Influence of Nano – Sized Powder Content on

Mechanical Properties of Re-cycled Waste

Refractory Brick

1st 2st
Nabile Hassine E. M. Zindah
Materials and Metallurgical Materials and Metallurgical 1st
Hana Jamhour
Engineering Engineering Materials and Metallurgical

University of Tripoli University of Tripoli Industrial Reachar Center Tajoura

Tripoli, Libya Tripoli, Libya Tajoura, Libya

nabs65@hotmail.com e.zindah@uot.edu.com hanajamhoer@yahoo.comline

Abstract—The present research work involved cleaning
contaminated acid resistance refractory brick waste, i.e. that
which was in direct contact with the furnace contents. Three
powder batches were prepared. Each powder batch was made
up of three components; brick waste nano–powder, coarse
over–sized (+0.355mm) waste brick powder, and 75micron–
sized local Sebha Kaolin clay. These powder batches were
pressed, in a semidry state, at a pressure of 100 Pa. The
powder batches were then dried at a temperature of 110°C
before being fired at 1000, 1300, and 1500°C to produce shaped
final products. Characterization of starting refractory waste
bricks, waste coarse powder, Sebha kaolin clay, and waste
nano–powder using the technique of X – Ray Diffraction
(XRD) analysis was carried out. The work also involved the
measurement of mechanical properties of waste bricks and
sintered final products. The inclusion of 30 % of nano–sized
powder particles as a component in the refractory powder
batches had the most enhancing effect on the mechanical
properties of cold crushing strength and flexure strength of the
final shaped products fired at 1300°C.
Keywords—Nano-Crystalline, Recycled acid refractory,
Mechanical properties
I. INTRODUCTION
This There are several industries that use refractory
material for their furnace linings. these ceramic liners
undergo rapid temperature changes during each liquid metal
pouring cycle, which introduces stress gradients leading
ultimately to the nucleation and growth of cracks by
phenomena that is generally known thermal shock [1].
Thermal shock leads to loss of stiffness, mechanical strength
and overall material degradation. The damage caused results
in furnace shutdown for the replacement of brick and the
result is significant economic losses in the lost production
time and the brick replacement. It also represents the most
significant cost in maintenance of steel production plants.
Other factors contributing to damage of liners include
erosion refractory bricks because of high temperatures and
wear of refractories due to chemical attack slag[2,3]. The
concept of waste minimization and recycling has gained
importance modern research with emphasis shifting towards
natural resources saving and environment protection.
Approximately three million tons of spent refractory
materials are generated annually in the United States of
America by the ferrous, nonferrous, and glass industries[4]
while in Misrata Iron and Steel Complex it is about 5000
tons of spent refractory lining constitute a major percentage
of the industrial waste generated by metal manufacture
plants. the physical and mechanical properties of the
refractory are bulk density, apparent porosity, crushing
strength, refractoriness under load, thermal expansion,
thermal conductivity, thermal shock resistance and modulus
of deformation[5]. These properties are expected to be
improved by the nano-crystalline structure having either
particle size or grain size less than about 100nm. This
structure can be obtained through a formation processing
technique such as high- energy ball milling[6]. This research
study focused on investigating the processing and
mechanical properties of the powder of an acid refractory
brick waste after being ground and milled to nano-crystalline
size. The waste brick was obtained from the sixth furnace of
Misrata Iron and Steel Complex. characterization of starting
refractory waste powder, Kaolin clay was ground powders
as well as sintered shaped products was carried out via X-
Ray Diffraction technique.
II. EXPERMINTAL WORK
A. Section of Refractory Brick Waste Samples
Six samples where acid resistance refractory brick waste
were collected from Msrata Iron and Steel Complex. These
selected brick (240x115x100mm) was used in lining sixth
furnace which operated at a temperature 1000°C. Local
Sebha Kaolin clay powder was collected and prepared for
used as a binder in making of experimentally refractory brick
samples.
B. Cleaning and Hammering Milling of Brick Samples
The surface of waste brick samples were cleaned by a
water saw jet, pressed used a compression machine so as the
cleaned samples can be broken up into a small pieces. These
pieces are then crashed manually with a hammer to about
30mm in diameter pieces. These pieces were then milled to
a powder of overall particle size of about 1mm using a
crushing hammer mill (Hammer Muehel HW1-
2008,Garmmany).
C. Sizing( sieving) and Homogenization
The hammer milled powder samples were passed through
the different sieving (0.355,0.18,0.125,0.09,0.045mm)
.125,0.09,0.045mm) for fo
about 25minuteswhich produced various
arious sizes. The oversized
particles (+0.355) for all the six
x waste bricks were separated
and used to produce duce a homogeneous sample using
homogenizing machine. Thee rest of the various size were
rejected. The separated overr size powder was used later for
the production of nano- powder.
D. production of nano- powder
Milling of the over- sized (+0.355) refractory waste
powder was performed using a high energy centrifugal ball
mill [Model S100, Retsch GmbH]. Figure 1 shows a picture
for this mill.
Figure 1.The centrifugal ball mill used in the present work.
Dry milling was carried out in 250ml steel jar using 4,10,12
and 13mm diameter stainless steel balls. After every milling
run, the steel jar would be cleaned with ethanol and silica
sand to minimize iron contamination of the milled powders.
The time of milling, in hours, was varying from 5 to 15 in
steps of 5. The reversing of operation setting is 35 second
running time, rundown and stop for one second followed by
a change in direction of rotation,35 second running time, etc.
this is repeated until the total running time has expired. the
speed of the milling was set 300 rmp. Higher speeds were
practically not suitable due to increased agitation of the
machine. The ratio of the weight of the steel ball to the
refractory waste powder was chosen to be 10:1.
10:1 As quantity
of the material to be milled should not exceed approximately
1/3 of the grinding jar volume; the jar loaded with a fixed
amount, for all run ,of 50 grams of acid resistance refractory
brick powder. The weight of steel ball was 500 grams. X- X kaolin clay powder respectively. As mention above, the
Ray Diffraction was used to confirm attainment of nano- nano
powder particles.
E. X-Ray Diffraction Analysis
X-Ray
Ray (XRD) diffraction was used to estimate crystalline
size of milled powder particles. The XRD patterns were
taking using a computerized X-ray ray diffractmeter (model
:pw1800 of n/v Philips NV, Holland) at the petroleum
recherché center, Tripoli all X-ray
ray diffractograms were taken
by Cu Kα radiation (wave length, λ=0.15405nm) at the
scanning speed of 0.1 per second in 2θ, a tube voltage of 40
kV, atube current of 30mA,and the time of 10 second were
used. The fine powder were run at 0.002 ◦θ step and scan
step time of 0. 5000. Sherr equation, L=Kλ / βcosθ was
developed in 1918, to calculate the crystalline size (L) by X-
X
ray radiation of wave length λ(nm) from misread full width
at the half maximum of peaks β in the radiation located at
any 2θ in the pattern. Shape factor of k can be 0.62-2.08 and
is usually taken as about 0.89
0.89.but if all of the peaks of a
pattern are going a similar value of L, then βcosθ must be
identical. This means that for a typical 5nm crystalline size
and λ CuKα = 0.15405nm , the peak at 2θ = 170◦ must be
more than ten times wide with respected to the peak at
2θ=10◦◦ which is never absorved. A Modified Scherrer
equation put for word by Moshi et al [7] to provide a new
approach to kind of using Scherrer equation, so that at least
squares technique can be applied to minimize the source of
error. Modified Scherrer equation plots lnβ against (ln
1/cosθ) and obtainedined the intercept of least squares line
regression form which a single value L is obtained through
all of available peaks. The novel technique is applied to
calculate crystalline grain size of the milled waste refractory
brick powder used in the present research work.
F. Sintering Trials
Sintering is curried out on a powder mix made up of the
following components :-
a) Acid resistance brick waste homogenization powder
(+0.335) used as coarse powder component .
b) Sebha kaolin clay 75 µ used as a medium particle and a
source of bonding material and
c) Nano- size refractory waste powder with varied fractions
designation as N1=10,N2=20,N3=30 wt%.
 Mixing
Three powder batches were prepared, with each weighing
100gram. Mixing g of the above-mentioned
above powder
components was performed in closed plastic container with
the addition of 15ml of distilled water. The mixing was
carried out manually by shaking the closed plastic container
and with the use of polyethylene balls as a mixing medium
to improve blending. Polyethylene balls are suitable for
mixing and blending since they are light weight and
approximately soft. Hence they will not lead to crushing of
the powder particles and also, any remained polyethylene in
the powder mixture
xture will be evaporated easily upon heating.
The composition of the aboveabove- mentioned three powder
batches is given below;
1. 45:N1:45
2. 40:N2:40
3. 35:N3:35
The equal first and Third numbers represent the fraction of
the over-sized(+0.355)
sized(+0.355) coarse waste refractor
refractory powder and
designation N1,N2,and N3 represent The weight fraction of
nasno-sized
sized refractory waste powder.
 Compaction
Carried out by pressing 100gram of powder at a pressure
100bar with a holding timee 15
15-30 minutes in a die using a
hydraulic pressing machine (Model; sassuolo, ceramic
Instruments, Italy).
 Drying
Prepared shaped green bodies were dried at a temperature of
110°C for 24 hours in a drying oven (Model; Memmert,
Germany). After drying were measured using avernier
Callipers.
  Sintering(Firing) III. RESULTS AND DISCUSSIONS
The shaped green sample were initially heated from room
temperature to 600°C and were held at this temperature for A. Powder Phase Composition
45 minutes. The temperature was then increased over a time A.1 Refractory Waste Brick Powder
period of 90 minutes to the firing temperatures of
The phase composition of the six waste acid resistance
1000,1300, and 1500°C and using the same soaking time for
all three temperature of 60 minutes. The sample were then refractory bricks as determined by XRD analysis is given in
left to cool in the furnace until the following day. This Table 1shown below;
heating schedule was accomplished using a Nebertherm
N Table 1: Phase Composition of waste bricks samples.
samples
sintering furnace. Dimensions of sintered samples were then
measured using a vernier calipers. This work was carried out Brick sample Compound Chemical SemiQuant [%]
at the laboratories of the Industrial Research Centre, Tripoli.
Tripoli Number Name Formula
1 Quartz SiO2 44.12
G. Measurement of Mechanical Properties Bischofite MgCl2.6H2O 36.27
Mullite Al6Si2O13 19.61
 Cold Crushing Strength 2 Quartz SiO2 43.49
Cold crushing strength was measured for the starting waste Bischofite MgCl2.6H2O 32.29
brick pieces (50x50x50mm) and 3 batches of final sintered Mullite Al6Si2O13 24.22
3
shaped products at the sintering temperatures of Quartz SiO2 46.39
1000,1300,1500°C. The measurement was carried out at Bischofite MgCl2.6H2O 22.68
Mullite Al6Si2O13 30.93
room temperature by placing the specimen
men on a flat surface 4
followed by the application of a uniform load to it through a Quartz SiO2 43.00
Bischofite MgCl2.6H2O 33.78
bearing block the test was performed in accordance with the Mullite Al6Si2O13 23.22
standard ASTM C133-97(Re- approved in 2003) using a 5
hydraulic compression testing machine. The load at which Quartz SiO2 46.36
Bischofite MgCl2.6H2O 21.85
crack
ck appears on the refractory specimen represents the cold Mullite Al6Si2O13 31.79
crushing strength of the specimen which is then measured 6 Quartz SiO2 42.55
directly by software built in machine. Bischofite MgCl2.6H2O 36.17
 Bending Test Mullite Al6Si2O13 21.28

The flexure strength was measured for all sintered samples

using a Tecno Tester ( Model,el, E.DE Nicola, Italy) at a rate
1Newton/second . The total number of samples tested was
27,, where 3 samples were taken from each batch which in
turn had 3 differently composed powders shaped and 1000,
1300,and 1500 °C.
Samples dimensions weree fed into the machine built-in
built
software to calculate the flexure strength directly from
instrument shown in Figure2 below,
The above table shown that the six waste bricks contain
silica quartz, bischofite ore hydrous magnesium chloride and
mullite. The latter has the formula 3AL2O3.SiO2 ie. It
contains 72% AL2O3 and its refractoriness is 1810-1850°C
1810 .
It occurs rarely in nature, but is found in many fired ceramic
bodies. It forms long, needle like crystals interlocking of
which given good mechanical strength at high temperature,
Mullite also shows a uniform thermal expansion, and its
formation in body makes for good thermal shock resist
resistance.
All six brick sample were thoroughly mixed in a
homogenizing machine to produce one homogeneous
powder sample which was milled in a high energy ball mill
to produce nano powder. This homogeneous powder sample
was subjected to XRD to determine its phase
pha composition as
is shown in Table2
Table 2: Phase composition of the homogenized powder sample.
sample

Specimen No:- Compound Chemical SemiQuant

Name Formula [%]
Sample of six Quartz SiO2 39.83
mixed samples Bischofite MgCl2.6H2O 29.20
Mullite Al6Si2O13 30.97

A.2.Sebha kaolin Clay Powder

Phase composition of Sebha Kaolin Clay is as shown in
Table 3. The analysis shows the presence of some free silica
Table 3: Phase and oxides composition of Sebha kaolin clay.
Figure 2.Bending Tecno Tester and test samples.
samples
Compound Name Chemical Formula SemiQuant [%]
Kaolinite Al2[Si2O5(OH)4] 86.96
Quartz SiO2 13.04
A. 3.Nano Homogenized waste brick powder
The homogeneous powder sample was subjected to high
energy ball milling to convert it to nano-sized powder and
the results obtained are given Table 4.
Phase composition for the above-mentioned three nano
powder samples are shown below in Tables 5,6,and 7and
Figure 4 shows the XRD pattern for the powder milled for 10
hours.
Table 5: Phase composition of sample milled for 5 hours.

Table 4: Crystallite size of homogeneous powder. Specimen Compound Chemical SemiQuant [%]
No Name Formula
Milling time (hours) Crystallite size (nm) 5 hours of Quartz SiO2 40.91
milling Bischofite MgCl2.6H2O 30.00
5 51 time Mullite Al6Si2O13 29.09
10 47
Table 6: Phase composition of sample milled for 10 hours.
15 45
Specimen Compound Chemical SemiQuant [%]
No Name Formula
The conversion of the coarse homogeneous powder to the 10 hours of Quartz SiO2 41.67
milling Bischofite MgCl2.6H2O 27.78
nanometer size was found to be possible using a high energy time Mullite Al6Si2O13 30.55
ball milling technique using various sized medium. This sort
of grinding medium appears to reduce the problem of the
Table 7: Phase composition of sample milled for 15 hours.
powder caking onto the sides of the mill and not receiving
Specimen No Compound Chemical SemiQuant
any further size reduction. In other words, the use of Name Formula [%]
differently sized steel balls as the grinding medium seems to 15 hours of Quartz SiO2 44.12
milling time Bischofite MgCl2.6H2O 34.31
facilitate the subjection of powder particles to continuous Mullite Al6Si2O13 21.57

impact size leading eventually to the required nano-sized

Counts
particles. In the present research work, the crystallite size H-10
600

was successfully reduced to the size range over an increasing

milling time from 5 to 15 hours. The crystallite size was
calculated using the Modified Scherrer equation. The
obtained size are all less than 100nm and hence the powder 400

can be considered as nano-sized and should have the

potential advantages and properties improvement exhibited
by nano -materials. An illustration of computer soft ware
200

used for the calculations is shown in Figuer3.

0
10 20 30 40 50 60 70

Position [°2Theta]

Figure 4: XRD pattern for the powder milled for 10 hours.

Based on XRD investigative work of all powder samples

mentioned above , it was found that the nano-powder milled
for 10 hours was closely matching in composition the coarse
over sized (+0.355mm) homogenous powder. In addition,
this nano-powder had the least degree of agglomeration and
hence was the most suitable for preparing the three powder
batches used for the sintering trials.
Figure. 3. An illustration of the computer calculation of the crystallite size
for the powder milled for 5 hours.
B. Cold Crushing Strength 140
120

Crushing Strength
B.1.Waste Refractory Brick Samples Strength
100
The six waste brick samples were subjected to Cold crushing

(N/mm2)
strength measurement in which the cross-sectional 5x5= 80 cold cruching
45:N1:45
25cm2, as is shown in Table 8. 60 cold40:N2:40
cruching
40
Table 8 : Cold crushing strength of waste brick samples.
30:N3:35
cold cruching
20
Sample Number Max. load (N)
Cold crushing strength 0
(N/mm2)
800 1000 1200 1400 1600
1 97.1 38.82 Temp. (°C)
2 87.9 35.18
3 86.3 34.51 Figure .5.Cold crushing strength as a function of firing temperature.
4 143.9 57.56
5 204.5 81.81 C. Bending measurements of Sintered Final Products
6 154.8 61.92 The obtained values are as shown inTable10 and presented
graphically in Figure 6 all specimen batches show an
B.2.Sintered Final Shaped Products Strength increase in flexure strength as the firing temperature used
Cold crushing strength of sintered specimens was obtained
increased from 100to1500°C, with the batch 45:N1:45
values are given in Table 9 and shown graphically in Figure
showing the highest bending strength. Once again it can be
5 as van be seen from the presented value ,all specimen
observed that nano-powder fraction increased, this led to an
batches have the same trend of rising crushing strength when
improvement in flexure strength for the specimen batches
firing temperature being increased from 1000 to 1300°C. It
fired at 1300°C. This further shown the possible
can also noted that the second and third specimen batches
advantageous influence of having nan0-powder particles
suffered a drop in strength as firing temperature was
component in the powder mix used for the production
increased from 1300 to 1500°C. However, the most
refractory bricks.
encouraging result is shown by all the specimen batches fired
Table 10 : Bending strength values for sintered final shaped products.
at 1300°C, for which the crushing strength going up with
increasing nano-powder fraction content. This clearly shows Specimen Flexure Strength Sintering Temperature
Batch (N/mm2) (°C)
the potential benefit of using nano-sized powder particles as
2.80 1000
an important component of powder batches to enhance the 45 : N1 : 45
1300
20.59
cold crushing strength of refractory bricks. 38.46 1500
1000
40 : N3 : 40
2.84

22.19 1300
Table 9 : Cold crushing strength of final shaped sintered products.
25.53 1500
Specimen batch Strength Sintering 4.06 1000
(N/mm2) temperature 35 : N3 : 35
27.96 1300
(°C) 1500
32.87
19.83 1000
45 : N1 : 45
28.77 1300
60
flexure strength

36.36 1500
1000 40
(N/mm2)

17.88
40 : N2 : 40
57.48 1300 45:N1:45
20 40:N2:40
47.18 1500
30:N3:35
1000 0
16.07
35 : N3 : 35
1300 800 1000 1200 1400 1600
124.08
116.32 1500 Firing Temp. (°C)

Figure 6: Bending strength versus Firing temperature.

 IV. CONCOULASION
The following conclusion may be drawn;
 Nano- sized powder may be obtained by subjecting
coars waste brick powder to high energy centrifugal
ball milling for 5to15 hours, with the 10 hour time
period being considered the optimum milling time.
In addition, the powder milling time for 10 hours
had a composition closely that of the coarse-over
sized(+0.355mm) homogenous powder.
 Waste refractory brick piles at misrata Iron Steel
Complex may be reduced through the production of
recycled thermal brick which can find for lining high
furnace working at temperature to 1300°C . This will
contribute to words a better and cleaner having by
minimizing waste pollution.
 Melting and formation of glass phase fired at a
temperature of 1500°C. additional work involving
firing of shaped pure nano-powder specimens clearly
showed, by visual inspection and the specimens
shape loss, the occurrence of melting at the sintering
temperature of 1500°C.
 The presence of this phase had negative effect on the
mechanical properties. Hence, based on the obtained
results of the present research work this limited the
recommended maximum working temperature of the
produced brick to 1300°C.
 The inclusion of 30 %(N3) of nano-sized powder
particles as a component in the refractory powder
batches had the most enhancing effect on the
mechanical properties of cold crushing strength and
flexure strength of final shapes products fired at
1300°C. The fired specimens maintained their
shapes without undergoing any deformation, and had
no cracks and no colour change, compared to the
colour of the original specimens, up to 1300°C. This
would mean that the most suitable refractory brick
powder batch is 35:N3:35 with the local Sebha.
ACKNOWLEDGMENT
First of all, praise to Allah, the most gracious and most
merciful. We would like to express our gratitude all group of
work at Industrial Research Center, Libyan Petroleum
Institute and Tripoli university .
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