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ELSEVIER
Abstract
Slurry formulations and processing parameters of the water-based tape casting of ceramic powders are reviewed. Additives
include binders, like cellulose ethers, vinyl or acrylic-type polymers; plasticizers, like glycols; and dispersants, like ammonium salts
of poly(acrylic acids). Mostly alumina powders have been employed. Hydrophobing of ceramic powders permits the aqueous
processing even of water-reactive powders, like aluminium nitride. Non-toxicity and non-inflammability of water-based systems
represent an alternative to organic solvent-based ones. Aqueous slurries are, on the other hand, complex multiphase systems, very
sensitive to process variations. Statistical design of experiments was used for the improvement of the process.
Keywords: Tape casting; Ceramic powders; Slurries
1. Introduction
207
Binder
Plasticizer
Dispersant
Others
Reference
Alumina + MgO
Acrylic polymer
PEG + BBP
Condensed aryl
sulfonic acid
Octylphenoxyethanol b
wax emulsion c
[9]
Alumina + talc
PAA
Glycerol
[lO]
PAA
Glycerol + PVP
NH4PMA +
Dispex A40e
NH4PM +
Dispex A40 e
PUR
PVA
PVAc
NH4PA
POENPE
POENPE
POENPE
Primal 850 e
[11]
Glycerol
Glycerol
Glycerol + DBP
NH4PMA
[12]
NH 4 salt of a
polyectrolyte
[13]
Alumina
Alumina
Cellulose ether
(MC, HPMC or
HBMC)
Alumina
Acrylic
copolymer
Alumina
PVAc
Alumina
Acrylic polymer
(PEA + PMMA)
PPG
Mullite
Acrylic polymer
(PEA + PMMA)
Acrylic polymer
(PEA + PMMA)
PPG
PPG
NH4PMA
Alumina
HEC
PEG
NH4PA
Alumina
AE/AA
AE/AA
Alumina
PAA
BBP
NaCMC
Silicon organics c
[14]
NH4PMA
Pin oild
[15,16]
[17]
Acrylic
dispersants
PEG
NH4PA
[18]
[19,20,22,23]
[21]
[241
aBBP is benzyl butyl phthalate; DBP is dibutyl phthalate; POENPE is poly(oxyethylene nonylphenol ether); PUR is polyurethane; the remaining
abbreviations are Listed in Tables 2 and 3.
bwetting agent
~defoamer
dsurfactant
ecommercial name (no composition given)
2. Slurry formulation
Compared with non-aqueous solvents, the variety of
water-soluble binders, plasticizers and dispersants is
restricted to a few systems, which will be discussed in
the following sections. Table 1 summarizes the combinations used for aqueous tape casting of alumina and
mullite.
Some general rules can be inferred for the preparation of a tape casting slurry: (i) the ratio between
organic components and ceramic powder must be as
low as possible; (ii) the amount of solvent must be fixed
208
1oo
20/~
80
1oo.
0
. 0
20
40
60
80
100
Water, wt%
Fig, 1. Aqueous slurry formulations for tape casting. The ceramic powder is alumina, with the exception of Ushifusa and Cima [17], who used
mullite.
classification, however, is not absolute: some additives
have multifunctional characteristics. A certain binder,
for instance, can exhibit plasticizing or dispersing
effects. Two investigators use neither dispersant nor
plasticizer in the slurry formulations [12,19-23]; in the
other cases the binder corresponds at least to half of the
organic part of the slurry. The dispersant content is in
any case the lowest of all three organic additives ( < 20
wt.%). Plasticizers were generally used up to around 50
wt.%, but Kemr and Mizuhara [10] have used much
higher contents.
2.1. Solvent
The solvent dissolves the organic materials and distributes them uniformly throughout the slurry. It is the
vehicle that carries the ceramic particles in a dispersion
until it evaporates and leaves a dense tape on the
carrier.
A non-aqueous suspension dries quickly and produces green sheets having a high density and a fine
surface appearance. An aqueous suspension has the
disadvantages of high evaporation latent heat and inferior drying characteristics, and there are many quality
problems to be solved.
A comparison of aqueous and non-aqueous slurries
for tape casting was made by Nahass et al. [15] to
determine the effect of changing solvent systems on
slurry processing and green tape quality. An alumina
powder was utilized and the other slurry components as
well as the processing parameters were kept constant.
Green tapes from both systems had similar physical
properties, although the aqueous systems were more
sensitive to process perturbations.
2.2. P o w d e r
209
2o 8o
.N.agata(91-93)
0 ushifusa and Cima (91)
$ Burnfield and Peterson (92)
-~ Ryu et al. (93)
100 ~
0
~
20
~
40
.
60
0
80
1O0
Plasticizer, wt%
Fig. 2. Organic additive formulations used in aqueous slurries for tape casting.
2.3. Binder
CH2-X
OH
CH2-Y
rl
Fig. 3. Structural formula of cellulose derivatives.
D. Hotza, P. Greil / Materials Science and Engineering A202 (1995) 206 217
210
Table 2
Cellulose derivatives used in aqueous tape castinga
Compound
Side groups
X
MC
HEC
HPMC
HBMC
NaCMC
Cellulose
Methyl
Hydroxyethyl
Hydroxypropyl methyl
Hydroxybutyl methyl
Sodium carboxymethyl
OH
OCH 3
OC2H4OC2H4OH
-OC3 H6OH
-OC4HsOH
-OCH~COONa
DS
MS
1.5
1.5
1.5
1.5
1.0
1.5
2.5
1.5
1.5
1.0
OH
OCH 3
OC2H4OH
OCH 3
OCH3
-OCH2COONa
OH
-OCH 3
OCzH4OC2H4OH
OCH 3
OCH3
OH
--(~
PVA
PVAc
PVP
PAA
AE/AA
PEA
PMAA
PMMA
NHaPA
NHnPMA
CH2
n
Side groups
Vinyl radical
Poly(vinylalcohol)
Poly(vinylacetate)
Poly(vinylpyrrolidine)
Poly(acrylic acid)
Copolymer of acrylic esterb
and acrylic acid
Poly(ethylacrylate)
Poly(methacrylic acid)
Poly(methyl methacrylate)
Ammonium polyacrylate
Ammonium poly(methacrylate)
H
-H
H
-H
H
H
OH
-OOCCH 3
~ NC4H 8
-COOH
-COOCH 3
COOCH2CH 3
-COOH
-CH3 -COOCH 3
-H
COONH4
CH 3 -COONH4
CH 3
D. Hotza, P. Greil / Materials Science and Engineering A202 (1995) 206 217
211
10.0
1500 ~
Di~.
1000 t ~
..
if)
7.5
4,400g/mol
r \
52,000 g/mol
5.0
2.5
1203
500
0.0
2
10
10
5.0
o
0
2000
4000
6000
8000
Shear rate, s -1
Fig. 5. Viscosity of a 2% aqueous solution of HEC with different
molecular weights as a function of shear rate [31].
o~
9
4.0
co
O~
3.0
~O~
5.0
rJ~
2.5
3.4
3.0
o)
e.121
1:3.5 Dispersant/Plasticizer
Fig. 7. Strength (top) and elongation (bottom) of alumina green tapes
with different powder charges as a function of dispersant/plasticizer
amount [18].
2.4. Plasticizer
0.0
1.0
34 wt% AI203
7.5
.c-~
t-
2.0
10.0
Q-
LLI
2.6
2.2
Binder content, w t %
Fig. 6. Strength (top) and density (bottom) of alumina green tapes
with different powder charges as a function of HEC wt.% [18].
212
Table 4
Common plasticizers used in aqueous tape casting
Compound
Formula
Glycerol
Poly(ethylene glycol)
Poly(propylene glycol)
Dibutyl phthalate
Benzyl butyl phthalate
PEG
PPG
DBP
BBP
HOCH2CH(OH)CH2OH
HO-(CH2CH20).-H
HO (CH2CH2CH20).-H
C16H2204
C15H2oO4
2.5. Dispersant
A dispersant, sometimes also called deflocculant, wetting agent or surfactant, coats the ceramics particles
and keeps them in a stable suspension in the slurry due
to steric and/or electrostatic repulsion. Both mecha-
oo
50
40
Q.
E
e'-
30
._o
Co
20
"..
0
40
60
80
1O0
D. Hotza, P. Greil / Materials Science and Engineering A202 (1995) 206 217
200
10.0
150
9.5
>
1 O0
9.0
I~
50
8.5
u)
0
c~
d
E
0
r-
.__q
tI11
.~
8.0
1
213
After drying, the tape can be released and cut for use
in a shaping procedure, like punching [15,16] or laminating [17]. When the discontinuous process is used and
the tapes are cast on glass plates, a razor blade can be
214
used to remove them from the plates [15,40]. Multilayered ceramic packages were produced by a thermocompression (lamination) at 120 C, with a pressure of
2.5-17.5 MPa [17].
The burnout of organic slurry-based tapes has been
investigated and partially modelled [41,42]. In the case
of aqueous tape-casting, there is no rigorous study
about it. Thermogravimetric studies performed by Burnfield and Peterson [18] showed that HEC binder in the
presence of alumina burns out differently from the
polymer alone. In both cases, the polymer burns out
completely, but the rate and the temperature of
burnout differ.
Ryu et al. [24] performed an investigation about the
rheology of aqueous alumina slurries for tape casting
concerning changes in pH and its influence on properties of green and sintered tapes. The bulk density of the
sintered bodies followed the same tendency observed in
the green bodies, Fig. 10. The variation of green and
sintered t a p e densities on pH is a consequence of the
pH-dependence of the rheological characteristics of the
slurry, which presented the highest viscosity at the
isoelectric point, pH 2.4. Furthermore, this isoelectric
point is significantly lower in comparison to that of the
aqueous alumina suspension without organic components, which lays at pH 7.8. This effect is similar to that
described by Cesarano and Aksay [35] for the adsorption of a polyelectrolyte dispersant on alumina.
6o
/)
ca)
"0
>=
n-
8o
7o
--0---e--
1600C
1500oC
--B-
1400C
green tape
6o
5o
0
12
pH
Fig. 10. Relative density as a function of slurry pH for green and
sintered tapes of alumina [24].
D. Hotza, P. Greil / Materials Science and Engineering A202 (1995) 206 217
215
Table 5
Experimental design for aqueous tape casting slurriesa
Run No.
1
2
3
4
Factor levels
Viscosity (Pa s)
Z (dB)
xM
xD
xp
xB
XL
10 S-t
20 S-1
40 S I
50 S I
1
1
2
2
1
2
1
2
1
2
2
1
33.3
33.3
33.3
33.3
0.0
0.0
0.8
0.8
0.0
4.2
0.0
4.2
6.7
10.0
10.0
6.7
60.0
52.5
55.8
55.0
2.50
12.00
6.00
0.40
2.00
10.00
5.00
0.30
1.80
8.50
4.25
0.28
1.80
8.00
4.00
0.26
15.75
14.58
14.58
13.95
ax is the weight fraction respectively of ceramic powder (M), dispersant (D), plasticizer (P), binder (B) and solvent (L). A, B and C are the factors
that correspond to x D, xp and x a. Z is the signal-to-noise ratio
5. Summary
The use of water-based systems represents an alternative to the widespread non-aqueous tape casting. Nontoxicity and non-inflammability seem to be especially
216
D. Hotza, P. Greil / Materials Science and Engineering A202 (1995) 206 217
Table 6
Analysis of variance on mean viscosity of aqueous tape casting slurries a
Factor and level
A~
A2
B~
46.60
20.49
27.35
39.74
9.34
57.75
5.83
2.56
3.42
4.97
1.17
7.22
B2
Cl
C2
Reproducibility error
Pooled error
Total
p (%)
42.61
42.61
41.07 a
19.69
9.59
9.59
9.25"
4.05
146.47
146.47
141.19 c
68.89
12
12
15
12.45
12.45
211.12
1.04 b
as is the sum of the measured values; m is the average of the measured values; f i s the degrees of freedom; S is the sum of squares; V is the variance;
F is the Fisher test-value; p is the percentage contribution to variance
bpooled factor into error
Significant at 95% confidence
aSignificant at 99% confidence
Table 7
Analysis of variance on signal-to-noise ratios of viscosity of aqueous
tape casting slurries a
Factor and level
P (%)
A1
A2
BI
B2
C1
C2
30.32
28.53
30.32
28.53
29.70
29.19
15.16
14.27
15.16
14.27
14.85
14.58
0.80
0.80
10.74
43.33
0.80
0.80
10.74
43.33
0.07
0.07 b
1
3
0.07
1.68
Pooled error
Total
g
~
1
0.1
0.01
References
173-198.
10
tion
0.001
0.00
0.10
HEC Slurry
0.20
0.30
D. Hotza, P. Greil / Materials Science and Engineering A202 (1995) 206 217
[29]
[30]
[31]
[32]
[33]
[34]
[35]
[36]
[37]
[38]
[39]
[40]
[41]
[42]
[43]
[44]
[45]
[46]
[47]
[48]
217