MA TE RI A L S CH A R A CT ER IZ A TI O N 62 ( 20 1 1 ) 9 1 2–9 1 6

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Effect of binders on microstructural and mechanical properties

of sintered alumina

Rym Taktaka,⁎, Samir Bakloutib, 1 , Jamel Bouaziza, 2

a
National School of Engineers of Sfax, Tunisia
b
Faculty of Sciences of Sfax, Tunisia

AR TIC LE D ATA ABSTR ACT

Article history: This study examines the effects of organic binder content, plasticity and sintering
Received 6 August 2010 temperature on the microstructural and mechanical properties of sintered samples
Received in revised form prepared from alumina spray-dried powders.
29 March 2011 Measurements of mechanical strength of sintered samples prepared from spray-dried
Accepted 27 June 2011 alumina powders containing the two binders polyvinyl alcohol (PVA) or polyethylene glycol
(PEG) are reported. This analysis revealed that the introduction of an optimal amount of
Keywords: binder in the composition of spray dried powders enhances the relative density and the
Alumina mechanical strength of sintered samples prepared from these powders. The variation of
Binder mechanical strength of these samples with sintering temperature is compared to those
Mechanical strength prepared from alumina with no additive and discussed. For powders containing PVA as a
Sintering binder, the samples' properties are better when the amount of PVA is lower. It was also
observed a good deformability of alumina granules spray dried with the PEG binder which
leads to get more homogeneous microstructure and therefore a good sintering and
densification of samples.
© 2011 Elsevier Inc. All rights reserved.

1. Introduction the mold, (ii) compaction behavior during pressing, and (iii)
microstructure of the pressed green body. A hydrosoluble
Binders are typically long chain polymers that serve the organic polymeric binder is generally added to ceramic
primary function of providing strength to the green ceramic suspension before spray drying in order to improve the
body forming bridges between the particles. In some forming strength of the granules and the green products during
methods, they also provide plasticity to the feed material and (ejection from die) and after (handling and machining) the
aid the forming process. A large number of organic substances forming step [3–5].
can be used as binders, some of which are soluble in water, It was concluded that the addition of organic binder in
while others are soluble in organic liquids. They include the spray-dried ceramic powder increases the mechanical
vinyls, acrylics, and the ethylene oxides (glycols) [1]. strength of spray dried powder and pressed body [6].
Dry pressing involves the uniaxial compaction of spray The effects of binder content and binder plasticity on the
dried granules consisting of ceramic particles bound by an compaction of PVA/PEG containing spray dried ceramic powder
organic binder [2]. The spherical granules with a typical have been established. Although a lot of work has been
diameter of 100–200 μm, obtained by spray-drying, confer a published in literature concerning the influence of binders on
good flowability necessary to achieve reproducible (i) filling of the densification behavior of powder during compaction [7–11],

⁎ Corresponding author at: National School of Engineers of Sfax, BPW 3038, Sfax, Tunisia. Tel.: +216 96364268.
E-mail address: [email protected] (R. Taktak).
1
Tel: + 21697235972.
2
Tel: + 21698651720.

1044-5803/$ – see front matter © 2011 Elsevier Inc. All rights reserved.
doi:10.1016/j.matchar.2011.06.011
 M A TE RI A L S CH A RACT ER IZ A TI O N 62 ( 20 1 1 ) 9 1 2 –9 1 6 913

very limited knowledge is available on the effect of binders on The alumina green pieces were divided into groups, and
microstructural and mechanical properties of sintered bodies. sintered at different temperatures 1200,1300,1400,1500, 1600
The aim of the present work was to investigate the effects and 1700 °C with a ramp rate 600 °C h− 1 and held for 2 and 4 h.
of binders PVA/PEG on microstructural and mechanical The mechanical strength of sintered samples was estimat-
properties of sintered alumina using the combination of ed by the diametral compression method so called “Brazilian
“Brazilian test” and scanning electron microscopy (SEM). test” [13]. Just after sintering, the disk-shaped samples were
In this research, we report also how the amount of binder inserted in the testing machine, and the load F applied radially
and sintering temperature affect fracture behavior and at a speed rate of 0.5 mm mn−1 until the specimen fractured.
physical properties. The strength of samples was calculated using the following
expression

2Fmax
2. Materials and Methods σ=
πDe

2.1. Starting Materials and Preparation of Samples Where Fmax is the load applied at fracture, and D and e are
the diameter and the thickness of the sample, respectively.
The ceramic powder used in this study is an α-alumina The fracture strength of the samples was determined from
(P152SB, Péchiney, France). The surface area and the mean the compressive load-deformation displacement curves. The
particle size were respectively 3 m2 g−1 and 1.25 μm. The tensile surfaces of selected samples were examined by
amounts of binder added are 3 wt% for PEG and 1 or 3 wt% for scanning electron microscopy (SEM); a PHILIPS (XL 30) SEM
PVA (dry weight basis of alumina). Three batch compositions was used to study the microstructure.
(Table 1) were tested using binder 1 wt % PVA, 3 wt% PVA, and
3 wt% PEG. De-ionized water was used as the solvent and
ammonium polymethacrylate (Darvan C) was added as 3. Results and Discussion
dispersant [6].
According to literature data, the glass transition temperature 3.1. Effect of Binder on Alumina Sintering
(Tg) of the dry polymers are 79 °C and −60 °C for dry PVA and
PEG, respectively. These glass transition temperatures of PVA The effect of sintering temperatures on alumina pellet
and PEG are respectively located above and below room strength was investigated by discussing three factors: tensile
temperature at which pressing was performed [6]. The presence strength, shrinkage and porosity, which changed with sinter-
of residual moisture decreases these glass transition tempera- ing temperatures.
tures and then there deformability increases. The strength of compacts prepared from PEG 3 and PVA 3
Samples were prepared by dry pressing spray dried powders is plotted versus sintering temperature and nature of
granules. The as-received and spray-dried alumina were binder in Fig. 1, where the data are also compared to the
uniaxially compacted by single action in a universal machine strength of compacts prepared from the original alumina
(Lloyd EZ 50) at room temperature under 100 and 70 MPa, powder, without organic additive.
respectively, to produce disk-shaped samples (20 mm diam- According to these results, the mechanical strength of
eter, about 4 mm thickness). Under these pressures, all the alumina samples prepared from AP152 SB increases with
samples have a relative density of about 57%. The pressure temperature to reach at 1600 °C a region where the evolution is
was released immediately once the desired value was less pronounced, and looks like a plateau; the maximum of the
reached, and the sample was ejected [12]. strength is 60 MPa. This result indicates that alumina compact
The pellets were measured and weighed immediately after densify with temperature and that the natural sintering
ejection to allow comparison between the green density and temperature of the original alumina powder is probably
the in die density. 1600 °C.
Sintering was conducted in air from 1200 °C to 1700 °C after
debindering operation at 400 °C for 3 h with ramp rate 120 °C
h− 1 in electric furnace.

Table 1 – The three batch compositions tested [14].

Powder Average size of Flowability
particles (μm) (g s− 1)

AP152 SB 1. 25 Weak
(Sedigraph) Lot of time
AP 152 + 3 wt% PEG + 0.6 wt% 200 Good
residual moisture content (PEG3) 4.36
AP 152 + 3 wt% PVA + 0.6 wt% 200 Good
residual moisture (PVA3) 4.36
Fig. 1 – Evolution of the tensile strength versus sintering
AP 152 + 1 wt% PVA + 0.25 wt% 200 Good
residual moisture (PVA1) 4.73
temperature for samples prepared from AP152 SB, PVA3 and
PEG 3 powders.
914 MA TE RI A L S CH A R A CT ER IZ A TI O N 62 ( 20 1 1 ) 9 1 2–9 1 6

Fig. 2 shows the microstructure of sintered alumina Table 2 – Properties of samples obtained from alumina
without binder at 1600 °C and 1700 °C; these results indicate AP152 SB without binder at different sintering
that the densification of used alumina with natural sintering temperatures.
is limited because of the grain growth and the samples contain Sintering Relative Volume
macropores. temperature (°C) density (%) shrinkage (%)
Table 2 gives the properties of different samples obtained 1400/2h 67 16
from alumina AP152SB without binder and sintered at different 1500/2h 73 31
temperatures. These results show that the relative density 1600/2h 80 32
increases significantly with the temperature from 1400 to 1700/2h 82 32
1600 °C and remains almost constant from 1600 to 1700 °C.
The volume shrinkage has also the same evolution with
temperature. Then, at these conditions, the sintering temper-
ature of the studied alumina (AP152 SB) without organic additive the compact until a value 90 MPa at 1600 °C then decreases
is also probably 1600 °C. due probably to the presence of big grains and big pores
According to Fig. 1, the sintered strength of compact whereas the presence of 3 wt% PVA in the composition
prepared from powders containing binder increases also decreases the rate of strength evolution.
with temperatures but with different rates. In fact, the In order to evaluate the effect of the binder kind, the
presence of 3 wt% PEG increases more rapidly the strength of microstructures of samples containing the PVA or the PEG as
binder were compared (Figs. 3 and 4). These results show that
samples prepared from PEG 3 powder are relatively homoge-
neous. Granules are therefore more deformable permitting a
better densification. However, at 1600 °C, the densification is
not achieved completely; it is then a relatively porous product
(Fig. 3(a)).

Fig. 2 – SEM micrographs of the fracture of AP152 SB sintered Fig. 3 – SEM micrographs of fracture surface of sintered
compacts at two sintering temperatures: (a) 1600 °C/2h, and samples prepared from PEG 3 powder at (a) 1600 °C, (b)
(b) 1700 °C/2h. 1700 °C.
 M A TE RI A L S CH A RACT ER IZ A TI O N 62 ( 20 1 1 ) 9 1 2 –9 1 6 915

Fig. 4(b) illustrates the presence, in the sintered samples at

1700 °C, of an important porosity at the triple points that can
be the main causes of a mechanical property's fall.
A marked difference is shown in the fracture of granules for
the two bodies: the sample prepared from PEG 3 again present
at 1700 °C a residual intergranular porosity (triple point) but
smaller than that observed in samples prepared from PVA 3
and sintered at the same temperature.
According to these results, the nature of the used binder has
a significant effect on the mechanical properties of sintered
samples. Then whatever is the sintering temperature and with
a 3 wt% of binder content, the compact obtained from spray
dried alumina with polyethylene glycol sinters rapidly and
exhibits a tensile strength more important than those prepared
from spray dried alumina with the polyvinyl alcohol.
This difference is probably linked to the good deformability
during compaction of alumina granules spray dried with the PEG
binder which leads to get more homogeneous microstructure
and therefore a good sintering and densification of samples.

3.2. Effect of Binder Content

It was noted that the binder has a considerable effect on the

densification of the ceramic compact. Also as the binder content
increases, granule becomes hard and difficult to distort during
compaction. This phenomenon is accentuated more in the case
of the PVA because of its glass transition temperature which is
higher than the pressing temperature. In these conditions
granules are not sufficiently soft in compaction and the relative
density of compact is low. On the other hand, the samples
containing the PEG present more elevated relative density.
Fig. 5 shows the evolution of the tensile strength of
samples versus sintering temperature and the PVA content
(0, 1 and 3 wt%).
These results show that whatever is the sintering tempera-
Fig. 4 – (a) and (b): SEM micrographs of fracture surface of ture, the mechanical strength of samples prepared from PVA 1
samples prepared from PVA 3 powder sintered at (a) 1600 °C powder is higher than those prepared from PVA 3. The difference
(b) 1700 °C. is probably due to a better densification of samples containing a
less amount of PVA (Fig. 6).
In fact, spray-dried granules with 3 wt% PVA have a
By increasing the sintering temperature, of samples relatively high cohesion and become harder. It cannot be
prepared from PEG 3 powder, from 1600 °C to 1700 °C, a little
modification of the microstructure occurred (Figs. 3(a) and (b)).
The microstructure is regular and homogeneous and presents
big grains and big pores at the surface. These observations of
SEM fractographies are in agreement with mechanical
strength.
On Fig. 4(a), it can be seen that, for samples obtained from
PVA 3 composition and sintered at 1600 °C, the trace of
granules is clearly visible in the compact. The granules
remained intact probably because they are rigid and unde-
formable. The rupture is then localized between granules.
Thus, the fracture surface shows intergranular propagation
with an important microcracking of granules. These micro-
cracks are related to the elongation of the external layer
containing a brittle PVA polymer, with a glass transition
temperature higher than the forming room temperature [5].
Then, the densification of this material occurred within Fig. 5 – Evolution of the tensile strength versus sintering
granules, each of them being separately densified. It is then a temperature for samples prepared from AP152 SB, PVA 1 and
local and not homogeneous densification. PVA 3 powders.
916 MA TE RI A L S CH A R A CT ER IZ A TI O N 62 ( 20 1 1 ) 9 1 2–9 1 6

Table 3 – Properties of different alumina compacts

sintered at 1700 °C.
wt% of PVA Relative density Volume shrinkage
binder (%) (%)

0 82 32
1 94 40
3 84 36

sample property. It was also observed a good deformability of

alumina granules spray dried with the PEG binder leads to getting
more homogeneous microstructure and therefore a good sinter-
ing and densification of samples. This study clearly shows also
the effects of binder content on mechanical properties. For
powders containing PVA as a binder, the sample properties are
better when the amount of PVA is lower.

Fig. 6 – SEM micrographs of fracture surface of sintered

samples from PVA 1 powder at 1600 °C.
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