 ham numuneleri 1170 Cde 90 dakika
sinterlemidir. Younluklar 1,3 ile 2,0 g/cm arasnda olan kpks metallerin maksimum basma mukavemetini 5-15
MPa arasnda, younlamann balad ekil deiimlerini %50-60 arasnda bulmutur. Bu yntemin dezavantaj
yapda atlak oluumunun ska gereklemesidir. Bram ve dierleri [8], Park ve Nutt [9], Tuncer ve Arslan [10] ile
Ahmed ve dierleri [11] toz metalurjisi yntemiyle boluk yapc kullanarak yksek oranda gzenek ieren metal
retiminde; gzenek miktar, i yap ve basma davran gibi zelliklerin boluk yapc miktar ve ekli ile balang toz boyutunun yan sra sinterleme scakl ve sresi gibi parametrelerle kontrol edilebileceini belirtmilerdir.
Jiang ve dierleri [12], artan sintreleme scakl ile tozlar arasnda balanmann iyileerek basma mukavemetini
arttrdn tespit etmilerdir.
Artan sinterleme scakl, yksek oranda gzenek ieren Distaloy AB numunelerinde daha fazla hacimsel ekme
ve younlamaya neden olmaktadr. 1200 Cde 60 dakika sinterleme yerine 120 dakika sinterlemenin hacimsel
ekme ve younlama zerine nemli bir etkisi olmamaktadr. Sinterleme scaklnn artmasyla numunelerdeki
gzeneklerin kresellik deerleri artm, ortalama gzenek boyutlar azalmtr. Ancak artan sinterleme sresi ile
gzenek boyutlar ve kreselliklerde ok az deiiklik meydana gelmitir. Numunelerin maksimum basma mukavemetlerinde meydana gelen art; gzenek duvarlarndaki ksmi sinterlemenin yol at mikro gzeneklerin azalmas sonucu gzeneklerin kresel aplarnn azalmas ve kreselliklerinin artmasyla mmkn olmutur.
Teekkr
Bu alma T-1431 proje numarasyla stanbul niversitesi Bilimsel Aratrma Projeleri Birimi tarafndan desteklenmitir.
KAYNAKLAR
1. BANHART, J., Manufacture, Characterisation and Application of Cellular Metals and Metal Foams, Progress in
Materials Science, 46, 559-632, 2001.
2. KREMER, K., LISZKIEWICZ, A., ADKINS, J., Development of Steel Foam Material and Structures, Technology
Roadmap Program 9913 Final Report, The United States Department of Energy and American Iron and
867

Steel Institute, 2004.

3. BANHART, J., Properties and Applications of Cast Aluminium Sponges, Advanced Engineering Materials,
4:188-191, 2000.
4. BAKAN, H.I., A Novel Water Leaching and Sintering Process for Manufacturing Highly Porous Stainless Steel,
Scripta Materialia, 55, 203-206, 2006.
5. WEN, C.E., MABUCHI, M., YAMADA, Y., SHIMOJIMA, K., CHINO, Y., ASAHINA, T., Processing of Biocompatible Porous Ti and Mg, Scripta Materialia, 45, 1447-1153, 2001.
6. ZHAO, Y.Y., SUN, D.X., A Novel Sintering-Dissolution Process for Manufacturing Al Foams, Scripta Materialia,
44, 105-110, 2001. 7. HGANS HANDBOOK-6, Sintering, Sweden, 2004.
8. BRAM, M., STILLER, C., BUCHKREMER, H.P., STOVER, D., BAUR, H., High Porosity Titanium, Stainless
Steel and Superalloy Parts, Advanced Engineering Materials, 2, 196-199, 2000.
9. PARK, C., NUTT, S.R., PM Synthesis and Properties of Steel Foams, Materials Science and Engineering,
A288, 11-18, 2000.
10. TUNCER, N., Metalik Kpk Malzemelerin retimi ve Karakterizasyonu, Yksek Lisans Tezi, Anadolu niversitesi Fen Bilimleri Enstits, 2006.
11. AHMED, Y.M.Z, RIAD, M.I., SAYED, A.S., AHLAM, M.K., SHALABI, M.E.H., 2006, Correlation Between Factors Controlling Preparation of Porous Copper via Sintering Technique Using Experimental Design, La-Metallurgia Italiana, 41-46, 2006.
12. JIANG, B., ZHAO, N.Q., SHI, C.S., LI, J.J, Processing of Open Cell Aluminum Foams with Tailored Porous
Morphology, Scripta Materialia, 53, 781-785, 2005.
13. ALY, S.M., High Temperature Mechanical Properties of Cast as well as Powder Metallurgical Manufactured Metallic Foams, Doctorate Thesis, Stipendiat am Institut fr Eisenhttenkunde, Aachen, Deutschland,
2004.
14. HGANS-A.B., Hgans Iron and Steel Powders for Sintered Components, Sweden, 1996.
868

42CrMo4 ELNN KIVILCIM PLAZMA SNTERLEME YNTEM LE

YOUNLATIRILMASI
Rdvan YAMANOLU*, William BRADBURY**, Eugene OLEVSKY**, Randall M. GERMAN**
*Kocaeli niversitesi, Mhendislik Fakltesi, Metalurji ve Malzeme Mhendislii Blm, 41380, Kocaeli,
ryamanoglu@kocaeli.edu.tr
**San Diego State niversitesi, Makine Mhendislii Blm, 92182-1323, San Diego, California, USA,
wbradbur@gmail.com, eolevsky@mail.sdsu.edu, rgerman@mail.sdsu.edu
ZET
Bu almada, 42CrMo4 eliinin kvlcm plazma sinterleme (SPS, Spark Plasma Sintering) yntemi ile younlatrlmas incelenmitir. retilen tozlar farkl scaklk, sre ve zellikle etkili stma hz deiimleri altnda sinterlenmi
ve proses parametrelerinin sinterleme karakteristii zerine etkileri saptanmtr. Elde edilen kompaktlarn younluklar, mikroyapsal karakteristikleri ve sertlikleri incelenerek sonular deerlendirilmitir. Mikroyapsal zelliklerin
tayininde optik ve taramal elektron mikroskobu kullanlmtr. 42CrMo4 elii iin elde edilen en yksek younluk
deerine ( % 99,2) 1000 oCde 7 dakika bekleme sresi ve dakikada 200 oC stma hz ile ulalmtr.
Keywords: Kvlcm Plazma Sinterleme, 42CrMo4 elii, Mikroyapsal Karakterizasyon
CONSOLIDATION OF 42CrMo4 STEEL BY SPARK PLASMA SINTERING

ABSTRACT
In the current study, a 42CrMo4 steel powder was consolidated by spark plasma sintering. The effect of processing parameters on the sintering characteristics was determined through variation of temperature, holding time and
particularly heating rate conditions. Sintered samples were characterized in terms of relative density, microstructure
and hardness. Optical and scanning electron microscopy was used to examine the microstructural characteristics.
The 42CrMo4 steel powders were successfully sintered to 99.2 % density at 1000oC for 7 minutes using 200 oC/
min. heating rate.
Keywords: Spark Plasma Sintering, 42CrMo4 Steel, Microstructural Characterization
1. GR
eliklerin sinterlenmesi zerine bir ok alma yaplmaktadr. zellikle Cr ierikli eliklerin sinterlenmesinde kromun oksidasyona yatknl nedeniyle oluan oksit tabakas sebebiyle sinterleme olduka zor olmaktadr. Bu nedenle sinterlenemenin atmosfer kontroll bir ortamda yaplmas gerekmektedir [1]. Bu almada da kvlcm plazma
sinterleme yntemi yoluyla vakum altnda Cr ierikli 42CrMo4 elii younlatrlmtr.
42CrMo4 elii orta karbonlu dk alaml elikler gruba girer. Isl ileme olduka yatkn olan bu elik zellikle
yksek mukavemet gerektiren uygulamalarda tercih edilir [2]. Krom ve molibden ierii srasyla % 0.030-1.20 ve
% 0.08-0.35 arasnda deiir. Krom oksidasyon ve korozyon direncini, sertleebilirlii ve yksek scaklk mukavemetini arttrr. Ayn ekilde molibdende mukavemeti artrr, sertleebilirlii kontrol eder ve temper krlganlna
yatknl azaltr. % 0.40 karbon ieren 42CrMo4 elii en yaygn kullanlan eliklerden birisidir ve olduka yksek
ekme mukavemet deerlerine sahiptir [3-4].
869

Kvlcm plazma sinterleme teknii prensip olarak genellikle bir grafit kalp ve zmbalar ierisinde bulunan metal
veya seramik tozunun, yksek akm younluundaki doru akm ile stlmas esasna dayanr. st ve alt zmbalardan kalp boyunca akan akm (tipik olarak birka 1000 A ve birka V) eer sinterlenecek toz malzemede iletken
ise malzemenin iinden de akarak devre tamamlanm ve SPS prosesi ile toz partiklleri arasndaki boluklarda
yksek enerji ak retilmi olur. Bu yntem sahip olduu yksek stma hzlar nedeniyle olduka fazla avantaja
sahiptir. [5-9].
2. DENEYSEL ALIMA
Kocaeli niversitesi Metalurji ve Malzeme Mhendislii Blmnde plazma destekli dnel elektrot yntemi (PREP,
Plasma Rotating Electrode Process) ile retilen 42CrMo4 elii tozlarnn kimyasal bileimi izelge 1de, tarama
elektron mikroskobu grnts ise ekil 1de verilmitir. Tozlar retim ynteminin doas gerei uular srasnda
yeterli sreyi bulup kreselleerek katlamalarn tamamlamlardr. Ayn tozlarn dalanm halde kesit mikroyaplarnn grntleri ekil 2de verilmitir. Geleneksel dkm teknikleri ile retimin aksine toz metalurjik yntemle
retilen tozlar yksek souma hzlar sayesinde martenzitik dnme uramlardr.
izelge 1. Bu almada kullanlan matriks alamnn kimyasal bileimi.
42CrMo4
%C
0,42
% Si
0,23
% Mn
0,62
%P
0,02
%S
0,027
% Cr
0,99
% Mo
0,17
ekil 1. almada kullanlan 42CrMo4 elii tozlarnn SEM grntleri
ekil 2. Tozlarn kesit grntleri, a) SEM, b) optik mikroskop.

retilen bu tozlarn 150-250 m aralna sahip olanlar elek analizi ile gruplandrlarak kvlcm plazma sinterleme
teknii ile younlatrlmtr. Sinterleme iin San Diego State niversitesinde bulunan Dr. Sinter Lab 515S SPS
(SPS Syntex, Co., Japonya) cihaz kullanlmtr. PREP yntemi ile retilen 42CrMo4 elii tozlarnn kvlcm sinterleme yntemi ile younlatrlmasnda 3 farkl sinterleme deikeni kullanlmtr: 800 ile 1000 oC arasnda deien
scaklk, 5 dakika ile 8 dakika arasnda deien tutma sresi ve 100 ile 225 oC/dak. arasnda deien stma sreleri
kullanlmtr. Sinterlenen kompaktlarn younluklar arimet yntemi ile, sertlikleri Fisherskop marka vickers sertlik
cihaz ile belirlenmitir. Numunelerin mikroyapsal karakterizasyonlar iin Zeiss Axiotech k mikroskobu ve Jeol
6060 tarama elektron mikroskobu kullanlmtr.
870

3. SONULAR
izelge 2de 42CrMo4 elii tozlarnn kvlcm sinterleme ile younlatrlmas srasnda kullanlan parametreler ve
sonular sunulmutur.
izelge 2. 42CrMo4 elii iin SPS parametreleri ve younluk deerleri
Numune
Kodu
Scaklk
(oC)
Sre
(dakika)
Istma Hz
(oC/dakika)
Younluk
(%)
T1
800
100
83,6
T2
900
100
93,3
T3
1000
100
98,4
T4
800
200
85,3
T5
900
225
94,2
T6
1000
200
98,5
T7
800
200
86,6
T8
900
225
95,2
T9
1000
200
99,2
Scaklk younluk zerinde en etkili parametre olmutur. 800, 900 ve 1000 oCde uygulanan ilemlerde younluk
scaklkla birlikte etkili bir ekilde artmtr. Scaklk etkisinin daha net grlebilmesi iin elde edilen deerler diyagramlar zerinde gsterilmitir. ekil 3de ayn bekleme sresi ve 100 oC/dak. stma hzlarnda 800 ve 1000 oCde
yaplan sinterleme iin scaklk ve younluk diyagramlar verilmitir. Scaklk hari tm parametrelerin ayn olduu
bu iki farkl deneyde diyagramlardan da grld gibi artan scaklk ile younluk ok etkili bir ekilde art gstermitir. 800 oCde younluk % 83,6 iken,a)
1000 oCde % 98,4e ykselmitir.
b)
ekil 3. Younluk zerine scakln etkisi, a) 800 oC, b) 1000 oC
871

Yaplan deneylerde scaklk kadar olmasa da stma hznn da younlama zerine etkisi olduu grlmtr.
100 oC/dak. stma hznda younluk % 83,6 iken stma hz 200 oC/dak. olduunda % 85,3e kmtr. 800 oCde
yaplan almada elde edilen younluk art % 1,7 iken artan scaklk ile stma hznn etkisi younluk zerinde
neredeyse kalmamtr. 900 oC ve 1000 oCde yaplan deneylerde artan stma hz ile elde edilen younluk art
srasyla % 0,9 ve 0,1 olarak bulunmutur. Burada yksek stma hzlarnda partikller arasnda oluan plazma
younluk artnda etkili olmutur. Yaplan SEM incelemeleri de partikller arasnda oluan etkileimin artan stma
hz ile arttn gstermitir.
Scaklk ile karlatrldnda stma sresi ile daha etkisiz bir ekilde deien younluk, bekleme sresinin uzamas ile artmtr. 800 oCde yaplan iki deneyde stma hz ile artan younluk, yaplan nc bir deneyde bekleme
sresi sadece 3 dakika arttrldnda belirgin ekilde ykselmitir. Bekleme sresi etkisi stma hznn aksine btn
scaklk deerlerinde grlmtr. 800 oCde 200 oC/dak. stma hznda bekleme sresi arttrldnda younluktaki
art % 1,3, 900 oC iin % 1 ve 1000 oC iin % 0,7 olarak belirlenmitir.
Tm parametre etkileri incelendiinde en uygun koullarda younluk % 99,2 olarak elde edilmitir. Dolaysyla 1000
o
Cye 200 oC/dakika stma ile ulalp 7 dakika beklendiinde maksimum younluk kazanlmtr. Parametrelerin etkilerinin daha ak bir ekilde incelenebilmesi iin ekil 4de bekleme sresi, scaklk, younluk ile ekil 5de stma
hz, scaklk ve younluk ilikileri verilmitir.
ekil 4. 42CrMo4 elii iin bekleme sresinin scaklk ve younluk ile ilikisi
ekil 5. 42CrMo4 elii iin stma hznn scaklk ve younluk ile ilikisi
872

Elde edilen sinterlenmi kompakt malzemelerin parlatlm konumda k mikroskobu grntleri ekil 6da gsterilmitir. ekil 6ada % 83,6 younlua sahip numunenin olduka fazla gzenekli yaps grlmektedir. ekil 6bde ise
en yksek younlua (% 99,2) sahip numunenin ayn bytmedeki optik mikroskop grnts verilmitir.
ekil 6. Sinterlenmi numunelerin parlatlm konumda k mikroskobu grntleri,
a) % 83,6 younluklu, b) % 99,2 younluklu numune.
Yaplan sertlik lmlerinde % 83,6 younluklu numunenin sertlii 140 HV, % 99,2 younluklu numunenin ise 380
HV olarak llmtr. Sinterlemenin grafit kalpta yaplmas nedeniyle yzeyden karbon difzyonu olmu ve zellikle yzeylerde sert sementit ve martenzit fazlar grlmtr. ekil 7de % 99,2 younluklu numuneye ait sertlik
profili verilmitir. Karbon difuzyonu ve buna bal olarak deien mikroyapsal karakteristik nedeniyle farkl sertlie
sahip blgeler tespit edilmi ve bu yaplar incelenmitir (ekil 8). Malzemenin genel sertliini yanstan sertlik deeri
yaklak 350400 HV arasnda deimektedir. Yzeyde meydana gelen kalnt stenit nedeniyle sertikte nce azalma daha sonra ise martenzit nedenli bir ykseli grlmektedir.
ekil 7. T9 nolu numunede sertlik dalm
ekil 8. % 99,2 younluklu numunede yzey ile merkez arasndaki mikroyap fark
873

42CrMo4 eliinin SPS yntemi ile younlatrlmasnn ardndan, ayn tozlar karlatrma amac ile geleneksel
scak presleme ile de sinterlenmitir. SPS deneylerinde en yksek younluun elde edildii 1000 oC scaklk ve
50 MPa basn deeri altnda tozlar 20 dakika sre ile sinterlenmelerine ramen % 90,5 gibi SPS yntemine gre
olduka dk bir deer elde edilmitir.
Numuneler kvlcm sinterleme yntemi ile younlatrldktan sonra gevrek krlm ve elektron mikroskobunda
krlma yzeyleri incelenmitir. ekil 9da en dk (T1) ve en yksek younlua sahip (T9) numunelerin SEM
grntleri verilmitir. Younluk fark net bir ekilde dikkati ekmektedir. T1 numunesinde dk younluk nedenli
partikller arasndaki zayf balantlar (taneleraras krlma), T8 numunesinde ise kuvvetli balantlar (yer yer tane
ii krlma) grlmektedir.

a)
b)
ekil 9. En dk ve en yksek younlua sahip numunelerin SEM grntleri, a) T1, b) T9
SPS ile sinterlenen numunlerde kullanlan farkl parametrelerin etkileri daha nce aklanmt. Ayn scaklk, basn ve bekleme sresine sahip fakat farkl stma hzlarndaki numunlerin (T1 T4) krlma yzeyleri ekil 10da
verilmitir.
a)
b)
c)
d)
ekil 10. Farkl stma hzlarnda T1 ve T4 numunelerinin SEM grntleri

Srasyla % 83,6 ve 85,3 younlua sahip bu numunelerin krlma yzeylerinden yksek stma hzna sahip numunedeki partikller arasndaki balantnn daha etkili olduu anlalmaktadr. ekil 10dde T4 numunesinde dekohezyon etkisi net bir ekilde grlmektedir.
874

Bu almada PREP ile retilmi olan demir esasl DIN 42CrMo4 (AISI 4140) eliinin son yllarda olduka fazla ilgi
eken ve zerinde ok fazla aratrmann yapld kvlcm sinterleme teknii ile younlatrlmas zerinde durulmutur. Bu malzemeye ounlukla boyut olarak byk paralarda ihtiya duyulmaktadr. Fakat mekanik zelliklerden dn verilemeyecek hassas paralarn kk boyutlu ve karmak ekilde retilme ihtiyac nedeniyle bu tarz
malzemelerin de toz metalurjisi ile retimi zerinde durulmaya balanmtr. Sadece otomotiv deil silah paralar
gibi farkl bir ok uygulamada yksek mukavemetli paralarn retimi nem arzeder hale gelmitir.
PREP ile baarl bir ekilde retilen 42CrMo4 elii basn destekli sinterleme yntemi ile younlatrlmtr. Geleneksel basnl sinterlemeye gre aradaki fark, stma hzlarnn ok yksek olmasdr. Kvlcm sinterleme sayesinde PREP ile retilen 42CrMo4 eliinde % 99,2 teorik younlua ulalmtr. Ayn malzeme ayn koullar altnda
geleneksel basnl sinterleme ile younlatrldnda ise % 90,5 gibi olduka dk bir younluk elde edilmitir.
TEEKKR
Bu almaya Atomizasyon Teknikleri ile Toz retimi isimli proje kapsamnda verdii destekten dolay Kocaeli
niversitesi, Bilimsel Aratrma Projeleri Komisyon Bakanlna teekkrlerimizi sunarz.
KAYNAKA
[1] Campos, M., Sanchez, D., Torralba, J. M., Sintering behaviour improvement of a low Cr-Mo prealloyed powder
steel through Mn additions and others liquid phase promoters, Journal of Materials Processing Technology,
143-144, 464-469, 2003.
[2] Bayrak, M., ztrk, F., Demirezen, M., Evis, Z., Analysis of tempering treatment on material properties of DIN
41Cr4 and DIN 42CrMo4 steels, Journal of Materials Engineering and Performance, 16, 597-600, 2007.
[3] Brady, G. S., Clauser, H. R., Vaccari, J. A., Materials Handbook, Fifteenth Edition, McGraw-Hill, New York,
2002.
[4] Chuang, J. H., Tsayt, L. W., Chen, C., Crack growth behaviour of heat-treated 4140 steel in air and gaseous
hydrogen, International Journal of Fatigue, 20, 531-536, 1998.
[5] Orru, R., Licheri, R., Locci, A. M., Cincotti, A., Cao, G., Consolidation /synthesis of materials by electric current
activated/assisted sintering, Materials Science and Engineering R, 63, 127-287, 2009.
[6] Menapace, C., Lonardelli, I., Molinari, A., Phase transformation in a nanostructured M300 maraging steel obtained by SPS of mechanically alloyed powders, Journal of Thermal Analysis and Calorimetry, 101, 815-821,
2010.
[7] Skiba, T., Hausild, P., Karlik, M., Vanmeensel, K., Vleugels, J.,Mechanical properties of spark plasma sintered
FeAl intermetalics, Intermetallics, 18, 1410-1414, 2010.
[8] Yanagisawa, O., Kuramoto, H., Matsugi, K., Komatsu, M., Observation of particle behavior in copper powder
compact during pulsed electric discharge, Materials Science and Engineering A, 350, 184-189, 2003.
[9] Bernard-Granger, G., Addad, A., Fantozzi, G., Bonnefont, G., Guizard, C., Vernat, D., Spark plasma sintering
of a commercially available granulated zirconia powder: Comparison with hot-pressing, Acta Materialia, 58,
3390-3399, 2010.
875

SiCp Takviyeli Zn-Al Matriksli Metal Matriksli Kompozit

Malzemeleri Akm Sinterleme Yntemiyle retilmesi
Ramazan KARSLIOLU, Mehmet UYSAL, Hatem AKBULUT
Sakarya University Engineering Faculty, Department of Metallurgical and Materials Engineering,
rkarslioglu@sakarya.edu.tr
zet
Bu deneysel almada Zn-Al matriks ierisine hacimce farkl oranlarda(%0, %10, %20, %30) SiC takviyelenmitir.
stenilen bileimdeki numuneler toz metalurjisi yntemi kullanlarak hazrlanmtr. SiC takviyeli Zn-Al alamlar
akm destekli sinterleme yntemiyle 200 A akm altnda 10 dk sreyle sinterlenmitir. sinterlenen numuneler taramal elektron mikroskobu(SEM), Optik mikroskop, mikro setlik cihazlar kullanlarak analiz edilmitir. Akm sinterleme
yntemi ile Zn-Al alamlarnn rtilebilirlii ve SiC orann etkisi incelenmitir.
Anahtar Kelimeler: Zn-Al alam, Toz Metalurjisi (T/M), kompozit, akm destekli sinterleme
Abstract
In this study, Zn-Al matrix was reinforced with different ratio SiC(0 vol%, 10 vol%, 20 vol%, 30 vol%). Intended compositions of samples were prepared by Powder Metallurgy. SiC reinforced Zn-Al alloys were produced by current
activated sintering under 200 A with 10 min. Sintered samples were characterized by optic microscope, Scanning
Electron Microscope (SEM) and Microhardnes. Reproducibility of Zn-Al alloys by current activated sintering and
effect of SiC ratio were investigated
Keywords: Zn-Al alloys, Composite, Powder metallurgy, current activated sintering,
1.Giri
Metal matriksli kompozit malzemeler, tek bileenli yaplarla baarlamayan, gerekli ve istenen zellikleri salamak
zere en az biri metal veya alam dieri takviye malzemesi (srekli fiber, wisker ve partikl eklinde genel olarak
metaller aras bileik, oksit, karbr veya nitrr bileikleri gibi) olan iki veya daha fazla farkl sistemin birleimi ile
elde edilen malzeme grubudur. Yksek elastik modl, yksek mukavemet ve yksek anma direnci gibi zellikleri
salamak zere metal alamlarna yaplan ilaveler, partikl eklinde SiC, TiC, B4C ve Al2O3 gibi seramik takviyeler
olabilmektedir [1].
inko alminyum alamlar son yllarda srekli gelien ve sk kullanm alanlar bulan alamlar haline gelmitir. Gnmzde ZA alam ailesi olarak bilinen ZA-8, ZA-12 ve ZN-AL alamlar, deiik alanlarda yaygn olarak kullanlan
ZAMAK alamlarnn uygulama alanlarn daha da genileterek, birok endstriyel uygulamalarda (konstrksiyon,
otomotiv, madencilik vs.) yer almaktadr [2]. inko-alminyum alamlar mukavemetli, korozyon ve anma direnci
iyi, ayn zamanda kolay dklebilirlie sahip alamlardr. Ancak younluklarnn yksek olmas ve scaklk art
ile mukavemetlerini nemli oranda kaybetmeleri gibi dezavantajlar vardr [3]. stn tribolojik zelliklere sahip olan
inko alminyum esasl alamlar, pek ok uygulamada beyaz metal, bronz, pirin ve dkme demir gibi geleneksel
yatak malzemelerinin yerini almaktadr [4-5].
Toz metalurjisi yntemi ile retilen inko-Alminyum alamlarnn sinterlenmesinde byk problemler yaanmaktadr. Bunun nedeni sinterleme esnasnda inkonun buharlaarak yapdan uzaklamasdr. Bu nedenle son yllarda
876

ilgi eken akm sinterleme yntemi inko-Alminyum alamlar iin de uygulanabilir gzkmektedir. Bu yntemde
inko tozlar buharlamaya vakit bulamadan Alminyum tozlar ile etkileime girerek birbiri ierisine difze olurlar.
stenilen bileimi ve yapy ok ksa srede oluturabilirler.
Bu almada, olduka iyi anma direnci, mkemmel sertlik zellikleri ve yksek mukavemete sahip SiC partiklleri
kullanlarak, Zn-Al alamnn anma zelliklerinin gelitirilmesi amalanmtr. Zn-Al alamnn ve MMK malzemelerin retimi akm destekli sinterleme yntemiyle gerekletirilmitir. Takviyesiz Zn-Al ve hacimce % 10, % 20 ve %
30 SiC partiklleri takviye edilerek kompozit malzemeler retilmitir. Alam ve kompozitlerde mikroyap incelemesi
ve sertlik lmleri yaplmtr.
2.Deneysel almalar
MMK malzeme retiminde kullanlan mariks malzemesi Zn-Al alamdr. Alam arlka %73 Zn %27 Al bileimindedir. inko ve alminyum tozlarnn boyutlar 45-90 m arasnda olup GTV Verschleiss-Schutz GmbH ticari
marka tozlar kullanlmtr. Matriks alam %10, %20 ve %30 orannda SiC ile takviye edilmitir. Kullanlan SiC tozlarnn partikl boyutu ~55mdir. Numuneler geleneksel toz metalurjisi yntemi kullanlarak hazrlanmtr. inko,
Alminyum ve SiC tozlar etil alkol ierisinde bilyeli deirmen kullanlarak 4 saat boyunca kartrlmtr. Kartrlan
tozlar n ekillendirme ile 20 MPalk basn altnda elik kalp kullanlarak numuneler hazrlanmtr. Numuneler
bakr elektrotlar arasnda ve elik kalp ierisine yerletirilerek 200 A akm altnda 10 dk sre ile 5 barlk basn
altnda sinterlenmitir. Sinterleme esnasnda elik kalbn scakl lazer termocouple kullanlarak 400 oC olarak
llmtr. Deney dzenei ekil. 1de gsterilmitir. retilen numuneler metalografik yzey hazrlama yntemi
ile hazrlanp fazlarn optik mikroskopla grnebilmesi iin dalama yaplmtr. Metalografik olarak hazrlanan alam ve kompozitler NIKON ECLIPSE L150A optik mikroskobu ile incelenmi ve partikl dalmlar aratrlmtr.
Daha sonra alam ve kompozit numuneler Future Leica VMHT MOT Mikro sertlik cihaz yardm ile 50 gr 15 saniye
sreyle uygulanarak mikrosertlik lmleri yaplmtr. Sertlik lmleri mariks fazndan alnmtr. lmn salkl
olabilmesi iin her numuneden beer adet lm alnarak ortalamalar kaydedilmitir. Taramal elektron mikroskobu
(SEM) incelemeleri ve EDS analizleri Jeol JSM 6060 LV marka cihazla yaplmtr.
ekil 1. Deney dzeneinin a)ematik gsterimi b)Deney esnasndaki grnm[6]

3. Deneysel Sonular
3.1. Optik Mikroskop Sonular
Zn-Al alamlarnn sinterlenmesinde gnmzde teknolojik glkler yaanmaktadr. inkonun ergimeden buharlama davranndan dolay geleneksel sinterleme ilemlerinde kontroll atmosferde yaplan sinterleme ilemlerinde bile nihai rnde ok nemli poroziteler ortaya kmakta ve bu da mekanik ve fiziksel zellikleri ok olumsuz
etkilemektedir. Benzer ekilde Cu-Zn ve bronzlarda da sinterleme hatalar ile karlalmaktadr. Bu hatalar zellik-
877

lerin d yannda ou zaman sinterleme sonrasnda malzemelerde boyutsal art (ime) ortaya karmaktadr.
Yaplan optik mikroskop incelemelerinden elde edilen grntler ekil 2-5 te grlmektedir.
Alamn mikro yaps incelendiinde, alamn lamelli tektik yap hakim bir yap gsterdii anlalmaktadr. Bu tr
mikroyap klasik dkm yntemleri ile retilen Zn-%27 Al alamndan farkldr. Lamelli tektik yapnn zellikle SiC
partiklleri etrafnda ekirdeklenme eilimi gsterdikleri ortaya kmaktadr. Kompozit mikro yaplarnn incelenmesinden SiC partikllerinin Zn-Al mariksi iinde olduka homojen daldklar, segregasyon gstermedikleri gzlenmitir. Saf Zn-Al alamnn sinterlenmesi Zn-Al nin birbirlerinin iine difzyonu iin deneysel parametrelerin yeterli
olduu grlmektedir. ekil 1 den de anlalaca zere toz metalurjisi ytemi ile retimi zor olan Zn-Al alamlar
baarl bir ekilde retilmitir. ekil 3 deki %10 SiC takviyeli Zn-Al alam incelendiinde SiC partiklerle matriks
malzemesi arasnda iyi bir birleme olduu yksek bytmeli fotoraftan da dorulanmtr. SiC oran oran % 20
ye ktnda yapda poroziteler grlmtr (ekil 4). % 30 SiC takviyeli yapy incelediimizde ise yap ierisindeki
porozite miktarn ve boyutlarnn artt grlmektedir (ekil 5). Bunun muhtemel nedeni SiC miktarnn art Zn
ve Al arasnda difzyonu engellemesi ve dolaysyla daha yksek scaklklar veya srelerde retimin yaplmasna
ihtiya duyulmasdr. Metal ve alamlarna ilave edilen sert seramik esasl fazlarn yksek scaklkta kullanlma
imkanlarn arttrmas da difzyonun engellenmesinden kaynaklanmaktadr. zellikle yksek miktarda SiC takviyeli
alamlarn retilmesinde engellenen difzyon neticesinde klasik Zn-%27 Al mikroyaps elde edilememektedir. Elde
edilen lamelli yaplar daha ok Zn-%5 veya Zn-%12 Al bileimlerini andrmaktadr. Dier taraftan matriks alamna
ilave edilen SiC partikllerinin faz dnm iin heterojen ekirdekletirici olarak davrandklar da mikroyaplardan
anlalmaktadr. tektik dnm genelde SiC seramik partiklleri zerinde olumaya balamaktadrlar.
ekil 2. Zn-Al alamn mikro yaps
ekil 3. Zn-Al+%10 SiC kompozit yapnn optik grnts
878

3.2. SEM ve EDX incelemeleri
ekil 6 SEM Fotoraf ve EDX analizi sonular

ekil 6 da geri salm dedektr kullanlarak elde edilen yksek bytmeli SEM mikroyap fotoraf verilmitir.
Mikro yap incelendiinde SiC ve matriks malzemesi olan Zn-Al alam arasndaki ban salanabildii buradan da
anlalmaktadr. Ayn zamanda alam yaps da ayrntl olarak gzkmektedir. EDX analizileri yardmyla SiC ve
Zn-Al yaplar mikro yap zerinde gsterilmitir.
3.3. Mikro Sertlik Sonular
retilen mariks (Zn-Al) ve deiik oranlarda SiC takviyeli kompozitlerin akm altnda sinterlenmesi sonrasnda matrikste ortaya kan mikro sertlik sonular ekil 7da verilmitir. SiC miktar arttka beklenildii gibi sertliin artt
gzlenmitir. SiC ierii fazla olan kompozitin sertlii en yksek deerde iken alamn sertliinin kompozitlere gre
daha dk kald grlmtr. retilen kompozit malzemeler arasndaki bu farkn nedeninin MMK malzemelerde,
takviye malzemelerinin yksek sertlik deerlerine sahip olmasdr. Bunun yannda yksek takviye orannda fazla
yk transferi ve bu malzemelerin souma srasnda kendisi ve mariks malzemesi arasndaki yksek termal genleme katsays farknn bir sonucu olarak ortaya kan dislokasyon younluunun etkili olduu dnlmektedir.
ekil 7. Elde edilen kompozitlerin sertlik deerleri

3. Sonular
Klasik sinterleme yntem ile sinterlemesi mmkn olmayan Zn-Al alam akm sinterleme yntemi ile baarl bir
ekilde retilmitir.Akm sinterleme ytemi kullanlarak ksa srede SiC takviyeli Zn-Al mariksli MMK malzemeler
baarl bir ekilde retilmitir. SiC partiklleri matrikste homojen dalmlardr. Artan partikl miktar mikroporozitenin artna yol amtr. Zn-Al ierisindeki SiC miktarnn art matriks sertliini artrd grlmtr.
Kaynaklar
1. Sornakumara T. , Senthil Kumarb A. journal of materials processing technology Vol. 202 pp 402405 2008
2. Smith W., Structure and Properties of Engineering AlIoys, 2nd Edn, p. 561. McGraw-Hill, New York 1993.
3. Lee P. P., Savaskan T. and E. Laufer, Wear Vol 117, pp 79 1987.
[4] Seah K. H. W., Sharma S. C. and Girish B. M., Mater. Des. in press (1996).
[5] Seah K. H. W.,_ Sharmas F S. C. and Grshs B. M. Corrosion Science, Vol. 39, No. 1, pp. 1-7, 1997
[6] Karslioglu R.,Uysal M.,Alp A.,Akbulut H., Tribology Transactions, Vol. 53, Issue 5 pp 779 - 785 2010
879

Proceedings - Toz Konfrensı

Uploaded by

Document Information

Original Title

Copyright

Available Formats

Share this document

Share or Embed Document

Sharing Options

Did you find this document useful?

Is this content inappropriate?

Copyright:

Available Formats

Proceedings - Toz Konfrensı

Uploaded by

Copyright:

Available Formats

6th INTERNATIONAL POWDER METALLURGY CONFERENCE & EXHIBITION

6. ULUSLARARASI TOZ METALURJS KONFERANSI ve SERGS

6th INTERNATIONAL POWDER METALLURGY CONFERENCE & EXHIBITION

6th INTERNATIONAL POWDER METALLURGY CONFERENCE & EXHIBITION

Sintering Furnaces - Ningbo Dongfang Heating Equipment

6. Iron and Copper Powder in China

6th INTERNATIONAL POWDER METALLURGY CONFERENCE & EXHIBITION

to supply PM components to emerging automotive, motorbike, electronics and furniture industries. As of

6th INTERNATIONAL POWDER METALLURGY CONFERENCE & EXHIBITION

6th INTERNATIONAL POWDER METALLURGY CONFERENCE & EXHIBITION

IPTECs HIP (Installed for a Chinese customer in 2009):

Nanjing East Precision Machinery Co., Ltd (EPM)

6th INTERNATIONAL POWDER METALLURGY CONFERENCE & EXHIBITION

6th INTERNATIONAL POWDER METALLURGY CONFERENCE & EXHIBITION

Trends of MIM in China

6th INTERNATIONAL POWDER METALLURGY CONFERENCE & EXHIBITION

THE PRACTICAL ANALYSIS OF FABRICATION OF A

Figure 1. Schematic diagram of MIM process.

6th INTERNATIONAL POWDER METALLURGY CONFERENCE & EXHIBITION

Figure 2. Geometry of sample.

6th INTERNATIONAL POWDER METALLURGY CONFERENCE & EXHIBITION

Heating Rate (C/min)

Debinding Temperature (C)

Debinding Holding Time (min)

Sintering Holding Time

Figure 3. The graph of debinding/sintering.

Figure 4. Sintered part.

6th INTERNATIONAL POWDER METALLURGY CONFERENCE & EXHIBITION

Figure 5. Schematic shape showing the separation phenomenon in an injected part.

Figure 6. Micrographs of sintered parts (x1000),

6th INTERNATIONAL POWDER METALLURGY CONFERENCE & EXHIBITION

6th INTERNATIONAL POWDER METALLURGY CONFERENCE & EXHIBITION

THE PROCESSING OF Ni-RICH TiNi FOAMS WITH Mg SPACE HOLDER

6th INTERNATIONAL POWDER METALLURGY CONFERENCE & EXHIBITION

6th INTERNATIONAL POWDER METALLURGY CONFERENCE & EXHIBITION

6th INTERNATIONAL POWDER METALLURGY CONFERENCE & EXHIBITION

6th INTERNATIONAL POWDER METALLURGY CONFERENCE & EXHIBITION

6th INTERNATIONAL POWDER METALLURGY CONFERENCE & EXHIBITION

TOZ METALURJS YNTEMYLE RETLEN KPREBLR

jonng of foamable precursor materals, produced by

6th INTERNATIONAL POWDER METALLURGY CONFERENCE & EXHIBITION

Elektrod ap, Tipi

2,4 mm, Tungusten

Kaynak akm (A)

ekil 1. Farkl akmlarda birletirilmi preform malzemeler

6th INTERNATIONAL POWDER METALLURGY CONFERENCE & EXHIBITION

3. DENEYSEL SONULAR VE TARTIMA

6th INTERNATIONAL POWDER METALLURGY CONFERENCE & EXHIBITION

ekil 3. Serbest olarak kprtlen numunelerin genleme oranlar

ekil 4. Kprtme ilemine tabi tutulmu numunelerin gzenek yaplar

6th INTERNATIONAL POWDER METALLURGY CONFERENCE & EXHIBITION

6th INTERNATIONAL POWDER METALLURGY CONFERENCE & EXHIBITION

WC-Co KESC U HURDALARINDAN PROMETALURJK

RECOVERY OF WC AND Co POWDERS FROM WC-Co CUTTING

6th INTERNATIONAL POWDER METALLURGY CONFERENCE & EXHIBITION

6th INTERNATIONAL POWDER METALLURGY CONFERENCE & EXHIBITION

6th INTERNATIONAL POWDER METALLURGY CONFERENCE & EXHIBITION

ekil 2. ematik erimi inko

ekil 3. WC-Co kesici u hurdasnn X-n analizi

6th INTERNATIONAL POWDER METALLURGY CONFERENCE & EXHIBITION

3.2. Pirometalurjik Yolla WC ve Co Geri Kazanm

ekil 5. inko banyosunda (a) 750C de ve (b) 800C de

ekil 6. inko banyosunda 800C de 3 saat ilem sonras elde edilen