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2004 11:57 Uhr Seite 126

Characterization of the Linear Viscoelastic Region in Suspensions

of Zirconium Oxide: Cohesive Energy Obtained From the Critical
Parameters

David Megías-Alguacil

Department of Applied Physics, University of Granada, 1807 Granada, Spain

Email: dmegias@ugr.es

Received: 22.10.2003, Final version: 26.2.2004

Abstract:
The linear viscoelastic regions (L.V.R.) of suspensions of zirconium oxide particles were determined and charac-
terized through the so-called "critical parameters". These are the values of shear-stress and strain at the crossover
between the linear and the non-linear viscoelastic responses. From these magnitudes, the cohesive energy
between the particles is calculated as a function of volume fraction of solids and at different electrolyte con-
centrations. The oscillatory measurements were carried out using a constant-stress rheometer at a fixed fre-
quency of 1 Hz and increasing shear-stress. The suspensions cover a volume fraction range between 3% - 25%
with electrolyte (sodium chloride) concentrations of 10-1 M, 10-2 M, 10-3 M and 10-5 M. Two different kinds of ZrO2
particles were used: commercially obtained -with no defined geometry- and spheres synthesized by us follow-
ing the method described by Aiken, Hsu and Matijevic [1].

Zusammenfassung:
Der linear viskoelastische Bereich von Zirkondioxid Suspensionen wurde mittels einiger sogenannter "kritischen
Parameter" bestimmt und charakterisiert. Dies sind die Werte der Scherrate und Deformation beim Übergang
von den linearen zu den nicht-linear viskoelastischen Antwortfunktionen. Aus diesen Groessen wird die Kohä-
sionsenergie zwischen den Teilchen als Funktion des Volumenanteils an Feststoff und bei verschiedenen Elek-
trolytkonzentration berechnet. Die Oszillationsmessungen wurden mit Hilfe eines schubspannungsgesteuerten
Rheometers durchgeführt wobei eine feste Frequenz von 1 Hz und eine ansteigende Schubspannung gewählt
wurden. Die Suspensionen umfassen einen Feststoffanteil zwischen 3 und 25% mit Elektrolytkonzentrationen
(Natriumchlorid) von 10-1, 10-2, 10-3 und 10-5 M. Zwei Arten von Zirkondioxidteilchen wurden benuzt: kommerziell
verfügbare Teilchen mit undefinierter Geometrie und Kugeln, welche von uns nach der Methode von Aiken, Hsu
und Matijevic synthetisiert wurden.

Résumé:
Les régimes viscoélastiques linéaires (L.V.R.) de suspensions de particules d’oxyde de zirconium ont été déter-
minés et caractérisés à travers les dénommés “paramètres critiques”. Ceux-ci sont les valeurs des contrainte et
déformation de cisaillement à l’intersection entre les réponses viscoélastiques linéaires et non linéaires. A par-
tir de ces grandeurs, l’énergie cohésive entre les particules est calculée en fonction de la fraction volumique des
solides et à différentes concentrations en électrolytes. Les mesures oscillatoires ont été entreprises à l’aide d’un
rhéomètre à contrainte constante à une fréquence fixe de 1 Hz et en accroissant la contrainte de cisaillement.
Les suspensions couvrent une gamme de fractions volumiques entre 3 et 25% avec des concentrations en élec-
trolytes (chlorure de sodium) de 10-1, 10-2, 10-3 et 10-5 M. Deux types différents de particules de ZrO2 ont été util-
isés: de source commerciale, ne possédant pas de géométrie définie, et des sphères synthétisées par nos soins
en suivant la méthode décrite par Aiken, Hsu et Matijevic [1].

Key words: zirconia, viscoelasticity, critical parameters

© Appl. Rheol. 14 (2004) 126-132 DOI: 10.1515/arh-2004-0007

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1 INTRODUCTION
The properties of a colloidal dispersion are deter-
mined in most cases by parameters like the size
and shape of the particles, the interaction forces
between them and the volume fraction [2]. The
latter provokes changes in the flow behavior of
the aqueous system, increasing the viscosity of
the suspension as the concentration of particles
is increased, resulting in deviations from New-
tonian character. In addition, the presence of an
electrolyte has an impact on the properties of liq-
uid dispersions of small solid particles by, for
example, promoting associations or particle
aggregation.
The study and description of the internal
network of particulate systems has focused
numerous works [3-5]. Several techniques are
available to obtain information experimentally
on microscopic properties of colloidal suspen-
sions, including rheological measurements, both
in the steady-state and in the frequency and time
domains. This technique is a powerful tool since
is not destructive and lets one to get information
on the system microstructure. Viscometric tech-
niques (ramp of shear-stresses applied to the sys-
tem and determination of the response) can also
provide information about the structure of the
system, but the knowledge about the complex
relationship between rheology and interaction
energy is limited [6 - 8].
Experimentally it has been demonstrat-
ed the existence of such an internal order in soft
matter state, i.e., sophisticated studies with neu-
tron scattering [9, 10] which have unequivocally
revealed that such systems not only are struc-
tured but this arrangement corresponds to crys-
talline lattices (b.c.c., f.c.c., etc.) completely anal-
ogous to those developed in solid state. This
manifestation -surprising from the classical
point of view which considers a liquid phase as
an intermediate state from the total disorder pre-
sent in a gas to the maximal ordering found in a
solid- corroborates the existence of large range
forces that induce three dimensional structures
between the particles prolonged in the space.
The relative strength of such forces
(diverse in nature) depends also on the distance
between the particles, and consequently on the
concentration of solid immersed in the fluid
phase, and thus, others especial distributions can
be observed, like aggregated states, arising from
Seite 127
attractive forces. In this set are included the floc-
culated, coagulated and clustered systems.
The aim of this work is to calculate
numerically the energy involved in maintaining
the particles in aqueous suspension in a floccu-
lated –reversible aggregation- structure, and we
use a rheological tool, oscillatory shear sweeps at
a fixed frequency, for calculating quantitatively
the energy that binds the particles. For such a
task, the particles were taken in the colloidal
range and this energy characterized according
several parameters like size and geometry of the
particles, volume fraction of solid and ionic
strength due to the presence of an indifferent
electrolyte.
This work follows this logic line: oscilla-
tory rheological measurements are performed to
each suspension in order to determine its linear
viscoelastic region; the value of G’LVR is fitted as
a function of solid concentration using a power
law relationship which enables us to know if the
suspensions are flocculated and, if this is the
case, to proceed to the calculation of the cohe-
sive energy and its discussion according to the
different experimental parameters.
The colloidal systems studied here are
composed of particles of zirconium oxide in the
colloidal range (< 1 mm) immersed in electrolytic
aqueous phases. This oxide was chosen because
it is possible to prepare monodisperse spheres of
ZrO2. In addition, zirconium oxide is an inorgan-
ic compound that has received a considerable
amount of attention as a component in high-per-
formance ceramics applications [11 - 13].
Dynamic or oscillatory tests are one of
the most important tools in the characterization
of viscoelastic properties of systems. This is due
to their capability in determining the elastic and
viscous components without total destruction of
the system structure. Nevertheless, if the defor-
mation is large enough, the structure can be
destroyed. The region beyond this critical strain
(which depends on volume fraction of solids) is
known as the non-linear viscoelastic region.
As mentioned above, in a flocculated, or
an ordered, structure exists an energy that keeps
the flocs, or the particles, conforming the spatial
particle distribution: the cohesive energy. It rep-
resents the work required to maintain the single
particles aggregated in the flocculated disper-
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Figure 1 (above): Elastic 10

5

modulus, G', as a funtion of

4
10
shear-stress, s, for
suspensions made of 10
3

commercial zirconia.
Frequency = 1 Hz. 10
2

G’ (Pa)
[NaCl] = 10-2 M. 1
10

Figure 2 (below): Linear 10

0

viscoelastic regions for -1

f = 0.03
10 f = 0.09
suspensions made of
sion. This energy can be obtained through the f = 0.14
f = 0.19
commercial powder and 10
-2

synthetic spheres at parameters that characterize the transition 10

-1
10
0
10
1

[NaCl] = 10-3 M. f = 1 Hz. between the linear and non-linear regions, the s (Pa)
so-called "critical parameters": strain, gcrit ,
shear-stress, scrit, and the elastic modulus value 10
6

spheres
of the linear viscoelastic region G'VLR [2]. The 10
5
f = 0.05
f = 0.09

cohesive energy can be related to shear-stress as 10

4 f = 0.15
f = 0.22

[14]: 10
3

2
10

G’ (Pa)
g crit 1
10
Ecoh = Ús( g ) dg 10
0

0 (1) 10
-1 com. powder
f = 0.04
-2
f = 0.08
10 f = 0.15

The critical strain is the limiting value of defor- 10

-3
f = 0.21

mation beyond which the material response is 10

-1
10
0
10
1

increasingly non-linear viscoelastic [15, 16]. In an
oscillatory test, the shear-stress is related to
strain through the elastic modulus [17]:
s = gG¢ (2)
Introducing Eq. 2 into Eq. 1, and taking into
account that in the viscoelastic linear region the
elastic modulus remains constant, it follows
finally from the integration:
1 ¢ 2
Ecoh = GVLR gcrit
2 Bohlin CS-10 and the chosen measuring geome-
(3)
The cohesive energy, Ecoh, is a volumetric ener-
gy, and so it has dimensions of energy per unit of
volume.
2 MATERIALS AND METHODS
Two kinds of zirconium oxide have been used in
this work: commercially obtained (Aldrich) and
synthesized as monodisperse spheres, both of
high purity. The zirconia spherical particles were
prepared following the method described by
Aiken et al. [1]. The chemical products used in the
synthesis were: Zr(SO 4 ) 4 H 2 O (Alfa),
polyvinylpyrrolidine PVP-40 (Sigma Chem.), urea
and nitric acid (both supplied by Panreac). The
deionized water employed in the preparation of
the suspensions was produced in a Milli-Q acad-
emic device.
TEM microphotographs showed that the
synthesized particles are spherical and consider-
ably monodisperse, with an average diameter of
540 ± 20 nm. The commercial particles had an
s (Pa)
average diameter of 300 ± 50 nm and no regular
shape.
The range of ionic strengths was extend-
ed to the interval 10-5 - 10-1 M in sodium chloride
(Fluka). Due to the difficulties involved in syn-
thesizing large amounts of zirconia spherical par-
ticles, their rheology was studied for different
volume fractions of solids and just at one single
electrolyte concentration (10-3 M NaCl).
Rheological behavior of the suspensions
was studied using a controlled-shear rheometer
try to carry our determinations out was a coaxi-
al cylinders Bohlin SSC25. To avoid losses of mate-
rial through evaporation, a cover was coupled to
the external jacket of the CS-10. Before measur-
ing, samples were subjected to a pre-shear
process in order to establish the same initial con-
ditions for all samples. The temperature at which
the experiments were performed was thermo-
statically controlled at 25.0 ± 0.1°C.
3 RESULTS
3.1 L.V.R. DETERMINATION
The linear viscoelastic domain of a sample is
obtained applying an increasing sinusoidal
shear-stress at a fixed frequency (1 Hz) and check-
ing the dynamic functions (elastic, G’, and vis-
cous, G", moduli) performance. The response of
the system must be predominantly elastic (that
is, in phase with the applied stress) and shear-
independent in this region. After a certain value
of shear-stress (critical shear, scrit) these dynam-

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50000 Figure 3: Elastic modulus

10 M
-2
-1
of the L.V.R. as a function
10 M
-3
10 M
-5
of volume fraction of
10 M
10000
-3
commercial particles and
- - - 10 M; sph

5000
spheres, for the different
electrolyte concentrations.

G’LVR (Pa)
Lines correspond to power
1000 law fits.
500

ical functions typically show a marked decrease

100
in G’ and a sharp rise in G". These features also 0.04 0.06 0.08 0.1 0.2

mark the onset of the non-linear behavior. f

Figures 1 - 2 show the L.V.R.'s for the dif-

ferent samples at [NaCl] = 10-2 M (Fig. 1) and for regions for suspensions made of synthetic
suspensions of commercial powder and spheres spheres and commercial powder (at the same
at the same ionic strength (Fig. 2), through G' vs. salt concentration) are represented. Here it is
s dependencies (the storage modulus is not plot- observed that, in general, the commercial parti-
ted in order to make the figures clearer). cles make more elastic suspensions than the syn-
The expected behavior is observed in the thetic spheres, with higher values of the elastic
graphs: the elastic modulus is shear-independent modulus and shorter range in shear-stress. This
until it falls down as a consequence of the rupture suggests that the smaller particles are able to
of the initial ordered state of the particles by the build more elastic structures. This is expected
action of the shear forces. It is possible to visualize since at a certain volume fraction there are more
the initial unsheared suspension as an array of par- particles with smaller radius, and consequently
ticles keeping a certain three dimensional structure they are closer and the structure is more compact
due to interparticle interactions with a certain (the spheres have a size 1.8 times bigger than the
degree of elasticity. In the linear region, this struc- commercial particles).
ture is able to absorb the energy provided externally Fig. 3 shows the values of the elastic
by the applied stress and it responds elastically, but modulus in the L.V.R. for the suspensions studied
when the external flow field is strong enough the here as a function of the volume fraction of solids,
structure is not capable of reacting elastically, and ∆. This rapid increase of G’ can be fitted with a
the particles are not able to recover their equilibri- power law relationship of the form [15, 18 - 20]:
um positions when they are separated to long dis-
tances. At this critical point, the structure breaks
down and the particles are forced to flow. The sys- G¢ = kf m (4)
tem behaves as a fluid and losses most of its solid-
like behavior. In terms of the dynamical functions where k is a constant and exponent m can be
this is shown as a dramatic decrease of G’ (several related to flocculation processes [21]. Parameters
orders of magnitude) and an increase of G" which k and m are shown in Tab. 1 for the different ionic
will be higher than the elastic modulus after the strengths. Solid lines in Fig. 3 correspond to these
critical point. fits. Values of parameter m (< 4.5) indicate a floc-
The mechanism depends on several fac- culated state, in agreement with several authors
tors: solid concentration (Fig. 1), size and geo- [2, 15, 22-24]. The parameter m is lower for com-
metrical shape of the particles (Fig. 2) and pres- mercial samples than for synthesized ones (at the
ence of electrolytes. Analysis of these parameters same ionic strength), indicating stronger inter-
will be carried out through the discussion of actions between the particles and more compact
results of elastic modulus in the L.V.R. and criti- structures.
cal parameters.
3.3 CRITICAL SHEAR-STRESS, scrit
3.2 ELASTIC MODULUS OF THE L.V.R.
This magnitude is numerically determined as the
We define here the elastic modulus value of the value of applied shear-stress corresponding to the
L.V.R. as the mean value of the plateau shown in
Figs. 1 - 2. The influence of the concentration of solid Sample NaCl log k m
particles in suspension is very clear from Fig. 1. As [M]
expected, higher values of G’ are observed as the
amount of solid increases, indicating the develop- com 10-5 6.4 ± 0.3 2.7 ± 0.2
ing of even more elastic structures due to the high- com 10-3 6.0 ± 0.3 2.3 ± 0.2
er amount of particles present in the system. com 10-2 5.2 ± 0.3 1.4 ± 0.3
Table 1: Power law fitting
The effect of particle geometry and size com 10-1 5.6 ± 0.7 2.0 ± 0.7
parameters of the elastic
is shown in Fig. 2, in which the linear viscoelastic sph 10-3 6.4 ± 0.5 3.1 ± 0.5 modulus at the L.V.R.

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Figure 4 (left): 7
1.4
Critical shear-stress as a -1
10 M
-2
6 10 M
function of volume fraction -3
10 M
-5
1.2
10 M
of solid, for the different 5
-3 1.0
suspensions at the ionic 10 M; sph

4
strengths employed. 0.8

gcrit (x10 -3)

scrit (Pa)
3 0.6
Figure 5 (right above):
2 0.4
Critical strain as a function 10 M
-2
10 M
-1

of volume fraction for all 1 0.2

-3
10 M
-5
10 M
the systems studied. Lines -3
0.0 - - - 10 M; sph
0
correspond to linear fits.
0.00 0.03 0.06 0.09 0.12 0.15 0.18 0.21 0.24
0.03 0.06 0.09 0.12 0.15 0.18 0.21
Figure 6 (right below): f
f
Cohesive energy as a
function of volume fraction
for the different electrolyte rapid decrease of G’ versus s (Figs. 1 and 2). Fig. 4 1600 -1
10 M
concentrations. Lines corre- shows the critical shear-stress, scrit, for both kinds 1400
-2
10 M
-3
10 M
spond to linear fits. of samples studied: made with commercial and -5
10 M
1200 -3
- - - 10 M; sph
synthetic particles, as a function of volume frac-

Ecoh (x10 -6 J/m 3)

1000

tion of solids, ∆. As well as in the case of the elas- 800

tic modulus, the stress limits of the L.V.R. increase 600

with the concentration of particle present in the 400

suspensions, indicating that the force necessary 200

for breaking the structure is higher and higher (see 0

also Fig. 1). As solid concentration increases, parti- 0.03 0.06 0.09 0.12 0.15 0.18 0.21 0.24

cles are closer and they adopt even more compact f

structures, which can support higher stresses.

Again, the values of scrit for the synthetic spheres
are significantly lower than those of commercial
powder at the same salt concentration. This is a
consequence of particle size, which reduces the
average distance between particles.
The presence of electrolyte in solution
also affects the behavior of the suspensions. The
critical stress increases as ionic strength decreas-
es, at a certain value of volume fraction. This is
due to interactions between the particles that
arise from their electric surface charge. This will
be discussed later.
3.4 CRITICAL STRAIN, gcrit
The limiting value of deformation from which
the non-linear viscoelastic region starts is shown
in Fig. 5 for both sets of suspensions. These val-
ues are calculated from the values of scrit and G’
by means of Eq. 2. As observed, gcrit decreases as
∆ increases, as shown previously [18, 19]. This
behavior reinforces the previous results of elas-
tic modulus and limiting shear-stress: at low vol-
ume fractions, particles affect only slightly to the
liquid medium properties, and as ∆ increases, the
particles are closer, building a more compact
structure whose deformation is hindered by the
reduction in mobility of the particles.
Respect to the geometry of the particles,
Fig. 5 shows that critical strain values are higher
for suspensions made with the commercial par-
ticles than the synthetic spheres, indicating that
the spheres can move to lower distances because
their bigger size and because the maximum
packing allowable is lower than for the polydis-
perse commercial powder; this could be related
to the extended elastic non-linear behavior of the
polydisperse samples, moderate stress would
allow for reorientation and redistribution of par-
ticles without much perturbation.
The effect of the added electrolyte is
clearer in this case, showing a high sensitivity of
this magnitude, gcrit, to electrical interactions. At
each volume fraction, the gcrit values follow the
sequence: 10-1 M < 10-2 M < 10-3 M > 10-5 M.
3.5 COHESIVE ENERGY, ECOH
Once the critical parameters are obtained, the
cohesive energy can be calculated using Eq. 3.
Results are shown in Fig. 6. Linear relationships
between Ecoh and volume fraction, ∆, are found
for all electrolyte concentrations. This behavior
agrees with the idea of a direct increase of the
size of the flocs by the progressive inclusion of
more particles as ∆ is increased.
As noticed in the analysis of the critical
parameters, the ionic strength has a remarkable
effect on the cohesive energy. The dependences
of Ecoh with [NaCl] at fixed values of volume frac-
tion agree with those found previously for gcrit.
In order to investigate this fact, deter-
minations of electrokinetic or z potential were
carried out for the two zirconium oxide species
employed (spheres and commercial powder).
Since this magnitude is not accessible directly,
electrophoretic mobility, me, was measured as a
function of NaCl concentration, and the zeta
potential was calculated using the theory of
O'Brien and White [25].
Figure 7 shows these calculations. The z
potential increases as the ionic strength increas-

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Figure 7: Electrophoretic
4.5 movility - sph
movility - com
80 mobility (solid symbols)
4.0 70
and zeta potential (open
3.5 simbols) -calculated using
60
the model of O'Brien and

me ( mms -1 / Vcm -1)

3.0
50 White- of commercial and

z (mV)
2.5
40 synthetized zirconia
2.0
particles as a function
30
1.5 of [NaCl].
1.0 20
zeta - sph
0.5 zeta - com 10
ulus, which in addition let us to classify our sus-
1x10
-5
1x10
-4
10
-3
10
-2
10
-1
pensions as flocculated systems. The electrolyte
[NaCl] (M)
concentration has a significant impact on the
developing of the three dimensional structuring
es until it reaches a maximum at [NaCl] = 10-3 M; of the particles.
after this point, z decreases. This behavior is, as From the knowledge of the critical para-
expected, the same for both kinds of Zr2O (the meters it was possible to determine the cohesive
spheres are bigger than the commercial particles energy necessary for aggregating the particles in
and so, they move slower under the application their packed structure. Experiments showed a
of the electric field, leading to smaller values of linear relationship between the cohesive energy
z). The electrokinetic potential governs the elec- and the volume fraction of solids. The depen-
trical interaction between the particles and so, its dence of the cohesive energy on the ionic
dependence on the ionic strength (Fig. 7) implies strength was correlated to the electrical interac-
that the electrostatic repulsion between the par- tion between the particles, which is governed by
ticles should follow the same trend, having a the electrokinetic potential. It was found that the
maximum at [NaCl] = 10-3 M. trend followed by the z potential is coupled by
The cohesive energy has a behavior the corresponding behavior of the cohesive ener-
respect to the electrolyte concentration in agree- gy at each volume fraction: increasing energy for
ment with the behavior of the electrokinetic maintain the flocculation up to [NaCl] = 10-3 M
potential: as the surface charge on the particles and a decreasing for the higher ionic strengths.
increases, the electrostatic repulsion between
the particles increases, and consequently, the REFERENCES
energy necessary for keeping them linked in the [1] Aiken B, Hsu WP, Matijevic E.: Preparation and
flocculated state is higher (Fig. 6). properties of uniform mixed and coated col-
In the other hand, the decreasing value loidal particles .5. Zirconium compounds, J. Mat.
of z for ionic strengths higher than 1 mM in NaCl Sci. 25 (1990) 1886-1894.
[2] Tadros TF: Correlation of viscoelastic properties
leads to a monotonic decrease of Ecoh -at each
of stable and flocculated suspensions with their
volume fraction of solid- which values follows interparticle interactions, Adv. Colloid Interf.
the sequence 10-3 M > 10-2 M > 10-1 M. In this case, Sci., 68 (1996) 97-200.
the reduction of the repulsive interaction [3] Yanez JA, Laarz E, Bergström L: Viscoelastic prop-
between particles demands less energy for erties of particle gels, J. Colloid Interf. Sci.,
aggregate them, as observed in Fig. 6. 209 (1999) 162-172.
[4] Rueb CJ, Zukoski CF: Viscoelastic properties of
CONCLUSION colloidal gels, J. Rheol., 41 (1997) 197-218.
[5] Grant MC, Russel WB: Volume-fraction depen-
The shear-stress regions of linear viscoelasticity dence of elastic moduli and transition tempera-
of suspensions of zirconium oxide were deter- tures for colloidal silica gels, Phys. Rev. E,
mined and characterized as a function of volume 47 (1993) 2606-2614
fraction of solid in the suspensions as well as the [6] Russel WB: Review of the role of colloidal forces
in the rheology of suspensions, J. Rheol. 24 (1980)
presence of sodium chloride as electrolyte. These
287-317.
linear viscoelastic regions (L.V.R.) have been char- [7] Buscall R: Effect of long-range repulsive forces
acterized throughout the mean value of the on the viscosity of concentrated lattices - com-
plateau of elastic modulus, and the so-called parison of experimental-data with an effective
"critical parameters" which are the limiting val- hard-sphere model, J. Chem. Soc. Faraday Trans
ues of shear-stress and strain between the linear 87 (1991) 1365-1370.
and non-linear behavior. [8] Megias-Alguacil D, Duran JDG, Delgado AV: Yield
It was observed that the structure in the stress of concentrated zirconia suspensions: cor-
relation with particle interactions, J. Colloid
suspensions depends mainly on the amount of
Interf. Sci. 231 (2000) 74-83.
solid content, being more and more compact as [9] Scott GD: Packing of equal spheres, Nature,
the volume fraction increases. This packing 188 (1960) 908-909.
effect has been quantitatively characterized [10] Magid LJ, Schurtenberger R: Characterizing com-
through a power law scaling of the elastic mod- plex fluids, MRS Bull., 28 (2003) 907-912.

Applied Rheology
Volume 14 · Issue 3 131
Applied Rheology Vol.14/3.qxd 22.06.2004 11:57 Uhr Seite 132
[11] Prica M, Biggs S, Grieser F, Healy TW: Effect of
calcination temperature on the electrokinetic
properties of colloidal zirconia, Colloids Surf. A,
119 (1996) 205-213.
[12] Heuer AH: Transformation toughening in ZrO2-
containing ceramics, J. Am. Ceram. Soc., 70 (1987)
689-698.
[13] Garvie RC: Microstructure and performance of
an alumina zirconia tool bit, J. Mater. Sci. Let.,
19 (1984) 315-318.
[14] Ramsay JDF: Colloidal properties of synthetic
hectorite clay dispersions, J. Colloid Interf. Sci.,
109 (1986) 441-447.
[15] Sonntag RC, Russel WB: Elastic properties of floc-
culated networks, J. Colloid Interf. Sci., 116 (1987)
485-489.
[16] Tadros TF: Use of viscoelastic measurements in
studying interactions in concentrated disper-
sions, Langmuir, 6 (1990) 28-35.
[17] Macosko CW: Rheology. Principles, Measure-
ments and Applications, VCH, New York (1994).
[18] Patel PD, Russel WB: An experimental-study of
aqueous suspensions containing dissolved poly-
mer .A. phase-separation, J. Colloid Interf. Sci.,
131 (1989) 192-200.
[19] Pons R, Rossi P, Tadros TF: Investigation of the
interaction between emulsions and suspensions
(suspoemulsions) using viscoelastic measure-
ments, J. Phys. Chem., 99 (1995) 12624-12630.
Applied Rheology
132 Volume 14 · Issue 3
[20] Russel WB: Concentrated colloidal dispersions,
MRS Bull., 16 (1991) 27-33.
[21] Liang W, Tadros TF, Luckham PF: Investigations
of depletion flocculation of concentrated steri-
cally stabilized latex dispersions using vis-
coelastic measurements and microscopy, J. Col-
loid Interf. Sci., 158 (1993) 152-158.
[22] Russel WB: Theoretical approaches to the rheol-
ogy of concentrated dispersions, Powder Tech-
nol., 51 (1987) 15-25.
[23] Miano F, Rabaioli MR: Rheological scaling of
montmorillonite suspensions: the effect of elec-
trolytes and polyelectrolytes, Colloids Surf. A,
84 (1994) 229-237.
[24] Tadros TF, Liang W, Costello B, Luckham PF: Cor-
relation of the rheology of concentrated disper-
sions with interparticle interactions, Colloids
Surf. A, 79 (1993) 105-114.
[25] O'Brien RW, White LR: Electrophoretic mobility
of a spherical colloidal particle, J. Chem. Soc.
Faraday Trans. II , 74 (1978) 1607-1626.