Copolymers dispersions designed to shaping of ceramic materials
Journal of Thermal Analysis and Calorimetry
Copolymers dispersions designed to shaping of ceramic materials
Radoslaw Zurowski 0 1
Malgorzata Gluszek 0 1
Agnieszka Antosik 0 1
Emilia Pietrzak 0 1
Gabriel Rokicki 0 1
Mikolaj Szafran 0 1
0 Faculty of Chemistry, Warsaw University of Technology , Noakowskiego 3 Str., 00-664 Warsaw , Poland
1 & Malgorzata Gluszek
The paper concerns the synthesis and the characterization of new water-thinnable binder such as poly(acrylic-styrene) with the addition of a new amphiphilic macromonomer and it application in shaping of unmodified and modified (by silanization) Al2O3 by die pressing. The organic additives decomposed thermally to non-toxic gases which is beneficial from ecological point of view. Thus, the careful thermal analysis of synthesized binder was done. To characterize the synthesized binder, the glass transition temperature, wetting angle and diameter of polymer particles size in water were also measured. In the next step of the work, the density, porosity, tensile and bending strength, and microstructure observations have been done for modified and unmodified Al2O3 samples obtained by die pressing. The results confirmed that the synthesized binder is eco-friendly, because it decomposed to non-toxic gases such as carbon dioxide and water vapor during heating up to ca. 527 C. The synthesized binders are characterized by low glass transition temperatures 5.6 C and - 0.5 C which are much lower than that of PVA (42 C). It provided the high tensile strength (0.22 ± 0.01 MPa) of green bodies, 57% higher than strength of bodies with commercially available PVA and bending strength around 192 MPa. Density of sintered samples was around 95% of TD. Nevertheless, the best results were obtain for bodies based on modified Al2O3 where tensile strength of green bodies and bending strength of sintered samples were 0.30 ± 0.04 MPa and 237 ± 19 MPa, respectively.
Water-thinnable binders; DSC; Thermal decomposition; Mass spectrometry; Alumina; Die pressing
There are many forming methods ceramics, mainly
depending on the final desired shape of a product and the
application. One of the most widespread method of
forming dense ceramics is forming by pressing. This process is
widely used in industry because of its easy simplicity for
large numbers of ceramic components characterized by
high density and mechanical strength. The disadvantages of
this technique are the limitations of the products shape and
difficulty in obtaining homogeneous distribution of density
across the element as a consequence of uneven distribution
of pressing force. The application of polymer binders can
successfully help to mitigate friction, providing a more
homogenous densification [
]. Favorable binders have a
low glass temperature Tg, suitable high molecular weight
and eco-friendly properties [
2, 4, 5
]. Another important
aspect is the interaction of binder–binder and
binder–particle powder. Polar groups (ester, carboxyl, hydroxyl)
present in the polymer chain, as well as the ability to form
hydrogen bonds, generate strong interactions with the
powder surface and increase the adhesion forces [
must be underlined that from ecological point of view
organic additives should be thermally decomposed to
nontoxic gases such as carbon dioxide and water vapor. Due to
differential thermal analysis (DTA) apparatus with mass
spectrometry, it is possible to observe type of gases
released to the atmosphere during decomposition of any
substances. DSC and DTA analysis allows to gain
knowledge about glass transition temperature and thermal
stability of materials as well as their environmental hazard
Water-soluble binders, such as poly(vinyl alcohol)—
PVA is most often used [
]. However, due to insufficient
mechanical strength of green bodies given by such type of
binders, machining or mechanical treatment of the bodies
is hindered. On the other hand, water-insoluble binders
providing more sufficient sample parameters, but they
require the addition of expensive and non-ecological
organic solvents. To reduce this obstacle, water-thinnable
polymer binders are utilized such as polyacrylate,
polyurethane or acryl-styrene, acrylic allyl or vinyl allyl
]. The above-mentioned studies have
confirmed the superiority of these kinds of binders over
water-soluble ones. In particular, polyacrylate dispersions
are shown desirable properties. Already in early 1995, a
polyacrylate binder—Duramax TM 1031B (Rohm&Haas)
was developed. Its additive in amount of 5 mass% resulted
in a huge tensile strength (6.5 MPa) of alumina green
bodies, while the addition of poly(vinyl alcohol) less than
1 MPa. Kumar et al. investigated the effect of polyacrylic
binders on the mechanical strength of alumina materials.
Their research has proven that the green alumina bodies
containing 3 mass% of prepared binder have sufficient
mechanical strength to allow the machining by turning and
]. However, in both discussed cases, high binder
loading has reduced the density and increased the porosity
after sintering process. Bukvic et al. [
] also investigated
the effect of various polymer binders on mechanical
properties and machining of green alumina bodies. They
obtained cylindrical samples of 10 mm diameter and
55 mm high using isostatic pressing under the pressure of
100 MPa. Each of prepared sample contained 2 mass% of
different binder: poly(vinyl alcohol), poly(vinyl butyral),
and two polyacrylic dispersions B-1007 and B-1022
delivered by Rohm&Haas. The samples were machined
using turning method. The smallest surface chipping was
achieved in case of polyacrylic binder B-1007. These
samples were also exhibited the highest bending strength
and the lowest surface roughness after the sintering
Szafran et al. [
2, 5, 21
] applied additionable amphiphilic
molecule of macromonomers to synthesize poly(acrylic–
styrene) dispersions. It was shown that the incorporation of
macromonomer in polymer structure allowed to reduce the
glass transition temperature of the binder and also
minimized the addition of the emulsifier needed to the emulsion
polymerization process. The use of these binders in
samples preparation was beneficial in mechanical properties
compared to PVA. However, for the last years, there are
not many articles devoted to developing new
water-thinnable polymer binders. Most of researchers use
commercially available polyacrylic dispersions [
As a continuation of the Szafran et al. study, the paper
presents research on water-thinnable copolymer binders
with the addition of a new amphiphilic macromonomer in
comparison with commercial poly(vinyl alcohol) binder.
Moreover, the authors show the effect of surface ceramic
powder modification using (3-aminopropyl)trimetoxysilane
on the properties of the obtained materials.
Materials and experimental procedure
Synthesis of amphiphilic macromonomer
The synthesis of amphiphilic macromonomer consisted of
two steps. In the first one, synthesis of glycidyl ether of
ethoxylated fatty alcohol by the reaction of fatty alcohol
containing poly(oxyethylene) fragments with
epichlorohydrin was conducted. The reaction was carried out at
60–65 C for 10 h according to the scheme presented in
Fig. 1a 2,6-di-tert-butyl-4-methylphenol (BHT) as an
antioxidant was used. In the second step, acrylic acid was
reacted with glycidyl ether of ethoxylated fatty alcohol in
the presence of N,N-dimethylbenzylamine as a catalyst
(Fig. 1b). Phenothiazine (PTZ) as an inhibitor was used.
This step of synthesis was conducted at 70–90 C until
complete conversion of carboxyl groups.
Synthesis and characterization of waterthinnable copolymer binders
Two water-thinnable poly(acrylic–styrene) binders were
prepared by emulsion copolymerization. Both of them had
the same weight ratio styrene/butyl acrylate/acrylic acid
(30:68:2). However, one of them contained a small amount
of obtained amphiphilic macromonomer. Ammonium
persulfate (APS), sodium dodecylbenzenesulfonate (SDBS)
and ammonium bicarbonate were used as an initiator,
emulsifier and pH buffer, respectively. The polymerization
was carried out at 70 C for 6 h. The physicochemical
properties of the substrates used in the synthesis of
amphiphilic macromonomer and water-thinnable polymer
binders are shown in Table 1.
For the obtained dispersions, the concentration of the
polymer in water, polymer particles size (Zetasizer Nano
ZS, Malvern, UK) and the wetting angle which influences
the ability of dispersion to wet the surface of alumina
powder were determined. After drying of the dispersions,
the glass transition temperature (Tg) of the binders was
determined by the differential scanning calorimetry (DSC)
C18H37(OCH2CH2)nOH n & 10
CH2 = CHCOOH
C6H5CH = CH2
CH2 = CHCOO(CH2)3CH3
method (DSC Q200, TA Instruments, USA). Tg was
evaluated by inflection point method. Measurements were
taken in a nitrogen atmosphere from - 100 to 200 C with
heating rates 10 C min-1. The sample mass was ca.
20 mg. Moreover, thermogravimetric analysis was
conducted. DTA/TG measurements were taken by using
Netzsch Jupiter STA 449C coupled with the mass spectrometer
Netzsch QMS 403C Aeolos. The quantity of polymer
sample took to the measurements equaled 0.04 g. They
have been covered by calcinated (non-reactive) Al2O3
powder in the quantity of 0.5 g in order to prevent the
polymer creeping from the crucible. The heating rate was
5 C min-1, and the final temperature was 1000 C. The
measurements were taken in the constant flow of two
gases: argon—10 mL min-1 (protective gas) and synthetic
air (75:25 N2/O2)—60 mL min-1. Mass spectrometer was
set to detect m/z values in mass range 10–300. The analysis
was conducted only for the polymer containing molecules
of amphiphilic macromonomer since the chemical structure
of prepared poly(acrylic–styrene) binders slightly differs
and thus, their behavior and elevated temperatures will be
For comparison, commercially available poly(vinyl
alcohol) (PVA) was used as a binder. The molar mass and
hydrolysis degree of PVA were 80,000 g mol-1 and 88%,
respectively. The binder was used in the form of 10 mass%
aqueous solution. Table 2 presents properties of all used
Characterization of used ceramic powder
Al2O3 powder (MARTOXID MR-52, Martinswerk,
Germany) with a density of 3.93 g cm-3 and specific surface
area of 6.31 m2 g-1 was used in the studies. Density of the
powder was determined using helium pycnometer
(AccuPyc 1340, Micromeritics, USA). Identification of
specific surface area was evaluated by a BET adsorption
isotherm method (ASAP 2020, Micromeritics, USA). The
where C, concentration of polymer in water; MC, concentration of amphiphilic macromonomer with
respect to the total mass of other monomers; Tg, glass transition temperature; a, wetting angle; d, diameter
of polymer particles size in water dispersion
alumina morphology and microstructure were investigated
by Scanning Electron Microscopy (Zeiss ULTRA Plus,
Zeiss, Germany). Figure 2 shows the irregular shape of
alumina powder and bimodal distribution of particle size. It
was also observed the presence of agglomerates.
The aqueous ceramic slurries containing 70.0 mass% of the
Al2O3 and 0.5 mass% (with respect to the alumina) of
selected polymer binder were prepared by milling in a
planetary ball mill (PM 100, Retsch, Germany) with
rotational speed 300 rpm for 45 min. The slurries contained
also a dispersing agent—Dispex A-40 (Allied Colloids
Ltd., UK) in the amount of 0.25 mass% (with respect to the
alumina) and an antifoaming agent—octanol. The
granulated product was obtained by water evaporation using
vacuum evaporator and screen sieve. The fraction of
0.2–0.5 mm grain diameter was applied for the studies.
One of the granulates was obtained using alumina modified
by silanization process. As a modifying agent, the
(3aminopropyl)trimetoxysilane in the amount of 1.5 mass%
(with respect to the alumina) was used. This process would
allow to permanent connection between the particle surface
and polymer molecule by ionic bonding according to
scheme presented in Fig. 3. The presence of modifying
agent on the alumina surface after silanization process was
verified by TG/DTA analysis (derivatograph 34-27 T
MOM Budapest, Hungary).
Shaping and characterization of green and sintered samples
All of the ceramic samples were obtained by die pressing
method using a hydraulic press under the pressure of
50 MPa. Twelve cylindrical samples of 20 mm diameter and
ca. 5 mm height were shaped from each of prepared
granulates. Green bodies were characterized by the density
measurements and tensile strength by the ‘‘Brazilian test’’ on
H10KS (Tinius Olsen, USA). The tensile strength of green
bodies was determined by the following dependence (1):
where rr, tensile strength (MPa); P, force causing the
sample destruction (N); d, sample diameter (mm); h,
sample high (mm).
Thirty cylindrical samples of 20 mm diameter and ca.
2.5 mm height were die pressed, dried at 105 C for 24 h
and then sintered at 1650 C for 1 h using HTF 1700
furnace (Carbolite, UK) from each of prepared granulates. All
of sintered materials were characterized by basic
parameters such as density, open porosity and wettability.
Moreover, bending strength obtained from the ‘‘ring-bowl’’ test
using H10KS (Tinius Olsen, USA) was investigated. It is
the biaxial bending method where gradually increasing
pressure causes sample destroy. The bending strength of
sintered samples was calculated based on Eq. 2.
rz ¼ 3P4ð1phþ2 vÞ 1 þ 2ln ab þ ðð11 þ vvÞÞ 1
where rz, bending strength (MPa); P, force causing the
sample destruction (N); h, sample high (m); a, supporting
ring radius (m); b, piston radius (m); r, sample radius (m);
v, Poisson’s ratio (v = 0.22 for ceramic materials).
Microstructure of sintered samples was determined by
Scanning Electron Microscopy (Zeiss ULTRA Plus, Zeiss,
The analysis of DSC studies of synthesized acrylic–styrene
binders and poly(vinyl alcohol) is shown in Table 1. The
results revealed the difference in the glass transition
temperature between these binders. This is due to the chemical
structure of the compounds which induced conformation
changes and therefore rigid of the polymer, which affects
the value of its glass transition temperature. In case of
PVA, the regular structure of main chain and the hydrogen
bonds between the polymer chains are responsible for the
high value of Tg which is above 40 C. Despite the fact that
both of prepared poly(acrylic–styrene) binders contain a
stiff phenyl group, they exhibit the lower glass transition
temperature compared to PVA. This is caused by the lack
of groups able to create the hydrogen-bonded network in
the structure of these binders. Moreover, the incorporation
of the amphiphilic macromonomer containing long and
flexible ethoxylated hydrocarbon chain into the structure of
B2 binder decreased Tg. Due to long oxyethylene
fragments which move the main polymer chains from each
other, the macromonomer had an internal plasticizer
Wetting angle of the synthesized binder
The presence of amphiphilic macromonomer molecules
containing hydrophilic groups in the poly(acrylic–styrene)
binder structure significantly affects the ability of prepared
dispersions to wet the surface of Al2O3 powder (Table 2).
The interaction between binder molecules and alumina
surface with hydroxyl groups is greater. In consequence,
the adhesion of the polymer binder to the alumina surface
was increased which is confirmed by smaller wetting angle
DTA/TG/DTG curves of thermal degradation of binder B2
indicate that the total mass loss was 97%, what means that
almost all of organic phase has decomposed. Polymer
decomposition goes in two main stages according to TG
curve. It begins at ca. 333 C and ends at ca. 527 C. The
exothermic peak on DTA curve with the maxima at 398
and 503 C is distinct. The main m/z values detected by
mass spectrometer were 17 and 18 which can be ascribed to
OH- and H2O molecules (Fig. 4b). This is therefore the
main gaseous product released from the polymeric sample.
The presence of CO2 is confirmed by m/z values 12 and 44.
There is the increase in the intensities of MS 44 and 12
signals with the maxima at 380 and 492 C what indicates
the decomposition of polymeric binder and oxidation of
decomposition products (light hydrocarbons) to CO2. The
stepped mass loss and the presence of a few maxima on MS
curves indicate that thermal decomposition of the
polymeric chain proceeds gradually. The MS signals 41, 42, 50,
51, 55, 56 are observed with the maximum at 367 C which
can be ascribed to the first stage of thermal decomposition
of the polymer (Fig. 4c). It must be underlined that the
intensities of these signals are very low in comparison with
signals 18 and 44. The major decomposition products come
from main chain scission, giving shorter polymeric chains
(C1–C5 hydrocarbons) like: oligomers, trimers, dimers and
]. MS 41 and 42 peaks of high intensity
may indicate the C3 hydrocarbons, acetates, acetyl groups
what corresponds to the polymer structure [
(b) QMID ∗10–9/A
(c) QMID ∗10–12/A
presence of the m/z value 44 is observed till ca. 600 C
which means that mentioned above organic groups undergo
further oxidation to CO2.
DTA/TG/DTG curves of thermal degradation of
modified alumina powder (Fig. 5) indicate that the total mass
loss was 1.97% what confirms a presence of the modifying
agent on the Al2O3. Decomposition of the sample goes in
two main stages according to TG curve. It is worth
mentioning that the 0.46% of mass loss is related to the
endothermal dehydration process, which is observed until
ca. 160 C with the maximum at ca. 90 C. The rest of the
mass loss (1.33%) is related to the exothermal process. The
exothermic peak on DTA curve with the maximum at ca.
290 C can be ascribed to the first stage of thermal
TG: –0.46 %
decomposition of organic compounds. Thermal
decomposition of organic substances ended at ca. 600 C. It must be
underlined that the silicone is not burned out from the
sample. It probably remains in the form of oxides.
Green bodies properties
The properties of green alumina bodies shaped using
unmodified and modified ceramic powder are shown in
Table 3. The non-functionalized green bodies exhibited
almost the same values of relative density and equals
67.5% of the theoretical density of Al2O3. However, the
data suggest that the binder content significantly influences
the tensile strength. In case of the green bodies based on
unmodified powder, the highest tensile strength was
measured for the samples with the addition of the B2 binder. In
this case, the tensile strength was 0.22 MPa which was
57% higher compared to those the bodies with
commercially available PVA which were the lowest (0.14 MPa).
Additionally, the use of the B2 binder allows to obtain
products with the most replicable parameters, which was
confirmed by the lowest values of standard deviation.
where dvo, density of the green samples; rr, tensile strenght of green
The samples prepared with modified Al2O3 granulate
were significantly less dense. The relative density (using
the same binder) was almost 9% lower in comparison with
the bodies based on unmodified powder. It is likely that a
presence of an additional organic layer on the surface of the
ceramic powder particles formed an additional steric
barrier. Nevertheless, these samples demonstrated higher
tensile strength 0.30 MPa (about 40% higher) in
comparison with those based on unmodified Al2O3 with the same
Sintered samples properties
The properties of the sintered ceramic materials based on
unmodified and modified alumina are shown in Table 4.
Among all of sintered materials based on unmodified
Al2O3, the highest densification during the thermal
treatment was achieved for samples shaped with binder B2. The
samples showed 1.3% greater density than those prepared
with commercially available PVA. The highest density also
influenced the lowest values of open porosity and
wettability. The data presented in Table 4 show also that the
presence of amphiphilic macromonomer molecules in the
poly(acrylic–styrene) binder structure strongly affected the
properties of sintered materials. In case of samples based
on B2 binder more than twice lower values of open
porosity and wettability as well as 2.7% higher
densification were noted in compared to those with B1 binder.
Application of the water-thinnable poly(acrylic–styrene)
binders allowed also to obtain samples with slightly greater
bending strength. To consider also this parameter, the best
result was obtained for materials based on binder B2. In
this case, the value of bending strength equaled 192 MPa
which was 4% greater than samples obtained using
poly(vinyl alcohol) as a binder (184 MPa).
The samples obtained using modified alumina were
characterized by much lower densification (around 5%) as
well as 4 times higher values of open porosity and
wettability in comparison with the samples prepared from
unmodified ceramic powder. However, they exhibited
23.5% greater bending strength (237 MPa). Thus, despite
lower density, materials prepared from modified alumina
showed significantly higher mechanical strength for both
green and sintered bodies. This not typical dependence can
be explained by different microstructure of studied
materials. During the strength testing of the samples, the
decohesion process has initiated at the defect. In case of the
bigger defects of microstructure, the lower force is needed
to fracture the sample. Despite the higher porosity, the
samples based on modified alumina did not exhibit defects
of large size in contrast to unmodified Al2O3 materials
(Fig. 6a, b). Moreover, lower densification of green bodies
affects the significantly less grain growth during thermal
Fig. 6 SEM images of sintered
samples based on unmodified
(on the left) and modified (on
the right) alumina powder
molded with B2 binder:
a magnification 9100;
b magnification 91000;
c magnification 910,000
where dv, density of the sintered samples; dr, relative density of the sintered samples; Po, open porosity of
the sintered samples; n, wettability of the sintered samples; rz, bending strength of the sintered samples
treatment. These are probably the reason of greater
mechanical strength of modified samples.
The aim of the work was the examination of poly(acrylic–
styrene) with the addition of a new amphiphilic
macromonomer as an environmentally friendly, water-thinnable
binder in shaping of unmodified and modified (by
silanization) Al2O3 by die pressing. The widely thermal
analysis showed that synthesized binder mainly
decomposed to non-toxic gases such as CO2 and H2O which
confirmed it eco-friendly behavior. Additionally,
comparison of the synthesized binder with commercially available
PVA showed that synthesized binders exhibit much lower
glass transition temperatures, respectively, 5.6 C for B1
binder and - 0.5 C for B2 binder which provide elastic
behavior and allows to enhance the strength of the sample
before sintering. The samples based on unmodified powder
obtained using B2 binder were also exhibited the highest
bending strength after sintering process. Densities of the all
sintered samples were comparable and approximately
equaled 95% of TD. Moreover, it was shown that the
application of the modified Al2O3 by silanization
additionally favorably enhances the mechanical strength of
samples before and after sintering.
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