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Preparation and characterization of porous alumina ceramics using different

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DOI: 10.2109/jcersj2.16233

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 Journal of the Ceramic Society of Japan 125 [5] 402-412 2017 Technical report

Preparation and characterization of porous alumina ceramics

using different pore agents
Mohammed Sabah ALI*,*****,³, M. A. Azmah HANIM*,***,‡, S. M. TAHIR*, C. N. A. JAAFAR*,
M. NORKHAIRUNNISA**,*** and Khamirul Amin MATORI****
*Department of Mechanical and Manufacturing Engineering, Faculty of Engineering, Universiti Putra Malaysia,
43400 Serdang, Selangor, Malaysia
**Department of Aerospace Engineering, Faculty of Engineering, Universiti Putra Malaysia, 43400 Serdang, Selangor, Malaysia
***Laboratory of Biocomposite Technology, Institute of Tropical Forestry and Forest Products, Universiti Putra Malaysia,

43400 Serdang, Selangor, Malaysia

****Department of Physics, Faculty of Science, Universiti Putra Malaysia, 43400 Serdang, Selangor, Malaysia
*****Department of Agriculture Machinery & Equipment Engineering Techniques, Technical College, Al-Mussaib, Iraq

Graphite waste from primary batteries, active yeast and commercial rice husk ash have been used as pore-forming agents to
fabricate porous alumina ceramics using a fugitive materials technique. The pore-forming agent ratios were between 10 to
50 wt %. The effects of the pore-forming agent ratios on the mechanical properties, the porosity and the microstructure have been
investigated in this study. The results showed that through increasing the pore-forming agent ratio for graphite waste, yeast and
rice husk ash, the porosity increased from 37.3 to 61.1%, 30.2 to 63.8% and 42.9 to 49.0%, respectively. The hardness also
decreased from 172.6 to 38.1 HV1 and from 160.6 to 15.0 HV1 for porous alumina ceramics using graphite waste and yeast as
pore-forming agents, respectively. However, the hardness of the porous alumina ceramics with rice husk ash as a pore-forming
agent increased at 30 wt % (150.9 HV1) and 50 wt % (158.9 HV1). The tensile strength for porous alumina ceramics using graphite
waste and yeast as pore-forming agents decreased from 24.9 to 14.3 MPa and from 26.2 to 5.4 MPa. The compressive strength
decreased from 112.3 to 34.3 MPa and from 19.5 to 1.8 MPa, respectively. However, for porous alumina ceramics using rice husk
ash, the tensile strength increased at 30 wt % (24.1 MPa) and 50 wt % (21.9 MPa). The compressive strength also increased at
30 wt % (69.7 MPa) and at 50% (60.1 MPa).
©2017 The Ceramic Society of Japan. All rights reserved.

Key-words : Porous ceramics, Graphite waste, Yeast, Rice husk ash, Porosity, Mechanical properties

[Received November 3, 2016; Accepted February 14, 2017]

membrane supports prepared from fly ash as an industrial waste.

1. Introduction
Up to now, many fabricating techniques have been used to
manufacture porous alumina ceramics such as the organic foam
method, the freeze-casting method, sol­gel synthesis, the partial
sintering method and the pore-forming agent method.1),2) Porous
alumina ceramics, because of their high porosity, high surface
area, high thermal resistance, chemical stability2) and corrosive
environments have been widely used in many industrial fields,
such as biomedical implants, hot-gas purifiers, molten metal
filtration, catalyst supports and thermal insulation.3),4) The pore-
forming method is one of the most common and effective in
porous ceramics manufacturing.5) Recently, there has been
renewed interest in using waste materials. In general, there are
two kinds of waste materials, agricultural waste materials such as
rice husk6) and kenaf waste,7) and industrial waste materials such
as waste fly ash,8) paper pulp waste and glass.9) These types of
waste have been successfully used in the fabrication of porous
ceramics. Dasgupta and Kumar Das9) have used paper pulp waste
as a new source to fabricate porous ceramic composites. While,
Donga et al.8) have reported on the use of porous mullite ceramic
³
Corresponding author: M. S. Ali; E-mail: mohammed.sabah94@
yahoo.com
‡ et al.14) used lamellar graphite as a pore-forming agent to fabri-
Corresponding author: M. A. A. Hanim; E-mail: azmah@upm.
edu.my
Also, many researchers have used the agricultural waste to fabri-
cate porous ceramic composites. Sengphet et al.7) used kenaf
powder wastes for the fabrication of porous clay ceramics, while
Mohanta, et al.6) used rice husk for the preparation of porous
alumina ceramics. The motivation behind these efforts are the
increasing raw materials cost and decreasing natural resources
consumption which requires the use of byproducts and wastes
as raw material for different industrial processes. This is a step
towards environmental protection and sustainable develop-
ment.10) Graphite waste from primary batteries is the new indus-
trial waste used in this study to fabricate porous alumina ceramics
as a pore forming agent. Even though the primary battery is
nonhazardous, however, the batteries waste pose a problem for
the environment.11) Graphite is used in the battery industry as a
material for electrodes, primarily for its low reactivity and high
electrical conductance.12) It is estimated that around 25000
ton/year of graphite (natural and synthetic) was used to produce
batteries as per 2013. Graphite in natural flake form has higher
purity levels than synthetics, which provides excellent prop-
erties for use in batteries. It is usually used in applications of
the highest quality using new purification techniques and more
efficient processing methods.13) A number of researchers have
reported using pure graphite as a pore-forming agent. Piazza
cate porous lead zirconate titanate (PZT) ceramics with uniform

402 ©2017 The Ceramic Society of Japan

DOI http://doi.org/10.2109/jcersj2.16233
Journal of the Ceramic Society of Japan 125 [5] 402-412 2017
porosity. Ding et al.15) used graphite as a pore-forming agent to
produce mullite­bonded porous silicon carbide by an in situ reac-
tion bonding technique. The size of the pores derived from the
burnout of graphite depends on the size of the graphite particles.
Bai16) used graphite as a pore former using the reaction sintering
method to prepare porous mullite ceramics from calcined carbo-
naceous kaolin and ¡-Al2O3. As for Rahmawati et al.11) used
graphite waste from batteries were utilized as anode material for
LiFePO4 (LFP) battery.
Also, in recent years, there has been interest in the study of
micro-organisms, such as yeast materials, which can be used as
pore-forming agents in manufacturing porous ceramic materials.
Chi et al.17) studied the sintering behaviour of porous SiC ceram-
ics using yeast material as a pore-forming agent with a particle
size 350­450 ¯m. The porosity was 61.4­62.1% and the pore size
was in range of 100­550 ¯m. Xu et al.18) reported on the prepara-
tion of porous mullite­corundum ceramics with a controlled pore
size using bioactive yeast as pore-forming agent with the aid of
the reaction bonding method. The porosity was about 55% when
the mass ratio of yeast to ceramic powders is 1:2 and the pore
size was 0.5­3 ¯m. Xu et al.5) studied the fabrication of porous
alumina ceramics with a controllable pore size using bioactive
yeast as a pore-forming agent using the biotemplated method.
The porosity of the porous alumina ceramics decreased from 59.2
to 26.5% and the surface area decreased from 38.4 to 1.3 m2/g
when the calcinations temperature increased from 1200 to
1600°C and the pore size was 0.1­3 ¯m. Unfortunately, most
of the pore agents that have been used to produce porous ceram-
ics are accompanied by a decrease in the mechanical properties
due to the porosity.
In this paper, three types of pore agent were used to produce
porous alumina ceramics: graphite (industrial waste), commercial
rice husk ash (agricultural waste) and yeast (micro-organism
material). The aim of this research was to study the effects of
graphite waste, yeast and commercial rice husk ash ratios on
the mechanical and physical properties and to produce porous
alumina ceramics with different ceramic phases such as mullite,
cristobalite, corundum and sillimanite, but low in cost through
the direct mixing of different pore forming agents and alumina
powder, followed by sintering at high temperature.
2. Experimental
2.1 Materials and methods
Graphite waste was collected from used batteries. The graphite
rods were cleaned using an acetone solvent to remove any oil and
residue materials, then dried in air for 24 h and after that dried for
1 h in an electric oven at 100°C. Crushing process was conducted
using an electric grinder (RT-02A, 3000 rpm). The ground gra-
phite waste powder was sieved in an electrical sieve (Retsch,
As 200) to a particle size of 250 ¯m. The yeast materials were
ground in an electrical grinder (RT-02A, 3000 rpm) for 1 minute
and sieved in an electrical sieve (Retsch, As 200) to a particle size
of 250 ¯m. The commercial rice husk ash was ground in an
electrical grinder (RT-02A, 3000 rpm) for 1 min and sieved in an
electrical sieve (Retsch, As 200) to a particle size of 250 ¯m as
well.
A commercial aluminium oxide Al2O3 powder (μ = 3.94
g/cm3) with high purity (99.9%) and 0.5 ¯m in particle size,
was used as the starting material, and a commercial sucrose
(sugar) was used as a binder. The binder (10­12%) was added
to the ceramic mixture according to the maximum solubility of
sugar in water (distilled water). A 60 wt % concentration solution
was considered for use as a binder in this study.19) The binder was
JCS-Japan
mixed with ceramic powder using an agate mortal (3­5 min). The
graphite waste, yeast and rice husk ash powders were added at
ratio of 10, 20, 30, 40 and 50 wt % to the ceramic slurry. All the
batches were mixed by mortar for around 5­10 min and then ball
milled for 3 h in a plastic bottle to make them more homogenous
in the ratio of weight of alumina balls to weight of powder of
3:1. Dry mixtures were pressed uniaxially in a circular steel die
(diameter = 20 mm and thickness = 5 mm) using an Instron
hydraulic press at a pressure of 90 MPa. Green compacts were
dried in an oven at 110°C for 24 h. The organic burnout of dried
samples was carried out in an ambient atmosphere in an elec-
trically heated programmable furnace. The rate of heating was
1.5 °C/min for each increment in the temperature. According to
the TGA (thermo gravimetric analysis) of all the pore-forming
agents, the graphite waste and rice husk ash samples were sintered
at 200, 300, 500 and 900°C at soaking time of 1 hr in an electric
furnace. While for yeast, the samples were sintered at 200, 325,
500 and 900°C for a soaking time of 1 hr in an electric furnace at
the rates of heating and cooling of 1.5 °C/min to remove the
organic, inorganic and sucrose materials. After that, the ceramic
samples were sintered in another furnace at 1600°C for a soaking
time of 2 h, with the rates of heating and cooling of 5 °C/min. All
samples with different ratios of different pore agent and binder
(sucrose) after sintering had a uniform shape without any cracks.
2.2 Characterization of the ceramics samples
The microstructure and chemical composition were examined
using a field emission scanning electron microscope (FESEM)
and an energy-dispersive X-ray spectroscopy (EDX) technique
(SE-440). The phase compositions of the sintered porous alumina
samples were determined using an X-ray diffractometer (XRD)
[PANAlytical (Philips)X’pert ProPW3050/60] with Cu radiation
(wave length = 1.54060 ¡) at 40 mA, 40 kV using X-pert soft-
ware. The linear shrinkage of the samples during the sintering
process was calculated using Eq. (1).20)
L ðgreenÞ  L ðfiringÞ
Shrinkage ð%Þ ¼  100 ð1Þ
L ðgreenÞ
The compressive strength was measured using an Instron
machine using a sample with dimensions of 20 mm in diameter
and 24 mm in height according to the ASTM-1424-10 standard21)
at a crosshead rate of 0.5 mm/min. The maximum mechanical
load and cross-sectional area were used to calculate the compres-
sive strength of the samples. All samples were ground and
polished using a polishing media and then thermally etched. The
hardness values of the samples were measured using a micro
Vickers hardness machine. The value of the hardness was mea-
sured according to equation HV1 = 1.8544*(P/d 2) for hardness,
where P = applied load and d = average length of the two
diagonals of the indentation. The applied force was 9.81 N (1 kg)
for 15 s at full load. The average hardness at five positions of one
sample have been calculated with five samples for each parame-
ter. The sizes of indentation were more than the pore size and are
believed to represent the porous material hardness as practiced in
other research work referred22)­24) on hardness measurement for
porous ceramics. A Brazilian test was performed for samples of
dimension 20 mm in diameter and 5 mm in thickness using an
Instron machine. An average of five samples was used to obtain
the average strength, and hardness for each composition. The
pore size distributions of the specimens were determined using
image processing software (Image-J). More in detail, by
(FESEM), the images can be analyzed using a suitable software
that are able to measure the porosity.25),26)
403
JCS-Japan Ali et al.: Preparation and characterization of porous alumina ceramics using different pore agents

The density, overall porosity and open porosity of the sintered caprolactam materials were detected by the XRD test. Paraffin
samples were determined by the water immersion method based wax is a type of polymer with a melting point at about 50°C.32)
on Archimedes’ principle,27) as specified in ASTM C20-00 using Polycaprolactam is a type of polymer with a melting point at
the following equations: around 60°C. These materials are normally used in the battery
Mwet  Mdry industry.12),33) For yeast, ammonium hydrogen oxalate hydrate
Popen ¼ ð2Þ
Mwet  Msuspended þ Mwire has been discovered, and for rice husk ash, amorphous silica
  (SiO2) has been detected in the powder.
μ
Poverall ¼ 1   100 ð3Þ
μtheoritical
Mdry  μwater 3.2 Porosity, density, shrinkage, microstructure
μ¼ ð4Þ and pore size distributions for porous alumina
Mwet  Msuspended þ Mwire
ceramic
Closed porosity ¼ Poverall  Popen ð5Þ Table 2 shows the ratio of pore-forming agent, bulk density for
where Mdry is the dry mass28) of the sample, Msuspended is the mass green and sintered samples, overall porosity, open porosity and
of the sample suspended in distilled water, Mwet is the mass of shrinkage for different pore-forming agent materials.
the sample after soaking in the water, Mwire is the mass of the The closed porosity was characterised quantitatively by deter-
suspending system, Poverall is the volume fraction of the overall mining the values of the overall and open porosities of the porous
porosity (vol.%) of the sample and Popen is volume fraction of the alumina samples. Figure 4 shows the variation of the total
open porosity of the sample. The theoretical density (true) of alu- porosities and bulk densities with the pore-forming agent ratio
mina (Al2O3) is 3.94 g/cm3, this is used as a reference measured for the porous alumina samples using graphite waste, yeast and
by Accupyc II 1340.29)­31) rice husk ash as a pore-forming agent.34) The lower porosities are
37.3, 30.2 and 42.9% and the maximum porosities are 61.1, 63.8
3. Results and discussion and 49.0% respectively.
3.1 Graphite waste, yeast, rice husk ash and Low density and an increase in the overall and open porosity
binder characterization are linked to the thermal decomposition of pore-forming agent
The true density of the graphite waste, the yeast and the rice materials. The liquid phase does not appear during the graphite
husk ash powder were measured using a gas pycnometer oxidation in air because graphite is a thermoset material. This
(Accupyc II 1340). Finally, a particle size analyser (Malvern, leads to the green bodies avoiding shrinkage causing by the sur-
master size 2000) used to analyse the particle size distribution of face tension of the liquid phase as a pore former when heated.
all the pore agent materials (see Fig. 1). At the same time, the oxidation temperature of graphite (600­
TGA and DTA (differential thermal analysis) were performed 850°C) is higher than that of other organic pore-formers such as
for the graphite waste, the yeast, the rice husk ash and the sucrose ³100°C for polyvinyl butyral (PVB) and ³270°C for polymethyl
(sugar) powders under nitrogen gas at a rate of temperature of methacrylate (PMMA). Before the graphite is burn out com-
10 °C/min as shown in Fig. 2. pletely, the skeleton of the green bodies is kept intact by the resi-
The chemical composition of the graphite waste, the yeast, the dual graphite, resulting in less shrinkage than for samples with
rice husk ash and the sucrose were measured using an EDX. polymer as the pore-forming agent.15) In the case of the yeast
Table1 shows the chemical composition of the materials. samples, yeast completes its pyrolysis at a higher temperature
Figure 3 shows the XRD and EDX tests for graphite waste, than the general pore former, which relieves the closing of pores
yeast and rice husk ash. For graphite waste, paraffin wax poly- to happen, without deleterious residua and reaction with the green
body. TGA of the yeast is performed to determine the thermal
decomposition range. Figure 2 shows the TGA curve of yeast at a
heating rate of 10 °C/min. It is observed that the yeast is decom-
posed in three steps. In the first step (100­200°C), there is only a

Fig. 1. Particle size distribution of different pore-forming agents. Fig. 2. a) TGA and (b) DTA for graphite waste, yeast and rice husk ash.

Table 1. The chemical composition of graphite waste, yeast, rice husk ash and sucrose materials
Materials Elements C O2 Si P S K AL Mg Ca
Graphite waste Weight % 95.72 3.46 0.34 ® 0.36 ® 0.12 ® ®
Yeast Weight % 64.12 28.12 ® 2.21 0.75 4.56 ® ® ®
Rice husk ash Weight % 6.78 56.40 35.74 ® ® ® ® 0.43 0.66
Sucrose (sugar) Weight % 59.13 40.88 ® ® ® ® ®

404
Journal of the Ceramic Society of Japan 125 [5] 402-412 2017 JCS-Japan

Fig. 3. EDX spectra and XRD patterns (insert) for A) graphite waste, B) yeast and C) rice husk ash powders respectively.

Table 2. Porosity characterization, density and linear shrinkage % with different types and ratios of pore-forming agent
Graphite waste content Al2O3 ratio Overall porosity Open porosity Closed porosity Green density Sintered density Linear shrinkage
(wt %) (wt %) (vol %) (vol %) % (g/cm3) (g/cm3) %
10 90 37.3 18.4 18.2 1.8 2.4 14.9
20 80 45.7 24.9 20.8 1.8 1.9 14.7
30 70 46.2 28.8 17.4 1.8 1.7 18.4
40 60 53.6 39.2 14.5 1.7 1.5 20.5
50 50 61.1 53.9 7.1 1.7 1.4 21.7
Yeast content Al2O3 ratio Overall porosity Open porosity Closed porosity Green density Sintered density Linear shrinkage
(wt %) (wt %) (vol %) (vol %) % (g/cm3) (g/cm3) %
10 90 30.2 15.6 14.6 1.8 2.8 16.3
20 80 37.5 21.7 15.9 1.7 2.5 17.5
30 70 47.3 32.5 14.8 1.7 2.1 17.9
40 60 55.7 47.7 7.9 1.6 1.8 17.9
50 50 63.8 59.4 4.4 1.5 1.4 17.8
Rice husk ash content Al2O3 ratio Overall porosity Open porosity Closed porosity Green density Sintered density Linear shrinkage
(wt %) (wt %) (vol %) (vol %) % (g/cm3) (g/cm3) %
10 90 42.9 24.3 18.7 1.9 2.3 8.5
20 80 48.1 27.4 20.7 1.8 2.1 8.1
30 70 47.6 23.9 19.2 1.7 2.1 10.3
40 60 49.5 24.00 20.1 1.6 1.99 11.6
50 50 49.0 20.2 19.1 1.5 2.0 14.4

405
JCS-Japan Ali et al.: Preparation and characterization of porous alumina ceramics using different pore agents
Fig. 4. a) Total porosity trends with increasing content of the different
pore-forming agents (b) the sintered bulk densities trend with increasing
pore-forming agent content. All samples were sintered at 1600°C for 2 h.
little change in weight. In the second step (200­900°C), decom-
position is basically completed through oxidation and generates
gas, resulting in a dramatic loss in weight. At temperatures
>900°C, the weight remains constant.17) The pyrolysis of rice
husk ash is in completed because it contains ceramic oxide
(SiO2). The pyrolysis includes the carbon, the binder (sucrose)
and the residual organic materials that exist, with the commercial
rice husk ash, giving a maximum weight loss according to the
TGA result at 300°C approximately. The weight loss of com-
mercial rice husk ash is around 6.5%. The removal of the
unburned elements and organic materials, such as carbon, started
from around 200 to 650°C. The maximum weight loss occurs
at approximately 300°C. While, the weight loss of sucrose is
88.3%. The removal of the unburned elements and organic mate-
rials started from around 180 to 500°C. The maximum weight
loss occurs at approximately 300°C as well. Therefore, producing
porosity in ceramic body not only comes from burning out proc-
ess of rice husk ash but also from sucrose burning out process.
The silica (SiO2) in rice husk ash is found either in amorphous or
crystalline form.35) In addition, the rice husk has an important
effect on the formation of ceramic phases in the ceramic body.
Due to reaction between silica (SiO2) and alumina (Al2O3) it
leads to formation of stable mullite (3Al2O3.2SiO2) and silli-
manite (Al2SiO5) or (Al2O3·SiO2) phases. Previously, several
researchers used the Al2O3­SiO2 system to produce porous
ceramics with good mechanical properties36)­38).
According to the TGA and DTA curves as shown in Fig. 2 for
different pore-forming agents, the sintering temperature of porous
alumina ceramics have been selected: this sintering is a process
to burn out the graphite waste and sucrose.39),40) The weight loss
during the thermal treatment of the graphite waste can be
attributed to removing any solvent and organic material such as
polycaprolactam at (150­400°C). Temperatures above 400°C
help with graphite oxidation for complete burning. Similarly, the
decomposition and burning of the organic matrix in sucrose takes
place between 180 and 500°C for the thermolysis of sucrose.
Based on the weight loss characteristics of graphite and sucrose,
the organic and graphite burnout schedule of the green compacts,
as mentioned in the methodology, was established in order to
achieve the controlled burn out of the graphite and sucrose and
thus obtain defect free samples. The reaction of carbon in air as
represented by Eq. (6) is considered.41)
CðSÞ þ O2 ! CO2ðgÞ
Both the sintered and green densities of the samples decrease
with increasing pore agent content because of the weight lost by
chemical decomposition of the pore-forming agent and the
binder. In addition, the porous alumina samples have a shrinkage
406
Fig. 5. Variation of linear shrinkage for different pore-forming agents
for porous alumna ceramic samples sintered at 1600°C for 2 h.
that increases with increasing pore-forming agent ratios42) as
shown in Fig. 5. The increase in the shrinkage is attributed to the
porosity, the pore size and the binder ratio (10­12%).43)
The linear shrinkage for the porous alumina ceramic samples
which used graphite waste as a pore-forming agent was in the
range of 14.9 to 21.7%. This is attributed to the porosity, the pore
size, the binder ratio and the polymer phases that have been
discovered using the XRD analysis. The linear shrinkage for the
porous alumina ceramics using rice husk ash as a pore-forming
agent was in the range 8.5 to 14.4%. This is because the rice husk
ash samples have a lower ratio of materials removed from the
ceramics compared to the other pore-forming agents in this study.
The linear shrinkage of the porous alumina ceramics which used
yeast as a pore-forming agent was in the range of 16.3 to 17.8%.
This was attributed to the porosity, the pore size and the binder
ratio. The above explanation has been supported by the micro-
structures of the samples as in Fig. 6. These micrographs show
an increase in the volume fraction of the porosity with increasing
pore-forming agent content.
Figure 7 shows the porous alumina sample at 50 wt % pore-
forming agent ratio for different pore-forming agent materials
after sintering at 1600°C for 2 h.
Figure 8 illustrates the pores, the grains and the neck shapes of
porous alumina samples using different pore-forming agents after
sintering at 1600°C for 2 h. The irregular, spheroidal and longi-
tudinal shapes of pores in the alumina porous ceramics samples
as shown in Figs. 8(a), 8(c) and 8(e) are attributed to the shape
and size of the pore-forming agent particles as shown by the
FESEM images in Fig. 3. The grain growth and the necks are a
result of sintering at high temperature,44) while every gap
between the particles and the necks becomes a pore in addition
to the pore-forming agent effect.45) In addition, the different size
of the pores is attributed to an increase in the graphite waste, the
yeast, and the rice husk ash ratios and sucrose burnout,6) which
links open pores and results in fine and big pores as shown in
Figs. 8(a), 8(c) and 8(e).
During the sintering at high temperatures (up to 1600°C) using
graphite waste, it can be seen from Fig. 8(b) that the glassy
corundum phase filled the porous structure. As a result, the sam-
ð6Þ
ple’s surface appeared to be almost without pores. The corundum
phase using yeast was a porous structure as shown in Fig. 8(d),
which makes the mechanical properties of alumina porous
ceramics lower than the mechanical properties of porous alumina
ceramics with graphite waste and rice husk ash. The glass
Journal of the Ceramic Society of Japan 125 [5] 402-412 2017 JCS-Japan

Fig. 6. Graphite waste, yeast and rice husk ash with different porosity, pore size and pore shape for porous alumina samples
sintered at 1600°C.

Fig. 7. Porous alumina samples of 50 wt % pore-forming agent ratio for different pore-forming agent materials.

sillimanite phase also appears at a high sintering temperature
[Fig. 8(f )].46)
Figure 9 shows the ceramic phases for the porous alumina
samples after sintering at 1600°C for 2 h. Only the corundum
(Al2O3) phase was detected using the XRD analysis for the porous
alumina samples with graphite waste and yeast as a pore-forming
agent as shown in Figs. 9(A) and 9(B). While with increasing the
rice husk ash ratio and sintering at high temperature, the phases
which were detected in the porous alumina samples using rice
husk ash were corundum (A2O3) for 10 wt %, cristobalite (SiO2)
and corundum for 30 wt %, mullite (3Al2O3.2SiO2) and sillimanite
(Al2SiO5) for 40 wt %, and mullite for 50 wt % rice husk ash, as
shown in Fig. 9(c). At 10 wt % rice husk ash ratio, only the corun-
dum (A2O3) phase was detected because the ratio of SiO2 is not
sufficient to react with Al2O3 to produce or to transform to another
ceramic phase like cristobalite (SiO2) and mullite (3Al2O3.2SiO2).
While at 30 % wt rice husk ash ratio, the cristobalite (SiO2) phase
was detected. During the sintering at a high temperature of

407
JCS-Japan Ali et al.: Preparation and characterization of porous alumina ceramics using different pore agents
Fig. 8. Pores, grains and neck shapes of porous alumina samples for different pore-forming agents.
40 wt % rice husk ash ratio, alumina reacts with cristobalite to
produce the mullite phase.47) While at 50 wt % rice husk ash the
alumina dissolved into the glassy phase of mullite to produce
sillimanite (Al2SiO5) phase.36) All of these ceramic phases affect
the mechanical properties of porous alumina ceramics.
Figure 10 presents the pore size distribution for the porous
alumina ceramic samples using different pore-forming agents, i.e.
graphite waste, yeast and rice husk ash. The pore size distribu-
tions were affected by the pore-forming agent ratios, and all
samples displayed a unimodal pore size distribution for all pore-
forming agent ratios.
3.3 Mechanical properties
3.3.1 Hardness
Table 3 shows that the mechanical properties are strongly
related with the graphite waste, yeast and rice husk ash content
and the porosity ratio of the porous alumina ceramic.48)
Figure 11 shows that the hardness decreases with increasing
pore-forming agent content. This is due to the increasing volume
fraction of the overall porosity for porous alumina ceramics. In
general, the mechanical properties of porous ceramics are related
to the porosities, the microstructure and the phase compositions.49)
For porous alumina samples using graphite waste and yeast as a
pore-forming agent, the hardness decreases with increasing pore-
forming agent content. While the hardness of porous alumina
408
ceramics with rice husk ash decreases at 20% and continues to
increase at 30 and 50%, due to the formation of the ceramic phases
mullite, cristobalite and sillimanite which have high a hardness
value.50)­52)
3.3.2 Compressive and tensile strength
The compressive strengths of porous alumina ceramic samples
were measured according to Eq. (7).
P
· ðcompressive MPaÞ ¼ ð7Þ
A
where ·(compressive) is in MPa, P = applied force (N) and A = the
original area of the ceramic sample (mm2).
The diametrical tensile strength of porous alumina ceramics
was measured according to the tensile strength equation of the
Brazilian test.
ð2  PÞ
· ðtensile MPaÞ ¼ ð8Þ
ð³  t  dÞ
where ·(tensile) is in MPa, P = applied force (N), d = the diameter
of the sample in (mm) and (t) = the thickness of the sample in
(mm).53)
Figure 12 illustrates the decreasing of the compressive and
tensile strengths with increasing pore-forming agent ratio. The
decrease in the compressive and tensile strengths is due to the
increase in the porosity formation according to Rice’s formula
Journal of the Ceramic Society of Japan 125 [5] 402-412 2017
Fig. 9. XRD patterns for porous alumina samples sintered at 1600°C for 2 h with, (A) graphite waste, (B) yeast and (C) rice
husk ash.
[· = ·° exp(¹bp)] where · and ·° are the strengths of the
porous and nonporous materials, p is the porosity of the porous
ceramics and b is the constant related to the pore character-
istics.48),54) The porosity in the porous alumina samples is a
function of increasing the graphite waste and yeast ratio leading
to a decrease in the mechanical properties of the porous alumina
ceramics because the pores reduce the cross-sectional area across
which a load is applied and the pores will also act as stress
concentrators.53) The compressive and tensile strengths of porous
alumina ceramics using rice husk ash were at a maximum value
at 30 wt %. This improvement in the mechanical properties for
these particular samples is attributed to formation of the ceramic
phases of mullite, cristobalite and sillimanite.
Figure 13 presents the stress strain curves of porous alumina
ceramic samples using the Brazilian test. The stress­strain curves
also illustrate highly interesting differences between the differ-
ent ratios of pore-forming agent content. With increasing pore-
forming agent ratio, the stress­strain curves varied from brittle
behaviour to quasi-elastic behaviour for the porous ceramics
using graphite waste and yeast as a pore-forming agent because
of the porosity formation and the pores that act as stress con-
centrators.45) While the stress­strain curves in porous alumina
ceramics samples with rice husk ash shows brittle behaviour. This
behaviour is attributed to the formation of the ceramic phases
such as mullite, cristobalite and sillimanite which have high
mechanical properties.50)­52)
The values of the strains in selected porous alumina ceramic
samples that have been sintered at 1600°C for 2 h fall in the range
³0.3% at 10 wt % to ³1.6% at 50 wt % for porous alumina
samples with graphite waste, ³0.3% at 10 wt % to 2.3% at 50
wt % for porous alumina samples with yeast and between 0.3% at
JCS-Japan
10 wt % to 0.5% at 50 wt % for porous alumina samples with rice
husk ash. Increasing porosity results in increasing the ratio of
strain. Increasing strain results in a linear increase of stress.53) At
10 wt % of pore-forming agent, the behaviour of porous alumina
ceramics displays brittle material behaviour, whereby after reach-
ing the yield stress, the fracture zone is clear and the stress drops
suddenly. The samples were destroyed completely at the ratio of
strain of ³0.3% but the deformation is not clear because the ratio
of pore-forming agent was very low with a minimum value of
porosity for all pore-forming agents. The behaviour of porous
alumina ceramics at ratio 50 wt % tends to be a quasi-elastic,
whereby after reaching the yield stress, the fracture zone is not
clear. In the cycle of this quasi-elastic zone, the fracture of a
single strut happens, usually at the area of contact of the sam-
ple fixation. This is common for porous ceramics.53) This strut
fracturing becomes clearer, after reaching the yield stress, and
leads to the spalling of small debris wherever the porous structure
parts are destroyed. This spallation is expressed by the sudden
reduction in the stress­strain curves as shown in Fig. 12 at a
ratio of 50 wt % of pore-forming agent with different values of
strain.53) This behaviour is attributed to the high ratio of pore-
forming agent with a maximum porosity of porous alumina
samples and different pore shapes. With increasing porosity, the
mechanical strength decreases, and the deformation tolerance is
improved resulting in higher strain at break in the more porous
ceramics. However, porous alumina ceramics using rice husk ash
as a pore-forming agent and strengthening factor tend to display
brittle behaviour for pore-forming agent ratios from 10 to 50%
due to the formation of the mullite, cristobalite and sillimanite
phases.50)­52) The increasing strain ratio (from 0.3 to 0.5) was
attributed to the porosity which formed.
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JCS-Japan Ali et al.: Preparation and characterization of porous alumina ceramics using different pore agents

Fig. 10. Pore size distribution for alumina porous ceramic samples sintered at 1600°C for 2 h using different ratio of graphite
waste, yeast and rice husk ash.

Table 3. Mechanical properties of alumina porous ceramic

Graphite waste content Porosity Hardness Compressive strength Tensile Strength
(wt %) (vol %) (HV1) (MPa) (MPa)
10 37.3 172.6 « 4.1 112.3 « 4.9 24.9 « 1.6
20 45.7 96.7 « 5.2 87.7 « 5.5 19.6 « 0.5
30 46.2 66.7 « 5.6 43.3 « 1.1 18.6 « 1.6
40 53.6 47.9 « 2.3 37.2 « 1.0 17.9 « 1.1
50 61.1 38.1 « 1.5 34.3 « 2.3 14.3 « 0.5
Yeast content Porosity Hardness Compressive strength Tensile Strength
(wt %) (vol %) (HV1) (MPa) (MPa)
10 30.2 160.6 « 3.9 19.5 « 0.6 26.2 « 1.1
20 37.5 98.1 « 4.7 17.5 « 1.1 24.2 « 0.6
30 47.3 51.0 « 2.4 5.6 « 0.7 11.6 « 0.7
40 55.7 38.3 « 1.3 2.9 « 0.3 8.7 « 0.4
50 63.8 15.0 « 1.5 1.8 « 0.1 5.4 « 0.4
Rice husk ash content Porosity Hardness Compressive strength Tensile strength
(wt %) (vol %) (HV1) (MPa) (MPa)
10 42.9 110.0 « 2.1 59.8 « 2.2 20.2 « 1.1
20 48.1 101.9 « 2.9 59.33 « 3.9 18.9 « 1.2
30 47.6 150.9 « 1.8 69.7 « 2.8 24.1 « 0.9
40 49.5 114.9 « 3.9 53.9 « 1.5 21.9 « 1.0
50 49.0 158.9 « 3.9 60.1 « 2.0 21.9 « 0.8

and sillimanite. Porous alumina ceramics with high mechanical

4. Conclusion
In conclusion, porous alumina ceramics have been fabricated
successfully using graphite waste from primary batteries, yeast
and commercial rice husk ash as pore-forming agents with
different ceramic phases such as mullite, cristobalite, corundum
properties and high porosity were produced using rice husk ash
as a pore-forming agent and as a strengthening factor at the same
time compared with using the graphite waste and yeast as pore
forming agent. The mechanical properties of alumina porous
ceramics are strongly related to the increase in porosity and the

410
Journal of the Ceramic Society of Japan 125 [5] 402-412 2017 JCS-Japan

Fig. 12. Relationship between the different pore-forming agent content

and the mechanical properties (a) compressive strength and (b) tensile
strength of porous alumina ceramics sintered at 1600°C for 2 h.
Fig. 11. Hardness variation with different pore-forming agent content
for porous alumina porous ceramic samples sintered at 1600°C for 2 h.

Fig. 13. Stress­strain curves of porous alumina ceramic samples with different ratios of pore-forming agent (10­50 wt %)
sintered at 1600°C for 2 h using the Brazilian test.

pore-forming agent ratio. With increasing porosity using graphite like to thank Iraqi government/Ministry of Higher Education and
waste and yeast as a pore-forming agent, the mechanical prop- Scientific Research for its financial support.
erties were decreased. While the mechanical properties of porous
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