RESEARCH ARTICLE | NOVEMBER 01 1985

Hard sphere colloidal dispersions: Viscosity as a function of

shear rate and volume fraction 
C. G. de Kruif; E. M. F. van Iersel; A. Vrij; W. B. Russel

J. Chem. Phys. 83, 4717–4725 (1985)

https://doi.org/10.1063/1.448997

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18 August 2023 10:25:59

Hard sphere colloidal dispersions: Viscosity as a function of shear rate and
volume fraction
c. G. de Kruif,a) E. M. F. van lersel, and A. Vrij
Van't Hoff Laboratorium voor Fysische en Colloid Chemie. Trans IlL De Uithof, Padualaan 8. 3584CH
Utrecht. The Netherlands
W. B. Russel
Department of Chemical Engineering. Princeton University. Princeton. New Jersey 08544
(Received 18 March 1985; accepted 19 July 1985)
The viscosities of s~spensions of ste~cally stabilized (hard) silica spheres in cyclohexane are
re~~ed as a functIon of shear rate (y) and volume fraction (6 X 10- 4 < ifJ < 0.6). The shear
thmn~g scales according to (7], -7]"" )/(7]0 -7]",,) = 1/(1 + l.317]Ya 3 /kT) with limiting low
and hIgh shear viscosities d~cribed up to ifJ-0.35 by 7]0 = 1 + 5/2¢J + (4 ± 2)ifJ2 + (42 ± 1O)ifJ3,
7] = 1 +. ~/2ifJ + (4 ± 2!ifJ + (25 ± 7W . At higher v~lume fractions the viscosity becomes
00

more .senSltIve to ifJ and dIverges at ifJm = 0.63 ± 0.02 (y-D) ,ifJm = 0.70 ± 0.02 (Y---+co) . The
expenmental results c~mpare well with ~xisting hard sphere theories and the data of Krieger
(1~72) f?r aqueous lattIces. Even at the hIghest volume fraction neither yield stresses nor shear
thlckemng are observed.

I. INTRODUCTION diffusion processes up to ifJ = 0.45 9 and the formation of or-

dered phases for ifJ > 0.50.10 At these volume fractions severe

18 August 2023 10:25:59

Sterically stabilized silica spheres dispersed in an or-
ganic solvent serve as a well characterized model colloidal
system. 1-4 The hard sphere model, taken from (simple) fluid
theories where it provides a convenient reference state char-
acterizing the hard core repulsions, 5 also applies for colloi-
dal dispersions, in particular for the silica particles with a
very short (1.5 nm), but dense, layer of stabilizing octadecyl
chains. The particles take the role of the molecules in simple
fluids, differing not only in scale, which greatly facilitates
experimental observations, but also in the presence of a sec-
ond, fluid phase instead of a vacuum. So hydrodynamic (fric-
tion) forces enter in addition to the hard sphere repulsion.
Dispersion of the particles in an oil, e.g., cyclohexane, with
virtually the same refractive index suppresses both electro-
static and van der Waals interactions.
Several studies6 of the (osmotic) compressibility via stat-
ic or time-averaged light scattering have established that
equilibrium interactions follow the Percus-Yevick equation
of state for the hard sphere (osmotic) pressure to high volume
fractions. Also the hydrodynamic interactions between the
particles in the limit oflow volume fraction conform to the-
ories for hard spheres developed by Einstein, 7 Stokes, and
Batchelor8 for the viscosity and sedimentation velocity. The
concentration dependence of the diffusion coefficient in the
zero wave vector (i.e., long wavelength) limit also agrees with
theoretical predictions. 4 Thus the thermodynamic behavior
of concentrated silica suspensions and the dynamic response
of dilute ones conform to the hard sphere model.
There is some evidence that the model also describes
alTo whom correspondence should be addressed.
experimental and theoretical difficulties arise. Satisfactory
treatments of the multi particle hydrodynamic interactions
remain to be established, although promising possibilities
have appeared. The liquid-solid phase transition, originally
detected by computer simulations, II now has been calculat-
ed by Haymet l2 from statistical mechanics. Although many
lacunae persist in both the theoretical and experimental un-
derstanding of concentrated dispersions, including the crys-
talline state, ample evidence suggests that the interactions
between the silica particles resemble the hard sphere model.
So far there are, apart from the dilute limiting viscos-
ities, no rheological data on the system. This study presents
the first part of a systematic investigation addressing the
dependence of the dispersion viscosity on both shear rate and
volume fraction for 0.OOO6<ifJ<0.6. In the next section we
will recall only a few results of basic theory. Several extant
papers review both theoretical and experimental results. 13
We then present new experimental results and compare
those with existing theories and the results of Kriegerl4 on a
highly crosslinked latex dispersed at high ionic strengths
which also closely resembles a hard sphere system.
II. THEORETICAL CONCEPTS
A. SuspenSion mechanics
For suspensions of hard spheres the shear viscosity 7]
varies with the solvent viscosity 7] s' the shear rate y,
the
thermal energy kT, the particle radius a, and the number
density n. 14 Dimensional analysis then dictates that the rela-
tive viscosity 7], = 7]/7]s depends only on the volume frac-
tion ifJ = 41ra 3 n/3 and the dimensionless shear rate
7] sa 3 Y/kT. The detailed functional form, however, remains

J. Chern. Phys. 83 (9), 1 November 1985 0021-9606/85/214717-09$02.10 © 1985 American Institute of Physics 4717
4718 de Kruif et a/. : Viscosity of hard sphere dispersion

to be determined from either theory or experiment.
Construction of a theory for the viscosity, or more gen-
erally the rheology, of a dispersion requires knowledge of the
hydrodynamic and potential interactions between the parti-
cles, the resulting microstructure, and a valid means for cal-
culating the macroscopic stress from this information. 13 An
exact theory is possible only in the dilute limit where three-
body and higher order interactions can be neglected. Even
there early treatments erred in one or more ofthe three nec-
essary components. Finally, Batchelor 15 synthesized the ex-
act hydrodynamics, a convergent integration of the interac-
tions, and the direct contribution from Brownian motion
into a complete theory for the low shear limiting viscosity of
dilute suspensions of hard spheres.
The dilute, or pair interaction, theory hinges on the
availability of exact two-sphere hydrodynamics and charac-
terization of the microstructure through the pair distribu-
tion function P. A conservation equation determines P from
the fluxes due to the imposed shear flow, Brownian motion,
and the interaction potential V IkT. In the absence of flow
the equilibrium radial distribution function g characterizes
the pair configuration. A weak flow with the rate of strain E
perturbs the system from equilibrium by an amount propor-
tional to the dimensionless rate of strain as
(1)
fIr) reflects the action of the shear field on the equilibrium
more pairs near contact. Judging from the difficulty in de-
tecting shear thinning at volume fractions below 0.3,14 these
effects probably cancel leaving the 0 (tP 2 ) coefficient insensi-
tive to shear rate.
The presence of other interaction potentials affects the
viscous and Brownian stress indirectly through the distribu-
tion functions but also can produce direct interparticle
stresses. For example, both sticky sphere and excluded shell
potentials increase the 0 (tP 2 ) coefficient. 17 The former gener-
ates a population of doublets which add both viscous and
Brownian stresses, while the latter reduces these terms by
excluding pairs from the near contact region but more than
compensates through the interparticle stress. With increas-
ing shear rate the viscous stresses drive the structure toward
the same hydrodynamically dominated limit as for hard
spheres, making the nonhydrodynamic contributions insig-
nificant. Hence the viscosity becomes shear thinning, direct-
ly reflecting the effect of the interaction potential on the low
shear viscosity.
At higher concentrations many-body interactions affect
the rheology in two ways. The most obvious is the increased
viscous contribution to the stress due to hydrodynamic in-
teractions among three or more spheres. But even for hard
spheres, thermodynamic interactions among several parti-
cles alter the equilibrium radial distribution function, mak-
ing g(r) an oscillatory function with g(2a) > 1 and g---+l as
r---+ 00 • Recent work by Beenakker 18 combines the method of

18 August 2023 10:25:59

state and, therefore, depends on the interaction potential. At
high shear rates the structure should be determined by the
hydrodynamics and independent of shear rate.
The various contributions to the macroscopic stress in-
dicate the rheological consequences of this nonequilibrium
structure. After renormalization to evaluate the nonconver-
gent integrals, the viscous stress assumes the form 16
O'hyd = 27Js E{ 1 + 2. tP + 2. tP 2 + 4cnr a6 ("" p2Jp dP} . (2)
2 2 3 J2
The largest contributions from Brownian motion and the
interparticle potential occur in the weak flow limit
where l5 .17
reflections to approximate the many-body hydrodynamics
with available results for gIrl (e.g., McQuarrie5) to calculate
the viscous contribution to the stress in the low shear limit.
The result can be expressed in terms of either a volume frac-
tion dependent 0 (tP 2 ) coefficient, which increases from 5.2 at
infinite dilution to 14.2 at tP = 0.45, or the corresponding
relative viscosity which increases from 1.0 at infinite dilution
to 5.0 at tP = 0.45. The effect is clearly significant, but insuf-
ficient to explain the strong concentration dependence of the
low shear viscosity observed by Krieger14 and reported here.
The increased O(tP 2 ) coefficients predicted by the dilute
theory for either attractive or repulsive potentials suggests a
second, more subtle effect of the structure in hard sphere
suspensions at finite concentrations. For hard spheres the
potential of mean force, defined by

VmflkT= -lng(r) ,

becomes nonzero at finite separations when g departs from

A, W, and J are known hydrodynamic functions.
For hard spheres in the low shear limit Batchelor 15 cal-
culated
7Jo==7JI7Js = 1 + 2.5tP + 6.2tP 2
with 2.5 of the 0 (tP 2 ) coefficient from the far-field hydrody-
namic interactions, 2.7 from the near-field hydrodynamics
for the equilibrium microstructure, and 1.0 from the Brown-
ian stresses induced by the nonequilibrium structure. The
hard sphere potential generates no direct stress because
A = 1 at contact. In the high shear limit the Brownian stress
should become insignificant, while the viscous contribution
should increase since the hydrodynamic interactions retain
unity. The contribution of this effective interaction potential
to the stress (3) would be 0 (tP 3 ) in the dilute limit, but rapidly
increasing at higher concentrations. At high shear rates the
viscous stresses would dominate as in the pair interaction
(4) limit. Thus such an effect would explain at least qualitatively
the sensitivity of the low shear viscosity to volume fraction
and the appearance of shear thinning for tP> 0.30.
While the results and ideas discussed above provide a
basis for understanding the rheology of concentrated sus-
pensions of hard spheres, no quantitative theory yet incorpo-
rates both the nonequilibrium microstructure and the many-
body hydrodynamics. Hence, we must analyze the data
through semiempirical correlations consistent with the theo-
retical concepts.

J. Chern. Phys., Vol. 83, No.9, 1 November 1985

 de Kruif st al. : Viscosity of hard sphere dispersion 4719

B. Simple models and correlations 'TI, - 'TI"" = 1_ [(1

Pe + ~)1/2 _1]
'TIo - 'TI"" 4 Pe
Many of the ideas presented above within the context of
with Pe = KPe. Figure 1 shows the difference between the
a formal theory were anticipated in Krieger and Dougher-
two to be significant but not enormous. Krieger l4,19 and Wil-
ty'sI9 derivation of a simple model for the shear rate depen-
ley and Macosk0 20 have successfully correlated several sets
dence of the viscosity of a suspension of hard spheres. They
of data with the first limit alone.
envisioned the suspension as a mixture of singlets and doub-
A variety of two parameter correlations exist for the
lets, at number densities n I and n2 , respectively, contributing
volume fraction dependence of the low and high shear limit-
independently to the viscosity as
ing viscosities. In each, one parameter measures the effect of
'TI, = 'TII'TIs =/In l +h,n 2 · the isolated particle, i.e., the Einstein coefficient, and the
The microstructure, i.e., the density of doublets, follows other interactions or crowding. For example, the equation l9
from the balance between the rate of formation by Brownian 'TI, =(I_tP1tPmax)-2.S4>max (7)
collisions and the rate of destruction by both Brownian mo-
tion and shear. The overall mass balance requires conforms to the dilute limit to 0 (tP) and diverges at tPmJ!x'
These simple expressions together with the dilute theories
no = n I + 2n 2. Expressed in terms of the high and low shear
limiting viscosities, 'TI and 'TIo, the dimensionless shear rate
00
suffice for the purposes of this work.

Pe = ba3'T1ylkT; III. EXPERIMENTAL

and the equilibrium constant A.Sample
K=kblkfn O; The dispersions of sterically stabilized silica particles in
the shear rate dependent viscosity takes the form cyclohexane were prepared by a condensation polymeriza-
tion oftetraethoxysilane (Fluka) and a subsequent esterifica-
'TI, - 'TI"" tion of the surface silanol groups with octadecyl alcohol. I
'TIo - 'TI"" The particle size is characterized by the hydrodynamic radi-
1 +!K(1 +Pe)(l- (1 + [8IK(1 + Pe)]J 1/2) us of 78 ± 2 nm calculated with the Stokes-Einstein equa-
=
1+!K [1- (1 + 81KjI/2] (5) tion from the diffusion coefficient measured at low concen-

18 August 2023 10:25:59

trations by dynamic light scattering.
b is an unknown 0 (1) constant. Simple analytical forms re-
sult in the two limits: B. General outline of experimental setup
We used a Deer rheometer (Deer, England) which ap-
K> 1 (few doublets), plies a (preset) constant stress to the sample and measures
'TI,-'TI"" 1 either the strain or the rate of strain by detecting the angular
=---,
'TIo - 'TI"" 1 +Pe displacement or velocity of the motor shaft applying the
(6) stress. The torque exerted by the motor shaft was calibrated
k<1 (all doublets) by both static and dynamic methods. The former consists of

1.0.--_ __

FIG. 1. Reduced viscosity against Peclet

number.

10
Pe, pe

J. Chem. Phys., Vol. 83, No.9, 1 November 1985

4720 de Kruif et al. : Viscosity of hard sphere dispersion
calculating the torque from the force exerted on the pan of an
electronic weighing balance. In the dynamic method we
measure the angular position of the motor shaft as a function
of time with an inertial mass mounted on the shaft. Results
were identical and linear up to nominal or preset torques of
6 X 104 dyn cm in accordance with specifications. For
torques (nom) > 6 X 104 dyn cm the relation becomes nonlin-
ear reqUlnng a software correction for 6 X 104
< torque(nom) < 105 • The resolution of the instrument is 20
dyn cm at an angular velocity of 0.01 S-I.
We found that a micrometer with digital readout (Hai-
denhahn, Austria), mounted at the same lateral position as
the motor shaft, sufficed to determine settings between par-
allel plates. The manual spindel for changing gap settings
was equipped with a stepper motor. These modifications put
all functions, i.e., preset torque, velocity readout, gapset
reading, and gap setting, under microcomputer control. All
measurements are made automatically with repetition to
check for (long term) drift or nonequilibrium properties. As a
rule, the infrequent drifts observed could be attributed to an
obvious cause such as evaporation of the solvent.
C. Measuring geometries
The dimensions of the measuring geometries were gov-
erned by several considerations. First, the lowest viscosity to
be measured is that of the solvent, i.e., cyclohexane, with
viscosity 1]s of 0.98 mPa s at 293 K. Measurement of this
with sufficient accuracy sets a minimum torque, producing a
minimum angular velocity. A conflicting requirement is that
sample volume be as small as possible. Furthermore, evapo-
ration of solvent must be avoided since cyclohexane is rather
volatile with Psat (298 K) = 140 mbar. The Couette geome-
try given in Fig. 2 provides a good compromise between the
indicated specifications.
Additionally, a parallel plate geometry with a nominal
radius of 4.5 cm was used with a similar vapor lock system.
FIG. 2. Schematic drawing of double-cylinder Couette geometry: A-Tef-
lon manchet; B-water trough; C-glass coverplate; D-stainless steel cup;
E--stainless steel bob; t, and t 2-filling and cleaning lines; t,-thermom-
eter insert.
J. Chem. Phys., Vol. 83, No.9, 1 November 1985
This geometry extends the shear rate capabilities at the high
end.
After mounting and careful alignment, the setup is not
dissembled until all measurements including calibration
have been completed.
D. Measuring procedure
The measuring chamber is cleaned by flushing chloro-
form and alcohol through the tubes t 1 and t 2 • Then the vapor
seal is filled with water, which is immiscible with cyclohex-
ane and can be removed more easily than silicone oil. A
blank run measures the residual friction of the air bearings
and the vapor lock. This stress varies linearly and reproduci-
bly with the angular velocity and, when not negligible, can be
subtracted from the shear stress applied to a sample. The
sample is then introduced through tube t 1 with an airtight
syringe. A computer controls accumulation of data by pre-
setting the torques and recording the measured velocities w.
As a rule, 40 regularly spaced values of w were acquired in
the interval 0--40 rad s -lor in the torque range 0-8 X 104
dyn cm depending on which limit is reached first. These raw
data are stored on a floppy disk together with temperatures
of the sample, the sample identification, and the details of the
measuring geometry. The primary or raw data of the torque
M vs ware preserved throughout further processing of the
data.
18 August 2023 10:25:59
E. Calibration of the Couette geometry
This geometry was calibrated with a number of Newto-
nian fluids including three silicone oils certified and issued
by TNO, Utrecht, and designated as oils 8301, 8302, and
8303. At the highest torques and angular velocities of the
most viscous fluids a small nonlinearity appeared, which we
thought originated in the motor drive. After this small cor-
rection the setup gave the correct Newtonian viscosity for all
fluids at all shear rates. Figure 3 summarizes these results.
The measured viscosities are found from the linear least
r.
squares slopes of plots of T against For the highest viscos-
ity oil (8303) we verified theoretically and experimentally,
J
.1O
~
Vl 10
E
u
<1.>2
c
»
TI
----
~13
~I
';"'1 9
0
1
7
56
4
23
0 5 10
:> ~/mPa 5
FIG. 3. Calibration plot for Couette geometry of measured apparent viscos-
ity against literature values for different fluids at a temperature of
20.0 ± 0.1 ·C. (1) Acetone; (2) n-heptane; (3) methanol; (4) cyclohexane; (5)
water; (6) oil 8301; (7) n-propanol; (8) n-butanol; (9) oil 8302; (10) oil 8303.
 de Kruif 6t a/. : Viscosity of hard sphere dispersion
:s
~30
6
<.9
z
<t:
.....J
<t:
Sd 20
f-
iX
u As the methods for preparation of the samples differ, we
.3 .5 .7 .9 1.1
~ KIN. VISC'/c St
FIG. 4. Onset of Taylor instabilities in Couette geometry for different fluids
in comparison with prediction of Taylor (dashed line). (I) Acetone; (2) n-
heptane; (3) toluene; (4) methanol; (S) water; (6) cyclohexane.
with a thin thennocouple inserted in the gap, that shear heat-
ing is negligible. For low viscosity fluids at high shear rates
Taylor instabilities appear. The observed onset of these in-
stabilities closely follows the semiempirical formula of Tay-
101.21 (Fig. 4), providing further evidence for the proper func-
tioning of the apparatus.
F. Calibration of parallel plate geometry
In this setup the applied torque (M) (dyn cm) is related to
the angular velocity w for a Newtonian fluid by
M = 1TR 4WTJ ,
2(L -Lo)
where R is the effective radius of the plate and (L - Lo) the
effective gap. Measurements of M vs w for different fluids ("I)
at a series of different gap settings (L - Lo) plotted as L vs 1/
(M / w -f), withf the residual friction, detennineLofrom the
intercept and R 4"1 from the slope. The frictionfwas obtained
for large "empty" gaps. The plots are perfectly straight and
give consistent values for Lo and R (45.71 mm) for different
fluids. Thus for each sample the torque is measured as a
function of w for at least ten different gaps from
(L - Lo) - 50 to 150 pm.
G. Sample concentration
For the double cylinder measurements the concentra-
tions were detennined as follows. After being dried over-
night at 70-80·C in a N2 stream, appropriate amounts of the
dry powder were weighed into a measuring flask of 250/
100/50/25 ml with the smaller sizes used for more concen-
trated samples. Then the flasks were filled with cyclohexane
and reweighed. The weight concentration was calculated as
g silica/(vol of flask) and converted to a volume fraction by
multiplying by 0.63 (see Sec. IV). These volumetric measure-
ments detennined the density of the silica to be 1.74 ± 0.02
g cm- 3 •
As repeated drying (> 10 times) appeared to alter the
samples, we decided to follow another procedure for the par-
allel plate measurements. A silica sample of - 20 g was dried
once and weighed precisely; then a weighed amount of cyclo-
J. Chem. Phys., Vol. 83, No.9, 1 November 1985
4721
hexane was added (and in some cases evaporated to increase
the concentration) and the concentration calculated from
- 3) g silica
(
cgcm =
g silica/8s + g chx/80
where 8 s is the volumetric detennined mass density of the
silica and 8 0 that of cyclohexane. There is no excess volume
of mixing involved.
checked the parallel plate measurements as follows. Three
samples (Nos. 25,.26, 27 of Table II) were prepared accord-
ing to the first, i.e., the volumetric method. Except for sam-
ple 26, the viscosities measured with the parallel plate meth-
1.3 od are consistent with the Couette data. But samples
prepared with the second procedure at the same nominal
concentrations of 0.755 and 0.756 g cm- 3 gave viscosities
which corresponded to a concentration of 1.05 (0.756). We
therefore multiplied all sample concentrations prepared
with the second procedure by 1.05. The results of Couette
sample 23 and parallel plate sample 31 further justify this
procedure. The highest shear measurement with the Couette
just overlaps the low shear end of the parallel plate data as
expected since samples 23 and 31 have the same concentra-
tion after correction.
The origin of the 5% correction is not clear but could
arise from any of several sources, such as the drying proce-
dure. In the second method we used a weighed bottle and
18 August 2023 10:25:59
evaporated the cyclohexane in a water bath, flushing dry N2
into the bottle. Furthennore, it is known that the silica parti-
cles can give up a few (up to 5) percent of water and reversibly
take it up again.
(8)
H. Data reduction
The raw M vs w data (and for the parallel plate for each
gap) are fitted to a suitable (polynomial) function for reduc-
tion and smoothing. Then the shear stress and shear rate and
the (apparent) viscosities are calculated from these polyno-
mials through appropriate calibration and conversion con-
stants. For the parallel plate, viscosity is verified to be inde-
pendent of gap setting. Each data set of M vs w is checked for
non-Newtonian behavior by fitting the data to a polynomial,
i.e.,
M = ao + a1w + a2w2 + a 3w3 + ... . (9)
When the higher coefficients do not differ significantly from
zero, the fluid is Newtonian in the shear regime considered
and the coefficient a 1 multiplied by a calibration factor is the
viscosity. The coefficient ao was always zero (within experi-
mental error); so yield stresses were absent. When non-New-
tonian effects appear we fit the data to the equation
(10)
since the residuals are lower than with a fourth or fifth order
polynomial. Although without theoretical basis, the equa-
tion confonns nicely to the idea of two limiting viscosities,
i.e., the zero and the infinite shear rate limits with
TJo=a l +a 2a3 "I", =a l •
,
Furthennore, the characteristic stress follows as
4722 de Kruif et al. : Viscosity of hard sphere dispersion

1]0 + 1] ""
2
=
.' .'
or
!a 3 1].rc = l_e- a,'T/,yc,
40
::::J
ci
..
(])
::::J
. ...
hence, CY
.
....
L
0
=
...
+'
a 3 1].rc 1.59361. (lOa)

...
Although the fit is good and the coefficients unique, the
so-called linear exponential fit has some drawbacks. Evalua-
,20
.....
..
....
tion of the coefficients takes more computer time. Further-
more, if the experimental data lie in one shear regime only,
the extrapolated or limiting viscosity in the complementary V·
shear regime may err by a factor of 2, even for a good fit.
The parallel plate measurements also must be corrected
to account for the nonuniform shear rate in the gap22 as
0 10 20
--
30
wis·'
40

FIG. 5. Sample No. 22, Table II, with c = 0.701 g cm-', ~ = 0.443, and
T = 293.15 K. Plotted is the nominal torque (dyn cm) against angular ve-
50

1]r(rmax) = 1]app(rmax)[ 1 +! 8 In(1]app)/8 In(rmax)] , locity of the bob, with 130 separate data points more densely spaced in the
(11) low shear regime.

where
(J)R drodynamic radius probably reflects a slight optical inhomo-
Ymax =L -Lo' geneity of the particles.
With Eq. (10) representing the raw data, the corrected values
B. Viscosity data
follow analytically from
Table II lists the viscosity data in order of increasing
.
1]r(Ymax) 3 (1
= a 1 + a; [ --. - e-a,'T/,Y). + a 3e- a3'T/,y.] concentration for both the Couette and the parallel plate
1].Y geometries. The limiting values were evaluated as indicated
(12) in Sec. III. The second column gives the number of indepen-

18 August 2023 10:25:59

yielding the same limiting values for 1] "" and 1]0 . dent measurements and the total number of runs on that
sample in measuring shear rate as a function of shear stress.
It should be noted that Table II does not indicate the order of
IV. RESULTS AND DISCUSSION the measurements; for instance, No. 24 preceded 11-16. Fig-
A. Optical and hydrodynamic radii of the particles ure 5 shows a typical run with a shear thinning sample. The
relative viscosity in the low and high shear limits plotted as a
In Table I we summarize some of the properties charac-
function of volume fraction in Fig. 6 provides the basis for
terizing the silica sample. The optical and hydrodynamic
the following discussion of several properties of the sample,
radii were obtained from static and dynamic light scattering
starting with the low concentrations.
methods. l -4 Periodic checks with dynamic light scattering
indicated that the system did not change during the eight
C. Specific viscosity and speCific volume
months over which measurements were made. That the opti-
cal radius is slightly smaller than the Stokes-Einstein or hy- The intrinsic viscosity is defined as
lim (1]r - 1)/¢ = [1]] . (13)
4>-..D
TABLE I. Optical and hydrodynamic radii of silica spheres: All measure-
ments at 25 ·C.
.+
160
Optical Optical Hydrodynamic +
c radius' radius b radiusc
(g cm- 3 ) (nm) (nm) (nm) Date
120
0.0507 75.4 73.7 78.8 Jan. 2, 1984 F
0.0299 78.1 75.9 77.2 +
0.0254 80.2 79.0 80
t
0.0199
0.0147
79.1
77.1
77.6
76.0 79.4 r 40 ..
0.0102 78.3 77.5 ~ .0
·0

....:~::".!.d··ti
0.0049 77.9 77.5 81.0
0.0010 74.5
0.0280 69.5 68.6 76.6 Feb. 14, 1984 1 ~+""".+-'.'.+.- .... +-"''''_'''II'·.·*'
0.0149 75.2 Feb. 14, 1984
0.005 77.2 Sep. 8, 1984 0 .1 .2 .3 .4 <II .5 .6
~

• Static light scattering at A = 546 nm. FIG. 6. Plot ofrelative viscosity against volume fraction at T = 293.15 K .
bStatic light scattering at A = 436 nm. The dotted lines represent equation 'Tfr = (I - ~/~max)-2 with ~max = 0.63
C Dynamic light scattering at A = 488 nm. and 0.71.

J. Chern. Phys., Vol. 83, No.9, 1 November 1985

 de Kruif et al. : Viscosity of hard sphere dispersion 4723

TABLE II. Experimental viscosities (bracketed numbers are interpolated values).

Meas. e ¢J "7,(r.....o) "7,(r~oo) "7c rc Tc

file (g cm- 3 ) vol. frac. reI. visco reI. visco reI. visco S-I (Nm-2)

Couette measurements
I 2/10 0.0010 6.32X 10-- 1.004 ± 0.002 1.004
2 2/9 0.0049 3.lOX 10- 3 1.006 1.006
3 2/8 0.0102 6.45 X 10- 3 1.018 1.018
4 2/8 0.0147 9.29X 10- 3 1.024 1.024
5 2/6 0.0199 1.26X 10- 2 1.032 ± 0.002 1.032
6 2/9 0.0254 0.0160 1.045 1.045
7 3/10 0.0299 0.0190 1.049 ± 0.005 1.049
8 3/11 0.0507 0.0320 1.082 1.082
9 3/10 0.0765 0.0483 1.137 1.137
10 3/12 0.1036 0.0655 1.1888 1.188
11 2/6 0.130 0.082 1.280 1.280
12 2/4 0.146 0.092 1.300
13 2/4 0.171 0.108 1.401
14 2/6 0.199 0.126 1.49 ±0.02 1.41 ± 0.02 1.45 574 0.82
15 4/15 0.200 0.126 1.48 1.43 1.45 393 0.56
16 2/5 0.225 0.142 1.596
17 2/6 0.303 0.191 2.00 1.76 1.88 548 1.05
18 2/6 0.398 0.251 2.50 2.22 2.36 562 1.30
19 2/5 0.500 0.316 3.77 2.99 3.37 565 1.85
20 2/12 0.601 0.380 5.98 ± 0.1 4.39 ± 0.1 5.19 409 2.09
21 2/11 0.648 0.409 7.76 5.09 6.42 380 2.39
22 2/8 0.701 0.443 10.35 6.32 8.33 346 2.82
23 2/12 0.885 0.559 83.5 ± 6 25.3 ± 2 54.4 45 2.40
24 1/8 0.94 0.594 175 ± 5 37.4
Parallel plate measurements
25 1/5 0.306 0.193 1.82 ± 0.2 1.73 ± 0.2 1.77 807 1.4
26 2/8 0.478 0.301 4.52 3.37 3.95 646
27 2/5 0.754 0.475 16.2 8.62 12.4 263 3.2

18 August 2023 10:25:59

28 1/5 0.793 0.500 21.3 10.5 15.9 148 2.3
29 1/5 0.795 0.501 20.7 ± 2 10.6 ± 1 15.6 203 3.1
30 1/7 0.836 0.527 [37.4] 13.3 [25.0] [69] [1.7]
31 1/5 0.880 0.554 [69] 17.7 [43.4] [29] [1.25]
32 1/5 0.918 0.579 [152] 25.3 ± 2 [88.6] [9] [0.75]
33 1/5 0.954 0.601 [472] 35.4 [253] [3] [0.65]
34 1/5 0.983 0.619 51.5 ± 4

A least squares fit of the data in Fig. 7 for Nos. 1-8 gives close packing at high concentrations. The origin of the dis-
[1J] = (1.58 ± 0.015)q, with q = l/J/c. The Einstein value for crepancy is not clear, but in the past Ubbelohde measure-
[1J] = 5/2 thus determines q = (0.63 ± 0.OO6)cm 3 g-l. ments on other silica dispersions have also yielded a relative-
We also determined the specific viscosity with a Ubbe- ly high specific volume. For consistency we use the Couette
lohde capillary viscometer but found a significantly (15%) specific volume of 0.63 cm3 g-l to calculate volume fraction
higher value for q, which leads to volume fractions exceeding from weight concentration, yielding column 4 of Table II.

10·~---------------------------' D. Shear thinning and characteristic shear stress

/
For l/Jo;;;;O.08 the shear stress vs shear rate plots are essen-
.
/
/
./
/ tially straight lines in the shear regime considered. For
./

./
./ 0.08o;;;;l/Jo;;;;O.30 some shear thinning is visible, but unambigu-
./
./
ous values for the limiting viscosities, the characteristic
./
./ stress, and shear rate could not be determined. Reliable val-
./

.
/"
./
v ues are obtained only for l/J:>0.30. With increasing volume
fraction the parallel plate measurements shift to the high end
/"
././" ofthe shear thinning regime, i.e., shear thinning is apprecia-
. ./ ble at the smallest angular velocity. These measurements
2 .
./
./
./
complement the Couette data from which zero shear viscos-
./
-: ities can be extracted. The low shear limiting viscosities for
~./
6 measurements Nos. 30--34 therefore were calculated from
o
Nos. 1-29. With the limiting viscosities we determined the
FIG. 7. Specific viscosity against concentration. Slope of plot gives specific characteristic shear stress and shear rate values in the last
volume q = 0.63 cm 3 g-I. columns of Table II, either from a plot of

J. Chern. Phys., Vol. 83, No.9, 1 November 1985

4724 de Kruif sf a/. : Viscosity of hard sphere dispersion

4r----------------------------------,
.6
40
-e
3 ~
C\i 20 •
I
y-o
z
'E
--
""2
u
o
o
--
-e
.,-
F
::::::
+ THISWORK
6 KRIEGER

i 1
o
o

o A •

o .1 .2 .3 ~.5 <I> .6
.4 .5 .6 .7
--<I>

FIG. 8. Characteristic shear stress against volume fraction. Lines are to FIG. 10. Plotof[(1/, -1)/(t{J - 5/2)/t{JJ againstt{J. The intercepts are equal
guide the eye. to the coefficients of the t{J2 term and the slopes to those of the t{J3 term.

(1/, - 1/ )/(1/0 - 1/ against shear stress or by direct calcu-

00 00 ) Finally we compile a representative number of the mea-
lation from Eq. (lOa). surements on a master plot of (1/, - 1/ )/(1/0 - 1/ ex> ) against 00

In Fig. 8 we plot the characteristic shear stress as a func- 'TI'Te in Fig. 9. Given the variation in 1/, of more than two
tion of volume fraction, with lines intended to guide the eye orders of magnitude the scatter is not excessive. But the sys-
and suggest the trend with volume fraction. Krieger7 defined tematic variations suggest that the three parameters, 1/0' 1/ 00 ,

the characteristic shear stress by and a 3'TJkT are not sufficient to correlate the shear rate
= kT Iba 3 ,
'Te dependent viscosity.
and found b = 2.32 independent of volume fraction. In our

18 August 2023 10:25:59

case (for t/J < 0.50), 'Te - 6t/J with a value at t/J = 0.50 corre-
sponding to b - 2.3-3.0, within experimental uncertainty of
Krieger's constant value. For t/J > 0.5 the characteristic shear
stress diminishes again and seems to go to zero at t/J-0.63.
Writing Eq. (6) as
1/, = 1/ + 1/0 'Tel'T
00
E. The vi rial expansion for the viscosity
Evaluation of the coefficients in the virial expansion for
the viscosity from the experimental data is not trivial due to
the ill-defined range of validity of the truncated series. The
best approach, a plot of [(1/, - 1)/t/J - 5/2)]/t/J against t/J,
yields the 0 (t/J2) coefficient from the intercepts as 4 ± 2 for

we see that 'Te--+O as 1/0 diverges at t/J-0.63 is consistent with
the idea that the viscosity at finite shear rates remains finite
up to volume fractions of t/J = 0.71. It is tempting to correlate
the abrupt change in 'Te at t/J = 0.5 with the hard sphere liq-
uid-solid transition. However, there are no other indications
of the disorder-order transition at this volume fraction.
both shear rate limits. The large uncertainty results from the
fact that a second derivative has actually been taken. Figures
lO(a) and lO(b) indicate that the volume fraction dependence
of the viscosity follows:

~.8
"
~
F
~.6
"

.25
+. 0
.2 + "
... 0
Q o
+ • + £'0 0
0 .1 .2 .3 .4 .5 .6
~ <I>

FIG. 11. Plot of 1/1/, against volume fraction. The volume fractions where
FIG. 9. Scaled plot of ('1/, - '1/ 00 )/(1]o - '1/ 00) against reduced shear stress. 1/, diverges are found as 0.63 ± 0.02 and 0.71 ± 0.02: + low shear limiting
Experimental points for t{J = 0.601, 0.554, 0.527, 0.475, and 0.380. Line is viscosities; 0 high shear limiting viscosities; 6., 6. Krieger's (Ref. 7) results;
Eq. (6a). line from Beenakker (Ref. 8).

J. Chern. Phys., Vol. 83, No.9, 1 November 1985

 de Kruif et a/. : Viscosity of hard sphere dispersion
TABLE III. Correlation parameters for limiting viscosity and volume fraction.
Reference Equation
Krieger" '1/, = (1 - tfo/tfomax) (~J~m..
Quernadab '1/, = (1 - tfo/tfomvT2
• Reference 7.
1/,(y-OO) = 1 + ~ ; + (4 ± 2);2 + (25 ± 10);3,
1/,(y-<» = 1 + ~ ; + (4 ± 2);2 + (42 ± 10);3
Up to ;-0.35.
In Fig. 11 we demonstrate that Beenakker's theoretical
results are satisfactory for ; < 0.3. The results of Kops-
Werkhoven from our laboratory on a silica system cited by
Beenakker l8 were still in the shear thinning region and not
correct limiting values. The theory, however, omits nonhy-
drodynamic contributions to the stress and uses the equilib-
rium radial distribution function, producing neither 1/0 nor
1/ '" at the higher volume fractions.
F. Correlations and maximum packing fractions.
The extrapolation of 1/1/, to zero in Fig. 11 is uncertain.
Plotting against ;1/3 as suggested by cell models does not
improve the result. The results compiled in Table III were
obtained by fitting the data to equation (7).19.23 This table
and Fig. 11 suggest the limiting packing fractions at which
the viscosity diverges as ;max (y-<» = 0.63 ± 0.02 and
;max(Y-oo) = 0.71 ± 0.02.
ACKNOWLEDGMENTS
The skillful assistance of Gerard Harder in making the
measuring sensors and Henk Mos in automating measure-
ments and data handling have been of prime importance.
One of us (C. G. de K.) wishes to thank W. B. Russel for his
stimulating guidance and hospitality when preparing the
manuscript at Princeton during the fall of 1984. This work is
part of the research program of the foundation of Funda-
mental Research of Matter (F.O.M.) with financial support
J. Chern. Phys., Vol. 83, No.9, 1 November 1985
4725
r~co
0.63 1.96 0.71 1.93
0.63 0.72
bReference 23 .
from the Netherlands Organisation for Pure Research
(Z.W.O.).
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