J. Ceram. Sci. Technol.

, 09 [3] 225-234 (2018)

DOI: 10.4416/JCST2018-00008
available online at: http://www.ceramic-science.com
© 2018 Göller Verlag

Surface Modification of Alumina Powder to Prevent

Exfoliation of Samples Fabricated by Gelcasting
A. Wieclaw-Midor *, P. Wiecinska, M. Szafran
Warsaw University of Technology, Faculty of Chemistry, 3 Noakowskiego Street, 00 – 664 Warsaw, Poland
received January 31, 2018; received in revised form April 4, 2018; accepted April 28, 2018

Abstract
The aim of this work was to study the influence of the Al 2O 3 surface modification 2-hydroxyethyl acrylate (HEA)
on the properties of green and sintered ceramic bodies. As a reference, non-modified Al 2O 3 was used in the research.
The modified Al 2O 3 powder was characterized with TEM and thermal analysis coupled with mass spectrometry. The
rheological behaviour of slurries containing modified and non-modified alumina powder was measured, as well as the
properties of green bodies. The proposed surface modification enables the production of green ceramic samples with
homogeneous microstructure, high mechanical strength and high density. Sintered materials presented high density
and favourable values for Vickers hardness. The obtained results showed that the presence of HEA on the powder
surface partially prevents the negative effect of oxygen inhibition during gelcasting of alumina. Oxygen inhibition is
a well-known problem in gelcasting but has still not been fully overcome for samples formed in an air atmosphere.
Keywords: Gelcasting, surface modification, alumina, mechanical strength

I. Introduction vironment, it is now important to look for low-toxic, in-

Nowadays, shaping of ceramics has become more and expensive and water-soluble organic additives. For this
more demanding to meet the needs of science and tech- reason, there is great interest in compounds such as sac-
nology. It is desirable to produce materials with com- charides, their derivatives and polysaccharides, for ex-
plex geometries, short moulding time and small quanti- ample: D-fructose 25, glucuronic acid 26, 3-O-acryloyl-D-
ties of environmentally friendly and water-soluble organic glucose 27, agarose 28, which could play the role of de-
compounds. Furthermore, to fabricate new products with flocculants, monomers or gelling additives for suspensions
novel and unusual properties, various powders for exam- containing alumina powder.
ple: Al 2O 3 1, 2, ZrO 2 3, 4, SiC 5, 6, ZnO 7, 8, Si 3N 4 9, 10, Ba- Gelcasting has many advantages, for example it is a
TiO 3 11 have been examined to ascertain their behaviour near-net-shaping method with relatively short moulding
during different compaction techniques. In this context, a time 29. However, this technique has some disadvantages
large number of novel shaping methods based on colloidal that hinder the use of gelcasting in industry for large-scale
processing has been developed 12. Of the colloidal shap- production. The main problems are: proper drying of
ing techniques for alumina powder, the most popular seem large ceramic parts and the oxygen inhibition that appears
to be: gelcasting 13, 14, tape casting 15, 16, direct coagulation during the shaping process. They lead to a decrease in the
casting 17, 18 and slip casting 19, 20. These methods allow mechanical strength of the green bodies and the formation
the production of thick or thin 21, dense 22 or porous 23, 24 of various defects (e.g. surface exfoliation, microcracks).
alumina materials. Alumina is the most commonly used The research in this paper concerns oxygen inhibition and
engineering ceramic material, owing to its unique com- prevention of surface exfoliation of samples, and therefore
bination of high hardness, good mechanical strength and this problem is described in greater detail.
high density. In the gelcasting process, oxygen is a known inhibitor
Gelcasting involves conducting in-situ polymerization of radical polymerization. If chain propagation has start-
which occurs in a ceramic slurry and, as a result, a macro- ed and oxygen molecules are present, the oxygen becomes
molecular polymeric network is formed which connects attached to the growing chain, creating peroxide radicals
the ceramic particles. The main challenge in this method is that are inactive in the polymerization process. This mech-
to obtain stable, homogeneous suspension with high sol-
anism has been explained more extensively elsewhere 30.
id loading. The selection of appropriate amounts of or-
Oxygen inhibition unfavourably influences the quality of
ganic additives such as monomer, dispersing agent, acti-
the polymeric network that holds the ceramic particles to-
vator or initiator of radical polymerization is necessary
gether. This problem can be partially mitigated, for exam-
to obtain slurries with favourable parameters. To meet
ple, by replacing the air atmosphere during casting with
the increased requirements for the protection of the en-
CO 2, N 2 or vacuum 31. Furthermore, new monomers that
* Corresponding author: awieclaw@ch.pw.edu.pl are more resistant to oxygen are still required 32. More-
226 Journal of Ceramic Science and Technology —A. Wieclaw-Midor et al. Vol. 9, No. 3

over, it is desirable to obtain a stable suspension with centrifuged powder was dried at 50 °C for 24 h and ho-
favourable viscosity and homogeneous distribution of or- mogenized in an agate mortar. Samples based on non-m-
ganic additives. The insufficient distribution of a small Al 2O 3 and m-Al 2O 3 were prepared in a gelcasting pro-
amount of organic additives causes the lack of perfect ho- cess, shown schematically in Fig. 1.
mogenization. As a result, gelation of obtained ceramic Three types of ceramic slurries (A – with non-m-Al 2O 3,
slurry does not occur in the total volume of the sample but B – with m-Al 2O 3 and C – containing the mixture of A
only in some areas. Consequently, green bodies with low and B) were first prepared in alumina containers. Dispers-
mechanical strength, microcracks and various deforma- ing agents were dissolved in deionized water followed by
tions are obtained. Literature data shows that one possible HEA in slurry A. In the case of slurries B and C, HEA
method to change the properties of ceramic powders is sur- was not added because the monomer was already present
face modification. There are known modifications of alu- on the surface of the modified powder. Then the appro-
mina powder with 1,6-hexanediol diacrylate and its appli- priate amounts of ceramic powder (non-m-Al 2O 3 or m-
cation in the preparation of UV-curable ceramic suspen-
Al 2O 3) were dispersed and the polymerization activator
sions 33 or stearic acid to improve the rheological proper-
was added. The slurries were mixed in a planetary ball mill
ties 34. In this work, the influence of surface modification
(PM-200, Retsch) for 60 min at a speed of 300 rpm. The
of alumina powder based on the impregnation method and
suspensions were then mixed and degassed in a Planetary
2-hydroxyethyl acrylate (HEA) on the rheological char-
Centrifugal Mixer THINKY ARE-250 for 2 x 4 minutes
acterization of slurries and selected properties of obtained
at a speed of 800 rpm (mixing) and 1800 rpm (degassing)
samples was examined. Additionally, the possible impact
of the presence of HEA on the powder surface on the limi- to remove bubbles > 1 μm. In the next step, the initiator
tation of oxygen inhibition and surface exfoliation of green was added to initiate the in-situ polymerization, then mix-
bodies has been studied. The results for modified alumina ing and degassing were performed for 2 x 30 s at a speed of
powder were compared with the results for non-modified 800 rpm (mixing) and 1800 rpm (degassing). The prepared
alumina. slurries with favourable viscosity (A and C) were cast in-
to PVC moulds with a diameter measuring 20 mm and a
II. Experimental height of 10 mm, where polymerization continued. The
obtained green bodies after gelation were removed from
(1) Materials
the moulds and dried for 24 h at room temperature. Then
The ceramic powder used in the research was a-Al 2O 3 the specimens were polished with SiC abrasive papers with
TM-DAR (Tamei Chemicals, Japan) with an average par- gradation in the range from P500 to P1500 to smooth the
ticle size of 115 nm and a specific surface area 12.98 m 2/g surface prior to mechanical strength measurement.
measured on an ASAP 2020 V3.01 (Micromeritics, USA).
The samples were sintered at 1400 °C/1 h, the heating rate
The density of the powder was 4.02 g/cm 3 measured on
up to 600 °C was 1 K/min, and then 5 K/min up to 1400 °C.
an AccuPyc 1340 Pycnometer (Micromeritics, USA). In
The cooling rate was 5 K/min down to room temperature.
this paper, abbreviated names of powders are used as fol-
The concentrations of all components are listed in Table 1.
lows: for non-modified powder – non-m-Al 2O 3 and for
modified powder – m-Al 2O 3. To obtain samples with the
gelcasting method, additional organic additives have been (3) Characterization techniques
used. Diammonium hydrocitrate, DAC (pure, POCh, The densities of non-m-Al 2O 3 and m-Al 2O 3 powders
Poland) and citric acid, CA (99.5 %, Sigma-Aldrich) were were measured with an AccuPyc 1340 Pycnometer (Mi-
used as dispersing agents for the ceramic particles in the cromeritics, USA). The microstructure of the modified
slurries. Commercially available 2-hydroxyethyl acrylate, powder was examined under a transmission electron
HEA (96 %, Sigma-Aldrich) was used as the monomer microscope (FE-SEM Hitachi S5500). Selected thermal
(for non-modified powder) and as impregnating agent analysis techniques were used. Thermogravimetry (TG),
(for modified powder). N,N,N’,N’-tetramethylethylene- derivative thermogravimetry (DTG) and differential ther-
diamine, TEMED (98 %, Fluka) and ammonium persul- mal analysis (DTA) were performed using a Netzsch STA
fate, APS (98 %, Sigma-Aldrich) were used as an activator
449C coupled with a Quadrupole Mass Spectrometer
and an initiator of polymerization, respectively. The sus-
(MS) Netzsch QMS403C.
pensions were prepared in Milli-Q deionized water.
The temperature was varied from 35 °C to 1000 °C;
(2) Modification of powder; slurries and sample prepa- the heating rate was 5 K/min. The measurements were
ration performed in the constant flow of two gases: argon –
The first step was the preparation of alumina powder 10 ml min -1 (protective gas) and synthetic air (75:25
with modified surface by using 2-hydroxyethyl acrylate. N 2:O 2) – 60 ml min -1. The important information from
The scheme of this process is shown in Fig. 1. Alumina thermal analysis is the temperature at which decomposi-
powder was dispersed in 2-hydroxyethyl acrylate with tion of organic compounds ends because it helps to deter-
mass ratio 5:4. The suspension was stirred with a mag- mine a suitable sintering programme. The ceramic samples
netic stirrer for 6 h at a speed of 400 rpm and kept at were sintered in the air, therefore thermal analysis was also
room temperature for 24 h. Then the suspension was cen- conducted in the flow of air. Additionally, the construc-
trifuged at 10 000 rpm for 10 min in an MPW-350R High- tion of the apparatus requires the constant flow of argon
Speed Brushless Centrifuge, MPW Med. Instruments. The as the protective gas.
September 2018 Surface Modification of Alumina Powder for Gelcasting 227

Fig. 1: Scheme showing the impregnation of Al 2O 3 powder and sample preparation applied in the research.

Table 1: Composition of the slurries used in the research. were plotted as a function of the frequency. The viscosities
of slurries as a function of shear rate were measured in
Concentration the range from 0.1 s -1 to 100 s -1and then back to 0.1 s -1.
The densities of the green and sintered specimens were
Component Slurry Slurry Slurry
measured with the Archimedes method in kerosene and
A [%] B [%] C [%]
water, respectively. The tensile strength of the green bod-
non-m-Al 2O 3 a 55 - 30 ies was calculated from the indirect tensile (Brazilian) test
m-Al 2O 3 a - 55 25 on a Tinius Olsen H10KS instrument with a head shift
H 2O a 45 45 45 speed of 0.1 mm/min. In the Brazilian tension test, a cir-
DAC b 0.3 0.3 0.3 cular disk was placed between two metallic flat plates and
compressed, producing a nearly uniform tensile stress dis-
CA b 0.1 0.1 0.1 tribution normal to the loaded (vertical) diametral plane,
HEA b 4 - - and leading to the failure of the disk by splitting. The con-
TEMED c 0.5 0.5 0.5 tact between the plates and the samples was direct without
APS c 0.7 0.7 0.7 any additional support. The speed of the head shift was
a vol%.
0.1 mm/min. The tensile strength (r) was calculated as r t =
b wt% with respect to the amount of ceramic powder. (2P/pTD), where P is the force causing the damage of the
c wt% with the respect to the amount of monomer. sample, T and D are the thickness and the diameter of the
disc-shaped sample, respectively.
The rheological properties of slurries A and C were A scanning electron microscope, SEM (Ultra Plus Zeiss),
examined using a Kinexus Pro rotational rheometer was used to observe the microstructure of green and sin-
(Malvern Instruments, UK) with a plate-plate geome- tered samples. Vickers indentations were made with a Dig-
try. The gap between the plates was 0.5 mm. At first, the ital Vickers Hardness Tester HVS-30T (Huatec Group
LVER (linear viscoelastic region) at a frequency of 1 Hz Corporation, China), applying a load of 196 N. For each
was determined and then the elastic (G’) and viscous (G") sample, five indentations were made. Photographs of the
modules at the strain corresponding to the LVER region indentations and the measurements of the diagonals were
228 Journal of Ceramic Science and Technology —A. Wieclaw-Midor et al. Vol. 9, No. 3

captured with a light microscope (Nikon Eclipse LV150N, The first step up to 213 °C with the mass loss 8.42 %, the
Japan). second step up to 386 °C with the mass loss 0.56 % and
The measurements were performed on ten samples ob- the third step up to the final temperature with the mass
tained from each slurry tested. The error was calculated as loss 0.24 %. The total mass loss for m-Al 2O 3 was 9.22 %.
the standard deviation. Fig. 3b shows more information from the mass spectrome-
ter for m-Al 2O 3. Degradation of 2-hydroxyethyl acrylate
III. Results and Discussion
proceeds in three steps and the main products of decom-
(1) Characteristic of modified alumina powder position in the oxidizing atmosphere are H 2O and CO 2.
The densities of non-m-Al 2O 3 and m-Al 2O 3 pow- The presence of H 2O and CO 2 are confirmed by m/z val-
ders were measured with a helium pycnometer and they ues 18 and 44, respectively. The maxima on m/z 18 and
equalled 4.03 g/cm 3 and 3.29 g/cm 3, respectively. The den- on m/z 44 at 209.6 °C and 317.9 °C are observed, which
sity of m-Al 2O 3 is lower owing to the adsorption of the corresponds to two effects: dehydration and decomposi-
compound of lower density (d HEA = 1.1 g/cm 3) on Al 2O 3 tion of hydrocarbon chain with the release of CO 2. The
surface. The morphology of m-Al 2O 3 is presented in endothermic peak on the DTG curve with the minimum
Fig. 2a, while Fig. 2b shows a single alumina particle with at 193 °C is visible.
the visible lighter coating and the darker core. It may indi-
cate the presence of adsorbed HEA on the powder surface. (2) Properties of ceramic suspensions
The thickness of the outer layer was approx. 10 nm. The Slurry B was characterized by high viscosity (too high for
powder was sputtered with carbon prior to TEM obser-
the gelcasting process), therefore it was not examined in
vations, therefore C was not examined by means of EDS.
terms of rheological properties. The surface of the modi-
fied powder was covered by a large number of adsorbed
monomer molecules. The dispersant could not therefore
act effectively in order to broaden the electric double layer
around particles. As a result, the value of viscosity of the
slurry from series B was not favourable for the gelcasting
process.
The content of the monomer in slurries A and C has been
calculated and equalled 3.21 % and 2.93 %, respectively.
The amount of the monomer in both slurries is similar,
therefore these slurries can be compared.
Fig. 4 shows viscoelastic features (elastic and viscous
modules) as a function of the shear strain and frequency of
slurries A and C. Firstly, linear viscoelastic region (LVER)
at a frequency of 1 Hz for both alumina slurries was de-
termined. The LVER was assigned at 54 % and 0.80 %
shear strain respectively for suspension A(Fig. 4a) and C
(Fig. 4b). For both slurries, the elastic modulus (G’) pre-
dominates over the viscous modulus (G") over the whole
frequency range. It follows that the elastic properties pre-
vail in these suspensions. For slurry A (Fig. 4c), G’ and G"
at a frequency of 5 Hz equal 12800 Pa and 1110 Pa, respec-
tively. For slurry C, (Fig. 4d) G’ and G" at a frequency of
5 Hz equal 125 Pa and 35 Pa, respectively. For slurry A,
G’ and G" curves intersect at shear strain of 1.57 %. In
contrast, for slurry C, the intersection of the G’ and G"
curves at a shear strain of 7.96 % was observed.
Fig. 5a shows the viscosity curves of slurries A and C.
Fig. 2: TEM images of morphology of m-Al 2O 3 (a) and single
particle of m-Al 2O 3 (b). Viscosity values for both slurries were low and at shear
rate 10 s -1 equalled 0.9 Pa⋅s and 2.4 Pa⋅s, respectively for A
Fig. 3 shows TG, DTA, DTG curves and the data from and C. Both slurries exhibited shear-thinning behaviour.
the mass spectrometer for m-Al 2O 3 in comparison with These results show a similar relationship to that described
non-m-Al 2O 3. On the basis of this measurement, the by Hu et al. 34. In Hu’s research, modified powder al-
amount of HEA adsorbed on the powder surface was so showed higher values of viscosity than pure powder.
determined. The total mass loss was 0.44 % (according However, the differences in viscosity were small, just like
to the TG curve, Fig. 3a) in the case of non-m-Al 2O 3, in this research. Fig. 5b shows flow curves of alumina
which indicates a high purity of the powder and a low suspensions and both of them exhibit slightly thixotrop-
content of water adsorbed on the particles. For m-Al 2O 3, ic behaviour. This indicates that the internal structure
three stages of 2-hydroxyethyl degradation are observed. of slurries is destroyed during shear and then rebuilds.
September 2018 Surface Modification of Alumina Powder for Gelcasting 229

Fig. 3: a) TG curves of non-m-Al 2O 3and m-Al 2O 3, b) DTG/DTA/MS curves of m-Al 2O 3.

Fig. 4: Viscoelastic properties (elastic and viscous modules) as a function of shear strain and frequency of alumina slurries A (a, c) and C (b, d).
230 Journal of Ceramic Science and Technology —A. Wieclaw-Midor et al. Vol. 9, No. 3

Fig. 5: Viscosity (a) and flow (b) curves of the alumina slurries A and C.

The yield stress of suspension A equals approx. 1.6 Pa. where the Vickers hardness of pure alumina equalled
Higher yield stress (approx. 7.5 Pa) is observed for the 17 – 17.5 GPa. Higher Vickers hardness was observed
suspension containing m-Al 2O 3.The monomer HEA is for the specimens containing m-Al 2O 3 and equalled
not a dispersing agent, and an excessively high quantity of 19.2 GPa.
this compound may cause an increase in viscosity of slurry, Exfoliation of green bodies is a common problem ob-
as it was in the case of slurry B. served in gelcasting as the result of the oxygen inhibition.
Figs. 6c and 6d show green bodies after gelation. It can be
(3) Sample properties
observed that specimens with m-Al 2O 3 (Fig. 6d) do not
Values of selected properties for green and sintered bod- exhibit any exfoliation layer. During mechanical machin-
ies are shown in Table 2. The specimens from series C seem
ing of samples with the use of abrasive papers, no crushing
to have better properties than samples from series A. Rel-
or cracking of samples was observed. It means that poly-
ative density of green and sintered samples C equal 61 %
merization has been completed properly in the whole vol-
and 98 %, respectively. In contrast, relative density of
ume of the specimen. The top part of samples contain-
green and sintered bodies A equal 56 % and 96 %, respec-
ing non-m-Al 2O 3 (Fig. 6c) was exfoliated as a result of
tively. For green bodies from series C the tensile strength
is almost two times higher than for green bodies from oxygen diffusion that blocked the reaction of polymer-
series A(3.57 MPa and 1.83 MPa, respectively). These re- ization. During mechanical machining, the samples were
sults are comparable with those described by Millán et crushed. The explanation why m-Al 2O 3 powder prevents
al. However, it is worth underlining the main difference the negative effect of oxygen inhibition is shown schemat-
between the applied processing agents. Millán has used ically in Fig. 6. Fig. 6a shows slurry A and free molecules of
polysaccharides (agar, agarose and carrageenan) as gelling HEA monomer which has low initial viscosity. This per-
agents, which enables all the problems associated with rad- mits oxygen to easily diffuse into the ceramic suspension,
ical polymerization to be avoided, but requires the use react with the free radicals and inhibit the polymerization
of elevated temperature. The use of modified alumina de- reaction. Fig. 6b shows slurry containing m-Al 2O 3 pow-
scribed in this paper enables gelcasting to be performed at der, which is characterized by shear-thinning behaviour
room temperature and avoids the exfoliation of samples. as shown in the viscosity curve in Fig. 5. Thanks to high
The Vickers hardness of samples with non-m-Al 2O 3 initial viscosity, diffusion of oxygen into the sample is
equalled 17.3 GPa. These values are comparable with the blocked. This hinders reaction of the oxygen with free rad-
literature data described by Auerkari 35 and Cassellas 36, icals.

Table 2: The properties of green and sintered bodies.

Green bodies Sintered bodies

Series Relative density [%] Tensile Relative density [%] Volumetric Vickers
strength [MPa] shrinkage [%] hardness [GPa]
A 56.0±0.1 1.83±0.45 96.2±0.1 34.1±0.9 17.3±0.2
C 61.1±1.3 3.57±0.77 97.8±0.1 32.9±3.1 19.2±0.2
September 2018 Surface Modification of Alumina Powder for Gelcasting 231

Fig. 6: The schematic explanation of oxygen inhibition phenomenon for ceramic slurries: A (a) and C (b). Images of surfaces of green bodies
from series A (c) and C (d).

Fig. 7 presents SEM images of green bodies from se- results of tensile strength measurement. Additionally,
ries A and C. It allows observation of the location of coverage of Al 2O 3 particles by HEA monomer might
the polymeric network. Photos indicate the high homo- contribute to more homogeneous distribution of the re-
geneity of the samples. The microstructure of the two sulting polymeric binder in the whole volume of the sam-
specimens looks similar. Fig. 7a and Fig. 7b show poly- ple. It confirms the higher value of tensile strength for
mer in the form of bridges holding alumina particles to- these samples. Fig. 8 shows SEM images of surfaces of
gether. For the sample containing m-Al 2O 3 (C), more sintered samples (a, b). Specimens obtained from sus-
polymeric bridges are visible than for the sample with pension based on m-Al 2O 3 (C) (Fig. 8b) have a more
non-m-Al 2O 3 (A), which is in good agreement with the homogeneous and dense microstructure and are almost

Fig. 7: SEM images of green bodies from series A (a) and C (b). Polymeric bridges are marked with yellow.
232 Journal of Ceramic Science and Technology —A. Wieclaw-Midor et al. Vol. 9, No. 3

free of pores in comparison with samples based on non- ments and the microstructure analysis with SEM. Addi-
m-Al 2O 3 (A) (Fig. 8a). It is also in good correlation with tionally, the Vickers hardness of alumina sintered bodies
the measurements of the relative density of these samples was high and equalled 19.2 GPa.
(96 % and 98 % for non-m-Al 2O 3 and m-Al 2O 3, respec-
tively). On the basis of calculations made from the pre- Acknowledgements
sented micrographs it was found that the average grain size This work has been financially supported by Warsaw
for samples A and C was 0.55 μm and 0.46 μm, respec- University of Technology, Faculty of Chemistry.
tively. For the sample containing non-m-Al 2O 3 (A), they
were five times and for the sample containing m-Al 2O 3 References
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