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6th INTERNATIONAL POWDER METALLURGY CONFERENCE & EXHIBITION 6.

ULUSLARARASI TOZ METALURJS KONFERANSI ve SERGS

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

APPLICATIONS

www.turkishpm.org

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

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

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

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.

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

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.

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

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.

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

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.

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

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.

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

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.

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

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.

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

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) 8 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.

Figure 4. Sintered part.

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

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.

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

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.

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

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].

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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. 2. EXPERIMENTAL PROCEDURE 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). 3. RESULTS AND DISCUSSION 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.

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Mg added (vol.%) 50 60 70 50 60 70

Porosity (vol.%) 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.

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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

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

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

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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 Gaz ak debisi Elektrod ap, Tipi Kaynak akm (A) Dolgu teli Alternatif 12 lt/dk 2,4 mm, Tungusten 130-170-190-230 Amper 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

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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

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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-

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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

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

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

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

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].

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

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)

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

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)

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

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.

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

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.

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

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-

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

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.

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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

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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

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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)

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

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

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

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

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

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.

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

BORON

www.turkishpm.org

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

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.

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

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

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

3. RESULTS AND DISCUSSION 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

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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) 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

30 min 45 min 60 min

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.

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Table 4. Maximum Test Results Borax (%) Tensile strength (MPa) Impact Energy (kg.m) 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. 5 5 Holding Temperature (0C) 1000 1000 Holding Time (min) 45 45 Pure 59.7 5.7 Max. Value 79.5 6.9 Increment 33% 21%

(a)

(b)

(c)

Figure 6. Microstructure of produced Al-B alloy: a) 10X b) 50X c) 100X

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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.

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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.

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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 Anti-sedimentation ratios (%, at the end of 25 days, = 25%) 67 73 93

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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

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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.

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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

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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

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Table 1.Configuration of FGMs. Coded Samples Alsingle(400) Alsingle(500) Al-5single (400) Al-5single (500) Al-10single(400) Al-10single (500) (Al+Al-5)two(400) (Al+Al-5)two(500) (Al+Al-10)two(400) (Al+Al-10)two(500) (Al+Al-5+Al-10)three(400) (Al+Al-5+Al-10)three(500) 100 wt.% Al 100 wt. % Al 95 wt.% Al + 5wt.% B4C 95 wt.% Al + 5wt.% B4C 90 wt.% Al + 10wt.% B4C 90 wt.% Al + 10wt.% B4C 100 wt. % Al and 95 wt.% Al + 5wt.% B4C 100 wt. % Al and 90 wt.% Al + 10wt.% B4C 100 wt. % Al and 90 wt.% Al + 10wt.% B4C 100 wt. % Al and 90 wt.% Al + 10wt.% B4C 100 wt. % Al , 95 wt.% Al + 5wt.% B4C and 90 wt.% Al + 10wt.% B4C 100 wt. % Al , 95 wt.% Al + 5wt.% B4C and 90 wt.% Al + 10wt.% B4C Composition Pressure (MPa) 400 500 400 500 400 500 400 500 400 500 400 500 Layer Single Single Single Single Single Single Two Two Two Two Three 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)

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(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)

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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]. Coded samples Alsingle(400) Alsingle(500) Al-5single (400) Al-5single (500) Al-10single(400) Al-10single (500) (Al+Al-5)two(400) (Al+Al-5)two(500) (Al+Al-10)two(400) (Al+Al-10)two(500) (Al+Al-5+Al-10)three(400) (Al+Al-5+Al-10)three(500) Theoretical density (g cm-3) 2.70 2.70 2.69 2.69 2.68 2.68 2.70 2.70 2.69 2.69 2.69 2.69 Green density (g cm-3) 2.52 2.60 2.51 2.59 2.49 2.57 2.52 2.59 2.51 2.59 2.50 2.59 Sintered density (g cm-3) 2.60 2.61 2.51 2.60 2.50 2.58 2.52 2.60 2.51 2.60 2.51 2.59 Green porosity (%) 6.54 3.70 6.74 3.82 7.12 4.27 6.63 3.75 6.88 3.84 7.09 4.20 Sintered porosity (%) 5.19 3.34 6.58 3.50 6.86 3.69 6.38 3.42 6.58 3.49 6.72 3.75

(a)

(b)

Fig. 6. The green densities of FGMs for different pressing pressure.(a) at 400MPa, (b) at 500MPa.

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

(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].

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

Table 3. The hardness properties of FGMs. Coded samples Alsingle(400) Alsingle(500) Al-5single (400) Al-5single (500) Al-10single(400) Al-10single (500) (Al+Al-5)two(400) (Al+Al-5)two(500) (Al+Al-10)two(400) (Al+Al-10)two(500) (Al+Al-5+Al-10)three(400) (Al+Al-5+Al-10)three(500) Brinell Hardness (BHN) 170 189 201 213 226 250 170-201 195-226 175-213 195-241 166-195-220 185-220-250

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.

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

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.

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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].

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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.

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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.

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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 Rubio, A., J. L. Corkill and M. L. Cohen, Theory of Graphitic Boron NitrideNanotubes, Physical Re1. view B, Vol. 49, pp. 5081-5084, 1994. Chopra, N. G.; Luyken, R. J.; Cherrey, K.; Crespi, V. H.; Cohen,M. L.; Louie, S. G.; Zettl, Boron-Nitride 2. Nanotubes A. Science , Vol. 36 269-966,1995 H. Zhang and Y. Chen Boron Nitride Nanotubes:Synthesis and Structure,Nanotubes and nanofibers, 3. pp 157-174, Australia,2006 Y. Chen and J. S. Williams Synthesis of Boron Nitride Nanotubes Using a Ball-Milling and Annealing 4. Method, Nanoengineering of Structural,Functional, and Smart Materials,pp 182-208, Australia,2006 Y. Chen, M. Conway, and J.S. Williams,Large-quantity production of high-yield boron nitride nanotubes, 5. J. Mater. Res., Vol. 17, No:8, Australia,2002 E.J.M. Hamilton, S.E. Dolan, C.M. Mann, H.O. Colijn, C.A.McDonald, S.G. Shore, Preparation of 6. 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. German R.M.,Sintering Theory and Practce, Joyn Wiley & Sons. Inc., USA,1996 7. 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

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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

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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. 2. DENEYSEL ALIMALAR 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. Tablo 1. Soket retiminde kullanlan matris gruplar ve retim parametreleri Sinterleme Sinterleme Basn Matris (% a.) CuSn 100 98 95 90 B 4C 2 5 10 700 3 35 scakl (C) sresi (dak.) (MPa)

No S1 S2 S3 S4

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Tablo 2. Kullanlan Tozlarn zellikleri Tozlar CuSn B4 C zellik % 85 Cu, % 15 Sn, % 99.9 saflk % 79 B, % 20.5 C, % 99.9 saflk Tane boyutu (m) 45-50 ~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

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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

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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 1 blgesi 2 blgesi 3 blgesi 4 blgesi Kimyasal bileim (% a.) B 0.000 0.000 0.000 0.000 C 13.425 0.000 99.142 0.000 Cu 53.142 85.461 0.000 62.281 Sn 33.433 14.539 0.858 37.719

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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

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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.

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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

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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

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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. 2. DENEYSEL ALIMALAR 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

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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

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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

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CHARACTERIZATION OF POWDER AND PARTS

www.turkishpm.org

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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.

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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%.

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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.

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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.

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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.

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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.

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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.

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[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.

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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.

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2. EXPERIMENTAL PROCEDURE 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. 3. RESULTS AND DISCUSSION 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.

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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.

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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.

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Table 1. Hardness values of Al-20 wt. %TiB2 and Al-10 wt. %TiB2 nanocomposites at different processing stages. Extruded sample hardness, VHN 180 173 Sintered sample hardness, VHN 206 196 Powder microhardness, VHN 480 460 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.

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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.

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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. 2. EXPERIMENTAL PROCEDURE Table 1 shows the code and the nominal chemical compositions of the materials investigated; TH and SH mean through hardening and sinter hardening, respectively.

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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. RESULTS AND DISCUSSION 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.

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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.

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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 0.031 mm IT 10 0.05 mm IT 11 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.

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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.

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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

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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.

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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. RESULTS AND DISCUSSION 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.

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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).

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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.

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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.

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(b)

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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

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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.

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(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.

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(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).

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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.

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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.

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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

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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

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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.

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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

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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.

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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

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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.

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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

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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 Ancorsteel 4300 Ancorsteel 4300L Cr 1 1 Chemical Composition (mass %) Si Ni 0.6 1 0.6 1 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) 0.7 1.6 2.2 0.7 1.6 2.2 Yield Strength (MPa) 752 896 1069 690 738 827 UTS (MPa) 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,

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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-

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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.

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COMPACTION AND MECHANICAL PROPERTIES

www.turkishpm.org

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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

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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. 2. DENEYSEL ALIMALAR 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 66.8 Cu 31.45 Mn 1.33 Fe 0.97 Si 0.38 C 0.1 P 0.013 S 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

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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.

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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.

3. DENEYSEL SONULAR VE TARTIMA 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.

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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 MN 1 MN 2 MN 3 MN 4 MN 5 MN 6 MN 7 MN 8 30 30 30 30 30 70 30 40 30 40 40 Elek aral (%) -125/tava (m) 100 100 100 100 -180/125 (m) -250/180 (m) -355/250 (m) d10 29,96 74,75 147,87 199,81 55,25 52,45 55,98 53,35 Ortalama toz boyutu (m) d50 69,72 128,605 209,99 305,99 97,97 110,79 152 107,61 d90 139,62 207,81 299,74 457,81 183,12 267,45 362 342,27

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 3,27 6,35 MN 2 3,01 6,39 MN 3 2,96 7,96 MN 4 2,90 8,3 MN 5 3,31 5,25 MN 6 3,34 5,77 MN 7 3,47 6,28 MN 8 3,43 5,88

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izelge 4. Monel 400 alam tozlarn hidrojen atmosferinde indirgeme sonras grnr younluk ve ak hz deerleri. rnek kodu Grnr younluk (g/cm3) Ak sresi (s) MN 1 3,46 5,03 MN 2 3,17 5,40 MN 3 3,14 6,10 MN 4 3,12 6,90 MN 5 3,34 4,90 MN 6 3,39 5,14 MN 7 3,49 5,40 MN 8 3,54 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 Ham younluk (%) MN 1 77 MN 2 80 MN 3 79 MN 4 79 MN 5 78 MN 6 79 MN 7 80 MN 8 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.

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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).

ekil 8. Preslenmi ham paradaki porozite ve parack deformasyonu (presleme basnc 360 MPa).

ekil 9. Preslenmi ham paradaki porozite ve parack deformasyonu (presleme basnc 480 MPa).

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ekil 10. Preslenmi ham paradaki porozite ve parack deformasyonu (presleme basnc 600 MPa). 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.

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COMPOSITES

www.turkishpm.org

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The effect of amount of methanol on the properties of Al-Al2O3 composite powders


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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.

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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)

Fig. 1. Morphology of as-received powders: (a) Al alloy and (b) Al2O3 particles. Table 1. The amount of PCA (methanol) and coded process. Coded Process 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 P2 P3 Ligamental Ligamental Ligamental + Flake Ligamental 2 Irregular Flake+irregular Ligamental + Flake 4 6 Semi Equiaxial Equiaxial Flake+ Semi Equiaxial Flake Semi Equiaxial 8 Equiaxial Equiaxial 10 Equiaxial Equiaxial Semi Equiaxial Amount of PCA (wt.%) 1 2 3

Flake+ Flake+ Semi Semi Equiaxial Equiaxial

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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.

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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.

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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. Table 3. Effect of PCA content on the apparent density. Milling time (h) 0 1.038 1.038 1.038 0.5 1.055 1.207 1.148 1 0.965 1.216 1.165 2 0.807 0.715 1.128 4 0.995 0.822 0.672 6 1.248 0,911 0.712 8 1.276 1,031 0.795 10 1.278 1.136 0.959

Apparent density (gr/cm3)

Amount of PCA (wt.%) 1 2 3

Fig. 6. Variation of the apparent density as a function of milling time at different processes for amount of PCA.

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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) 0 Particle size (m) P1 P2 P3 127 127 127 0.5 132 121 126 1 130 116 124 2 65 60 133 4 33 38 116 6 103 33 42 8 112 35 45 10 115 28 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

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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).

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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

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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 Acidic pre-treatment Chemical composition Sodium hypophosphite (NaH2PO2H2O) 30 g/l Lactic acid 98% (CH3CH(OH)COOH) 20ml/l In an air atmosphere in a heat-treatment furnace Applied parameters T=358K (85C), 35 min. At 1100C for 3h heat treatment, oxidation Mechanism The development of a thin hypophosphite layer can be expected on the surface. According to the Deal-Grove model, a continuous, compact oxide layer (SiO2) develops on the surface of ceramic particles.

Surface oxidation

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Sensitization

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. 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.

Activation

T=298K (25C), t=25 min

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).

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Figure 2. Particle size distribution of SiC powder

Figure 3. SEM photomicrograph of SiC particles

Figure 4. XRD spectrum of SiC powder 3. Results

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

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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

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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.

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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

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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. EXPERIMENTAL PROCEDURE 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). 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

Etial 65 AISI 1040

Table 2. Chips fraction used for this experiment. AISI 1040 (wt) 21 28 35 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. Sintering characteristics were investigated in a laboratory furnace in 650oC and for 2 hours [8]. All composites were heated to sintering tempera% 30 40 50 Aluminum(wt) 49 42 35 % 70 60 50

Figure 1. Compaction die for producing compressive specimens.

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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.

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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.

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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.

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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

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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. 2. EXPERIMENTAL PROCEDURE 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 Matrix AlCu ECKA Alumix 123 AlSi ECKA Alumix 231 Element, wt% Cu 4.5 2.5 Si 0.7 14 Mg 0.5 0.5 Zn Lubricant 1.5 1.5 Al Bal. Bal. Mean size m 24 17

Reinforcement SiC

C 0.08

SiO2 0.15

Si 0.04

Fe2O3 0.015

Al2O3 0.004

CaO 0.003

SiC Bal. 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.

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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

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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. 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

Set

AlCu

AlSi

Figure 3. Changes in the velocities of longitudinal and transverse waves with %SiC

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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.

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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.

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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. EXPERIMENTAL PROCEDURE 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/

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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. RESULTS AND DISCUSSION 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.

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Table 1. The results of hardness of metal matrix composite. Sintering times 45min Materials type Al matrix (C1) Al-3m-10wt.% Al2O3 reinforced MMCs (C2) Al-20m-10wt.% Al2O3 reinforced MMCs (C3) Hardness at 550C(HB1) 26.5 31.8 38.3 Hardness at 610C(HB1) 28 32.1 42 Hardness at 550C(HB1) 30 35.2 46 120min Hardness at 610C(HB1) 31.3 36.5 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.

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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.

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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.

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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.

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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]. 3. EXPERIMENTAL STUDY 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,

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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 1 2 3 Abrasive size, m 18 m 70 m Hardness, BHN 88 93.4 97.2 Applied load, N 5 15 25 Sliding time, s 30 60 90

4. RESULTS AND DISCUSSION 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%).

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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. Expert no. 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 Abrasive size, m (A) 18 18 18 18 18 18 18 18 18 70 70 70 70 70 70 70 70 70 Main factors Hardness, HB Load, (B) N (C) 88 5 88 88 93.4 93.4 93.4 97 97 97 88 88 88 93.4 93.4 93.4 97 97 97 15 25 5 15 25 5 15 25 5 15 25 5 15 25 5 15 25 Sliding time, s (D) 30 60 90 30 60 90 60 90 30 90 30 60 60 90 30 90 30 60 Diamond reinforced MMCs Weight loss S/N ratio (dB) in g 0.00370 48.6360 0.00550 0.01040 0.00160 0.00280 0.00740 0.00096 0.00290 0.00210 0.00890 0.01370 0.01730 0.00480 0.00860 0.00750 0.00400 0.00510 0.00720 45.1927 39.6593 55.9176 51.0568 42.6154 60.3546 50.7520 53.5556 41.0122 37.2656 35.2391 46.3752 41.3100 42.4988 47.9588 45.8486 42.8534

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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.

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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].

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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) 94 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. Nickel (Ni) 4 Copper (Cu) 1.5 Molybdenum (Mo) 0.5 Carbon 0.01

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].

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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.

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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.

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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

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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

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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.

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(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.

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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.

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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

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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. 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

Numune Saf Magnezyum Ti-50%Mg Ti-60%Mg Ti-70%Mg Ti-80%Mg

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.

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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

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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. 2. DENEYSEL ALIMALAR 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. 3. DENEYSEL SONULAR ve TARTIMA 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.

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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.

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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.

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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.

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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.

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FERROUS POWDER METALURGY

www.turkishpm.org

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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

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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. 2. EXPERIMENTAL PROCEDURE 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.

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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 pre- alloyed powder- mean values and standard deviation.

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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 + 52g FeMn (added in the form of a lump); not tempered (right) and after tempering (left).

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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 + 52g FeMn (added in the form of a lump); not tempered (right) and after tempering (left).

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 + 52g FeMn (added in the form of a lump); not tempered (right) and after tempering (left).

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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

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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).

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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.

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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.)

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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

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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.

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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 2.1.3 Heat Treated Properties

Figure 10. Microstructure of Distaloy AQ + 0.78%C

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 treatment at the same heat treatment conditions due to the graphite content in the part.

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Figure 13. Elongation variation after Q&T heat treatment at the same heat treatment conditions due to the graphite content in the part. 2.1.4 Typical Performances

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

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. 3. ASTALOY CrA

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

CHEMICAL COMPOSITION: Fe base + 1.8% Cr, Fully Pre-Alloyed

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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.

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Standard Sintering

Figure 22. Microstructure of Astaloy CrA with %0,4 sintered carbon content shows Pearlitic structure with around %5 ferrite inside.

Figure 23. Microstructure of Astaloy CrA with %0,6 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

Figure 25. Microstructure of Astaloy CrA with %0,4 sintered carbon content shows Pearlitic structure with around %5 ferrite inside.

Figure 26. Microstructure of Astaloy CrA with %0,6 sintered carbon content shows totally Pearlitic structure.

Figure 27. Microstructure of Astaloy CrA with %0,8 sintered carbon content shows totally Pearlitic structure.

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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. 4. CONCLUSIONS

Figure 29. Microstructure of Astaloy CrA + %1 Cu with %0,6 sintered carbon, shows Martensitic structure with around %10 pearlite and some Bainite.

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

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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

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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. EXPERIMENTAL STUDY 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. RESULTS AND DISCUSSION 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.

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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.

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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.

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Figure 8. Micrograph of DIN 1.3395 tool steel. Solution annealing temperature : 1100C, etched by nital + Beraha II solution.

Figure 9. Micrograph of DIN 1.3395 tool steel. Solution annealing temperature : 1200C, etched by nital + eraha II solution.

Figure 10. Micrograph of DIN 1.3394 tool steel. Solution annealing temperature : 1000C, etched by nital + Beraha II solution.

Figure 11. Micrograph of DIN 1.3394 tool steel. Solution annealing temperature : 1100C, etched by nital + Beraha II solution.

Figure 12. Micrograph of DIN 1.3394 tool steel. Solution annealing temperature : 1200C, etched by nital + 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.

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(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.

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FORMING PROCESSES

www.turkishpm.org

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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

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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 625 Ni 64,043 Cr 20,9 Fe 2,600 Nb 3,2 Mo 8,4 % arlk Al 0,01 Ti 0,01 Co 0,01 C 0,029 Si 0,31 Mn 0,39

Tablo 2. NI 625 speralam tozlarnn zellikleri zellik retici retim yntemi Toz ekli Vurgu younluu (g.cm3) Teorik younluk (g. cm3) Partikl boyutu (m) D10 D50 D90 NI 625 Osprey Gaz atomizasyonu Kresel 5,3 8,58 3,7 11,1 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.

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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

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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

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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

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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.

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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.

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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).

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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

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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.

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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.

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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.

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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

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SNTERLEME PARAMETRELERNN MONEL 400 ALAIMI TOZUNDAN RETLM PARALARIN MEKANK ZELLKLERNE ETKS
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, 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

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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. 2. DENEYSEL ALIMALAR 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 66.8 Cu 31.45 Mn 1.33 Fe 0.97 Si 0.38 C 0.1 P 0.013 S 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

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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. 3. DENEYSEL SONULAR VE TARTIMA 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

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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.

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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 6. Sinterleme sresiyle ekme mukavemeti ve kopma uzamasnn deiimi (sinterleme scakl 1180 C).

ekil 7. Sinterleme sresiyle ekme mukavemeti ve kopma uzamasnn deiimi (sinterleme scakl 1200 C).

izelge 2. Sinterleme sresine bal olarak mekanik zelliklerin deiimi. Sinter. sresi (dk.) 60 75 90 105 Sinterleme younluu(%) 1180 C 84 87 91 91 1200 C 88 91 94 93 Akma mukavameti (MPa) 1180 C 74 89 92 108 1200 C 102 90 92 71 ekme mukavameti (MPa) 1180 C 167 202 234 258 1200 C 211 248 259 244 Uzama (%) 1180 C 5,7 7,2 9,3 9,4 1200 C 6,0 11,3 11,7 13,2

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

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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 deiimi (sinterleme sresi 60 dakika).

ekil 12. 1200 oC scaklkta sinterlenen numunede sinterleme sresi ile i yapnn deiimi (sinterleme sresi 75 dakika).

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ekil 13. 1200 oC scaklkta sinterlenen numunede sinterleme sresi ile i yapnn deiimi (sinterleme sresi 90 dakika). 4. SONULAR

ekil 14. 1200 oC scaklkta sinterlenen numunede sinterleme sresi ile i yapnn deiimi (sinterleme sresi 105 dakika).

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.

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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

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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. DENEYSEL ALIMALAR 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.

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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).

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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. SONULAR VE TARTIMA 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.

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(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.

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(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].

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(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.

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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.

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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.

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(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.

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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.

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MECHANICAL ALLOYING

www.turkishpm.org

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The effect of reinforcement ratio on hardness of Al-Al2O3 composites fabricated by mechanical alloying technique
Aykut Canakci1, Temel Varol1, Saban Ertok1
1

Department of Metallurgical and Materials Engineering, Karadeniz Technical University, Trabzon, Turkey aykut@ktu.edu.tr, tvarol@ktu.edu.tr 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. Experimental Procedure 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

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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.

Fig. 1. Morphology of as-received powders: (a) Al alloy and (b) 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

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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

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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].

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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.

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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.

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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.

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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.

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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.

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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

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2. EXPERIMENTAL PROCEDURE 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 First Step Second Step First Step Second Step First Step Second Step 625 585 620 570 620 570 Time (min) 10 30 5 45 10 45 Pressure (MPa)/(KN) 339.5/110 462.9/150 401.2/130

3. RESULTS AND DISCUSSION 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.

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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) Sample 1 Sample 2 Sample 3 3.0230 3.0050 2.9870 Real Density (g/cm3) 2.9287 2.8452 2.9006 Density Percentage 96.68 % 94.68 % 97.1 %

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.

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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.

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Fig 5. SEM images of sample 2. (a) Scale of 100 m (b) Scale of 20 m.

Fig 6. SEM images of sample 3. (a) Scale of 100 m (b) Scale of 20 m.

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.

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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.

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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 Technical University, Metallugical and Materials Engineering,, 34469 Maslak, Istanbul, Turkey, ertug@gmail.com * Istanbul Technical University, Metallugical and Materials Engineering,, 34469 Maslak, Istanbul, Turkey, gokceh@itu.edu.tr ** Istanbul Technical University, Physics Engineering, 34469 Maslak, Istanbul, Turkey, altuncevahir@itu.edu.tr * Istanbul Technical University, Metallugical and Materials Engineering,, 34469 Maslak, Istanbul, Turkey, ovecoglu@itu.edu.tr * Istanbul Technical University, Metallugical and Materials Engineering,, 34469 Maslak, 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].

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

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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.

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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

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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

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METALLIC FOAM

www.turkishpm.org

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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-

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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-

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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. DENEYSEL ALIMALAR 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.

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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).

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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

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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

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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.

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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.

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TiCN Takviyeli 316L Paslanmaz elik Kpklerin retimi ve zellikleri


Halil . BAKAN1 ve Kemal KORKMAZ2
2

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

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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. 2. DENEYSEL ALIMALAR 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).

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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

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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.

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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.

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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

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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-

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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.

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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.

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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.

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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 38 43 51 59 5.3 2.1 4.1 4.3 Hgeri 8.6 4.4 7.5 8.5

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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-

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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.

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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.

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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 Materialia, Vol. 53, pp. 337-343, 2005. 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 Materialia, Vol. 57, pp. 1020-1023, 2007. 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.

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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.

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MODELING, SIMULTATION AND CHARACTERIZATION

www.turkishpm.org

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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,

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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.

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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)

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ve

(3)

Burada;

ve

(4) srasyla yerekimi kuvveti ve d kuvvettir (ayrk ve trblans yitim hz denklemleri aada veril(5)

Burada p statik basn, gerilim tens, vz swirl hz, faz ile etkileimden ykselme gibi).

Reynolds stress model (RSM) gre trblans kinetik enerji mitir.

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].

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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].

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Tablo 1 Saysal simlasyon iin azot gaznn zellikleri Fiziksel zellikler Younluk (kg/m3) C (J/(kg.K)) Termal iletkenlik (W/(m.K)) Referans viskosite (kg/(m.s)) Referans scaklk (K) Efektif scaklk (K) Molekler arl (kg/(kg.mol)) Standart hal entropisi (J/(kg.mol.K)) Deer 1.138 1040.67 0.0242 1.663 10-5 273.11 106.67 28.0134 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].

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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 Nozul Nozul As Boaz akl (mm) Boaz Alan (mm2) knt Mesafesi (mm) alma Basnc (bar) 8 Mevcut Nozul [9] 26 0,2 8,5 5 10 13 17 8 Model 1 26 0,3 12,7 6 10 13 17 8 Model 2 16 0,2 11 5 10 13 17 8 Model 3 26 0,2 11 6,84 10 13 17 Gaz Hz (m/s) 597 613 622 626 580 592 608 624 590 605 629 647 594 623 636 646 Mach Says 2,61 2,77 2,88 2,94 2,51 2,58 2,69 2,81 2,57 2,72 2,96 3,21 2,84 2,88 3,05 3,23 Gaz Debisi (kg/dak) 1,06 1,72 2,24 2,95 1,74 2,14 2,84 3,54 1,13 1,42 1,84 2,46 1,08 1,61 1,94 2,64 U Basnc (mbar) 1002 1023 1070 1166 965 1007 1086 1176 1009 1027 1061 1144 956 971 974 1023

ekil 6. Atomizasyon basncna gre nozullarn u basn deiimi.

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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.

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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.

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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

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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.

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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.

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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).

ekil 3. Mesh yaps ve snr artlar.

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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.

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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.

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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.

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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

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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 10 10 10 13 13 13 16 16 16 7 Darboaz akl (mm) 0,2 0,3 0,4 0,2 0,3 0,4 0,2 0,3 0,4 0,4 alma Basnc (bar) 13 13 13 13 13 13 13 13 13 13 Gaz Hz (m/s) 616,3 598,7 588,0 633,4 622,1 612,7 643,6 631,7 620,8 600,9 Mach Says 2,78 2,59 2,48 2,99 2,85 2,74 3,13 2,96 2,83 2,61 Gaz debisi (kg/dak) 2,099 2,821 3,533 2,259 2,942 3,668 2,435 3,172 3,876 3,441 U Basnc (bar) 0,896 0,901 0,988 0,939 0,961 1,178 1,078 1,159 1,372 1,037 Dzeltilmi U basn (bar) 0,784 0,788 0,865 0,822 0,841 1,031 0,943 1,014 1,201 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

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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).

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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.

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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).

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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 ** Gazi niversitesi Teknik Eitim Fakltesi, Metal Eitimi Blm, Teknikokullar, 06500, Ankara, hakangokmese@gazi.edu.tr *** Gazi niversitesi Teknik Eitim Fakltesi, Metal Eitimi Blm, Teknikokullar, 06500, Ankara, 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

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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. 2. DENEYSEL ALIMALAR 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.

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izelge 2. Isl ilem ncesi ve sonras younluk deiimleri Numune Kodu Numune 1 Numune 2 Numune 3 Numune 4 Numune 5 Isl lem Scakl (C) 550 550 550 550 550 Isl ilem Sresi (saat) 2h 4h 8h 12h 24h Isl lem ncesi Younluk (g/cm3) 2,77 2,76 2,75 2,74 2,73 Isl lem Sonras Younluk (g/cm3) 2,62 2,62 2,66 2,7 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

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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

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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.

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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.

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MKRO YAPIDA BOYUTLU YZEYLERN GZENEKLLK VE MKROSERTLNE RETM PARAMETRELERNN ETKS


Blent ZTRK1,2, mer Necati CORA2,3 ve Muammer KO 2,4
1

Karadeniz Teknik niversitesi, Mhendislik Fakltesi, Metalurji ve Malzeme Mhendislii Blm, 61080, 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-

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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. DENEYSEL ALIMALAR 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 83 103 155 Younluk (g/cc) 5.1 5.16 4.98 %Cu min 99.82 99.78 99.83 +80 2 max +100 20-50 2 max +150 50- 75 Bal Elek Analizi-Mesh- % +200 +325 10 max Tr 50-80 0.5 max 20-50 Bal -325 10 max 95 min

ekil 1. almada kullanlan kalp seti.

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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

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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).

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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. SONULAR VE TARTIMA 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].

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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.

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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.

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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.

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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.

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POROUS MATERIALS

www.turkishpm.org

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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 ** Gazi niversitesi Teknik Eitim Fakltesi, Metal Eitimi Blm, Teknikokullar, 06500, Ankara, 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

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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. DENEYSEL ALIMALAR 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] 2.3. Karakterizasyon 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.

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(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 (%) 0,5 0,75 1 1,5 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. 70 Deformasyon oran (%) Kprtme scakl (oC) 650 670 690 710 Kprtme sresi (dak.) 2-2,5 3-3,5 4-4,5 5

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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].

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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.

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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

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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

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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 pre- alloyed 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-

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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

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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-

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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

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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

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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.

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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.

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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

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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].

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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. 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 1W 250kW H2, CO2, CH4 Yksek verim, yakt eitlilii, ucuz katalizr, hzl ilk alma, Kat Elektrolit Katottaki aktivasyon kayb dk, sv elektrolit, yksek temas Safl dk hidrojen kullanlabilir, sv elektrolit, yksek temas Yksek verim, yakt eitlilii, ucuz katalizr, Yksek Scaklk, Sv Elektrolit, yksek Korozyon temas Dk verim, metanoln zehirli bir yakt olmas Yaktn elde edilmesi zor Yksek Scaklk, Korozyon, Hcre retimi zor ve pahal ok saf H2, Pahal katalizr

Yakt Hcresi Tr Proton geirgen zarl yakt hcresi (PEMFC)

alma Scakl 20-100C

Uygulama Alanlar Portatif Sistemler, Jeneratr, Askeri sistemler Elektrik santralleri, Orta lekli iletmeler iin s ve elektrik, Portatif Sistemler Uzay aralar Elektrik santralleri, Orta lekli iletmeler iin s ve elektrik

Kat oksit yakt hcresi (SOFC)

5001000C

Alkaline (bazik) yakt hcresi (AFC) Fosforik Asit yakt hcresi (PAFC)

50-100C

200W 10kW

H2

190220C

10kW 1MW

H2

Eriyik Karbonat yakt hcresi (MCFC) Dorudan Metanol (veya Etanol) yakt hcresi (DMFC veya DEFC) Dorudan Bor hidrr yakt hcresi (DBFC) Dorudan Glikoz yakt hcresi (Biyolojik yakt hcreleri) (DGFC)

600650C

200kW 10MW

H2,CO

Elektrik santralleri

50-100C

<1W 200W

CH3OH, Ucuz Yakt, Kolay (C2H5OH) depolanan sv yakt

Portatif Sistemler

20-100C

1W 200W

BH4-1

Alternatif yakt, yksek ak u gerilimi

Deneme aamasnda

10-50C

1W 20W

C6H12O6

Yakt vcutta bol miktarda bulunmakta, Glikozdan bakterisiz olarak akm retimi

Dk g younluu

Kalp pili, la pompas, sensr

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2. DENEYSEL ALIMALAR 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

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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).

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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.

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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.

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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.

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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.

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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).

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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.

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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. 2. DENEYSEL ALIMALAR 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

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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 200 MPa 250 MPa 300 MPa Ham Younluk (%) 89 91,5 94 500 C 91 92,6 94,4 540C 91,5 93 95,2 580 C 91,7 93,3 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.

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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

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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.

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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

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POWDER COMPACTION AND APPLICATIONS

www.turkishpm.org

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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.

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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

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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.

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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.

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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].

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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

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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.

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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