ChemicalEngineeringScience, 1967,Vol. 22, pp. 847-853. Pergamon Press Ltd., Oxford. Printed in Great Britain.

On the viscosity of a concentrated suspension of solid spheres

N. A. FRANKEI.and ANDREASACRIVOS
Department of Chemical Engineering, Stanford University, Stanford, California

(Received 8 December 1966; in revised form 27 December 1966)

Abstract-An asymptotic technique is used to derive the functional dependence of effective viscosity
on concentration for a suspension of uniform solid spheres, in the limit as concentration approaches
its maximum value. This result, containing no empirical constants, is intended to complement the
classical Einstein formula which is valid only at infinite dilution. Good agreement is found between
the asymptotic solution and available data, provided that the maximum concentration is determined
from the data themselves.

1. 1NTRoouc~10N surrounding fluid. That is, we shall treat the solid

FOLLOWINGEINSTEIN’S[l] classical analysis on the
viscosity of an infinitely dilute suspension of solid
spheres, a great many attempts were made to
extend the theory to the case of finite concentra-
tions. These have been comprehensively reviewed
by RUTGERS[2] who also compared certain of the
proposed theoretical models with an average
effective viscosity versus concentration curve that
contained the data of numerous investigators.
Rutgers and later on, THOMAS[3], concluded that
none of these models seemed to hold for highly
concentrated suspensions and suggested that
factors such as collisions among particles and size
distribution had to be taken into account before a
successful concentrated suspension theory could be
developed.
We shall presently show, however, that although
the analysis of the viscosity of a suspension of
arbitrary concentration is admittedly an extremely
difficult theoretical problem, a comparatively
simple, direct approach leads to an asymptotic
model for the viscosity of a highly concentrated
suspension which agrees exceedingly well with the
limited available data.
2. THE RATE OF ENERGY DIWPATION IN
A CONCENTRATEDSUSPENSION
Since we do not propose here to analyze statis-
tically the particle motions in a concentrated
suspension undergoing shear, we shall assume in
what follows that, at each instant, each solid
particle moves with the average velocity of the
spheres as fluid elements with regard to their
instantaneous motions, but shall investigate very
carefully the hydrodynamic interactions among
particles in relative motion and in close proximity
to one another. Wall effects shall be assumed
negligible and the suspension presumed to behave
as a Newtonian continuum on a macroscopic scale.
In developing the asymptotic solution we shall
adopt the point of view that the viscous dissipation
of energy in highly concentrated suspensions,
which by the method of EINSTEIN[l] is related to
the effective viscosity, arises primarily from the
flow within the narrow gaps separating the various
solid spheres from one another. Within each gap
this flow is clearly due to the relative motion of
two spheres which we can decompose into a com-
ponent along their line of centers and a component
normal to it. In general both of these have to be
taken into account when computing the effective
viscosity, but, as will be seen presently, the domi-
nant term in the asymptotic form of the viscous
dissipation at high concentrations is due solely to
relative motions of the first type.
Figure 1 depicts two representative spheres of
the suspension moving along their line of centers.
Due to the linearity of the creeping flow equations,
it is permissible to choose the plane y =0 as a
plane of symmetry, thus reducing the problem to
that of a sphere approaching a free surface. The
latter has already been solved exactly by BRENNER
[4]. Hence, letting
F = 6n/1a W/3 (1)

847
 N. A. FRANKEL
and ANDREAS
ACRIVOS

where which can be obtained most readily by noting that:

W+J (2)
p-q n(n + 1)
and F is the frictional force experienced by either + Wag Co (6)
“*‘a* “= 1 (4n* - 1)(2n - 1)(2n + 3)*
sphere of Fig. 1, we find from Brenner’s solution
that the Stokes correction, p, is given by As shown in the Appendix, this simplifies to
1
n(n + 1) /I-- as u--t0 (7)
fl=$sinha 2 2a2

1
“= 1(2n - 1)(2n + 3)
or,
4 cosh*(n + +)a + (2n + l)*sinh*a _ 1
2 sinh(2n + l)a - (2n + 1)sinh 2a (3)

with
%i I:
as -+O

so that the asymptotic rate of viscous dissipation

coshaEl+h (4) of energy in either half-space is given by
2a
The viscous dissipation rate, E, on either side of
the plane of symmetry is given now in terms of the
stress, II and the velocity, v, by means of
E-3npW2a
[I f (9)

An identical result for the asymptotic expression,

Eq. (9), can also be obtained by making use of the
E= (l-I : Vv)dV= (n * II * v)dS = WF
methods of lubrication theory. Actually, the
s half-space s sphere
(5) lubrication analysis is identical here, for h/a small
enough, to that of the classical problem of flow
where the transformation of the volume to the between two parallel discs narrowly separated and
surface integral follows directly from the absence approaching one another at a constant velocity
of any inertia terms, the incompressibility assump- (0. Reynolds, see LANDAUand LIFSHITZ [5]), so
tion and the fact that the shear stresses are zero on that, by neglecting terms of the order of the curva-
the free surface. ture of the “discs,” we obtain for the local dissipa-
tion rate in the gap shown in Fig. 1

where the gap thickness y(r) is given in cylindrical

coordinates by
y(r)=h+2a[l-Jl-r*/a*] (11)
Equation (lo), when integrated over half the gap
volume, then becomes

E-2npW*a[ -$-2+(2+$45+)j

FIG. 1 (12)

Equations (l), (3) and (5) then specify quite which in turn reduces to
generally the rate of viscous dissipation of energy --
in either half-space for all a and W, consistent with E-3rcpW’a a
the equations of creeping motion. However, of 11
particular relevance to our problem is the asymp- when h/a-+0. This expression is of course identical
totic solution in the limit h/a+O, implying a+O, to Eq. (9), a fact which confirms our contention

848
 On the viscosity of a concentrated suspension of solid spheres

that only the gaps need be considered in the
asymptotic limit h/a-+0.
A lubrication type analysis can also be applied
to the case of sliding relative motion of two spheres.
Referring once more to Fig. 1, with the sphere
velocities now directed parallel to the line y= z=O,
we find for the local rate of dissipation in the gap
w=
(D-lh+2a(l-Jl-r2/a=)]=
in which, terms of the order of the curvature of the
bounding surfaces have been neglected. The rate
of viscous dissipation of energy is thus
vanish or are negligibly small for viscometric flows.
This velocity field is identical for all Newtonian
fluids and must therefore characterize the motion
of the suspension in a macroscopic sense. We shall
henceforth refer to it as the continuum field.
Furthermore, in accordance with our earlier
assumption that the spheres of the suspension
(13)
behave as fluid particles, we can express the
relative velocity between the i-th sphere and a
neighbor by means of
a$=di. ri (17)
where d’ is the continuum rate of strain tensor

)I
evaluated at the center of the i-th sphere and
E+dJ2 -2a+(2a+h)lo 1,; (14) ri is the position vector drawn to the center
[ 8( of the neighbor. The squared velocity W2,
which, as h/a-+0, is clearly of smaller order than which appears in the asymptotic expression (9),
the term given earlier by Eq. (9). Hence, we shall can be related to the tensor field d by making
neglect the contribution from this type of motion. use of Eq. (17) and averaging over possible orienta-
tions of neighboring spheres. This averaging is
3. LIMITINGEXPRESSION FOR THE EFFECTIVE particularly straightforward if we assume either
VISCOSITY that all orientations are equally likely, or that six
Following BRENNER [6], we now define the of the neighbors are aligned along the principal
effective viscosity of a suspension as directions of strain, obtaining in both cases

P*_
-- Js,(a*l-l * es ; v=v(O) on So (15)
< W= > =A(2a + h)=(d’ : d’) (18)
p j&&l * l-I(“) * v’O’)dS where, respectively, A = l/30 or A = l/l 2. Equa-
in which the right-hand side denotes the ratio of tions (9), (16) and (18), when combined, yield then
the rates of work being performed by the stresses for the effective viscosity
at the boundaries of an apparatus containing,
respectively, the suspension in question or an 3zfia(2a+h)= ; -$di : d’
equivalent volume of pure liquid. This definition LAN 0
(19)
P 2&d : d&’
is consistent with the usual experimental methods
for determining viscosity, such as Couette vis- where N is the number of neighbors of each sphere
cometry. Furthermore, because of the steady contributing to the asymptotic dissipation rate
nature of the flow in these instruments, the drags and the summation is over all spheres within the
and couples on small particles tend to vanish, so apparatus. For the case of small particle-apparatus
that Eq. (15) becomes equivalent to volume ratios, however,

P* ET v=v(O)on so 4$Cdi : d’=pS (d : d)dV

7=-p; i V

where the subscript T denotes the total rate of to a high degree of approximation, so that Eq. (19)
viscous dissipation of energy within the confines of reduces to the simple form
the apparatus.
CL*-C!
The boundary condition v= v(O) on So is suffi-
cient to specify the velocity field at all points
within So independent of the viscosity, since the
P 0h,
asLO
a
(20)

where C= 4qAN and rp is the volume concentra-

inertia terms in the Navier-Stokes equations either tion of spheres in the suspension.

849
 N. A. FRANKEL
In order to compare Eq. (20) with existing models
and with available data and correlations, it is con-
venient to express the quantity u/h in terms of the
concentration of the suspension. We shall assume
that this functional dependence is the same as that
for cubic arrangements of spheres, yielding
(21) where u, v, w represent the x, y, z components of
in which (P,,,is the maximum attainable concentra-
tion. Equation (20) now becomes
which is the principal result of this work.
4. DETERMINATIONOF THE CONSTANT C’
The precise determination of the value of C’ is
an elusive problem and it is likely that a statistical
treatment would be necessary at this point. For-
tunately, however, a cage model similar to that of
SIMHA [7] is found to yield a value for C’ giving
good agreement with available viscosity data. The
cage is taken to consist of a particle surrounded
instantaneously by a cubic configuration of neigh-
boring particles (shown in Fig. 2) which is then
replaced by a spherical cell representing the
“region of influence” of the particle in question.
In other words, the velocity field on the boundary
of the spherical cell is supposed to be equal to that
on an equivalent surface in a pure liquid under-
going the same macroscopic shearing flow.
n ‘C*II
FIG. 2
and ANDREAS ACRIVOS
We shall further assume that the shear flow on a
macroscopic scale is given by
u = it/2X
v = lc/2y (23)
w= --KZ
velocity, respectively, in which case the rate of
deformation tensor is given by
Referring to Fig. 2, we see now that the neighboring
spheres shown there have the instantaneous velocity
values U= (2a+ h)rc/2 and that two additional
nearest neighbor spheres exist with velocity vectors
directed inwards towards the central sphere and of
magnitude (2a+h)rc. Other spheres of the suspen-
sion are situated in some random fashion. Adding
the contributions from the six neighbor spheres
which are given by Eq. (9), we find for the rate of
energy dissipation in the cell,
E cell +72a + h)2a ;
0
while, for an equivalent spherical cell of homo-
geneous liquid, undergoing the rate of strain
indicated by Eq. (24), the rate of dissipation is
E homogeneous = 3pn’b + h/2)‘] (26)
Thus, we find for the effective viscosity
c_
P 0
9a
G
so that, from Eqs. (21) and (22)
as h/a+0 (28)
C’ = 918 (29)
It should be stressed at this point, though, that
the numerical value of C’ is fairly sensitive to the
assumed geometry of the cell since, for example, a
value of 37c/16 for C’ results if a cubical instead of
a spherical cell is chosen. The data, however,
support the value 9/S
850
 On the viscosity of a concentrated suspension of solid spheres

5. COMPARISON
WITH EXPERIMENT
AND
OTHER THEORIES 6o - Jtulgerr (averagecurve)
6. _ &= 0.535
Viscosity data for suspensions of solid spheres &Thomas (reduced data 1
are quite numerous, but, unfortunately, the agree-
ment among the various investigations has been
rather poor in the high concentration regime. A
number of reasons have been proposed for these
conflicting results: wall effects in capillary visco-
meters, slip at particle surfaces, insufficient dis-
persion, adsorption, turbulence, sedimentation,
non-Newtonian behavior, etc. THOMAS [3] has Einstein- Simha
recently considered some of these problems, and
by appropriate extrapolation techniques, was able
to minimize non-Newtonian, inertial and non-
homogeneous effects and to fit the resulting
adjusted data to a smooth viscosity curve with
little scatter. Also, an attempt to sort out the
more reliable measurements was made by RUTGERS
[2] whose average curve, although quite arbitrary,
is in good agreement with the data of the (appar-
ently) most careful investigators.
FIG. 3
The data of Thomas and of Rutgers have been
plotted in Fig. 3 together with the asymptotic
expression, Eq. (22). In order to determine the
maximum concentration in each of the two cases,
we adopted a suggestion of Thomas which was to
IOO-
plot [(p*/p)- 11-l vs. cp and extrapolate to zero
60-
ordinate. The asymptotic expression is seen to 0 Rutgers (average curve)
60 - A Thomas (reduced data
agree quite well with the measurements for con-
centrations greater than eight-tenths of the maxi- 40-
mum, which corresponds to h/u= 0.16.
Also shown in Fig. 3 is the EINSTEIN[I] result,
20-
valid for infinite dilution and the quadratic correc-
tion as calculated by GUTH and SIMHA [8] and P
Y_

amended by SAITO [9]. The latter expression 3.

IO-
appears to give good agreement up to gol(p,=O*25. 6-

In Fig. 4 we present the dependence of the 6- q A

relative viscosity on 40 in order to indicate the Einstein-Simha
4-
disparity between the data of Thomas and of
Rutgers at high concentrations. It is apparent
that in this region the effect of maximum packing
density must definitely be considered and that the
asymptotic expression, Eq. (24), describes both
sets of data equally well.
Equation (22) is not in agreement with any of
the semiempirical or empirical expressions which FIG.4

851
 N. A. FRANKEL
and ANDREAS
ACRIVOS

have been proposed for highly concentrated sus- Acknowledgment-This work was supported in part by the
National Science Foundation.
pensions. We summarize here, several of the best
known models, one of which is totally empirical:
SIMHA [7]. The parameter f is empirical, 1 <f c2 NOTATION

radius
dimensionless number
dimensionless number
rate of deformation tensor
MOONEY [I 01. The parameter K is empirical, 1.35 I
rate of viscous dissipation
KS I.91 empirical constant
frictional force
minimum gap width
unit outer normal
number of nearest neighbors
EILERS[I 11. The entire expression is empirical radius in cylindrical coordinates
position vector from origin of i-th particle
(32) to that of a neighbor
boundary of viscometric apparatus
increment of surface area
Simha’s analysis is based on the idea that the X, y and z velocity components, respectively
neighbors of each sphere in the suspension can be velocity, defined in Fig. 1
replaced by a rigid spherical wall, while the Mooney velocity vector
relation is similar to one originally proposed by velocity on S,
volume
ARRHENIUS [13] with the addition of a crowding
velocity, defined by Eq. (2)
factor, 1 - Kcp. Cartesian coordinates
The present result is believed to be a funda- gap width, a function of distance from the
mental improvement over existing models since it line of centers
has been developed without recourse to empiricisms defined by Eq. (4)
Stokes correction, defined by Eq. (1)
or artificial boundaries. This result also indicates
increment of velocity
that the rapid rise of viscosity which is observed at shear rate
high concentrations can be accounted for solely by viscosity of pure liquid
the hydrodynamic interactions of neighboring effective viscosity
spheres. We presume, therefore, that collisions, stress tensor
concentration (volumetric)
aggregation and inertial effects are of minor
the local rate of viscous dissipation per unit
importance in the usual experimental arrange- volume, defined by (9=2pd:d, for an
ments. incompressible fluid

REFERENCES

111 EINSTEIN
A., Ann. Phys. 1906 19 289; Ann. Phys. 1911 34 591.
PI RUTGERS IR. R., Rheof. Actu 1962 2 202, 305.
[31 THOMAS D. G., J. Colloid Sei. 1965 20 267.
[41 BRENNER H., Chem. Engng Sci. 1962 16 242.
[51 LANDAU L. D. and LIFSHITZ E. M., Fluid Mechanics Vol. 6, p. 70, Pergamon Press 1959.
161 BRENNER H., Phys. Fluids 1958 1 338.
171 SIMHAR., J. Appl. Phys. 1952 23 9, 1020.
PI GUTH E. and SIMHAR., Kolloid Zh. 1936 74 266.
191 SAITON., J. Phys. Sot. Japan, 1950 5 4.
[toI MOONEYM., J. Colloid Sci. 1951 6 162.
f111 EILERSH., Kolloid Z. 1943 102 154.
U21 JOLLEYL. B. W., Summation of Series, pp. 383, 764, 224, 766, Dover 1961.
1131 ARRHLENIUS S., Z. Phys. Chem. 1887 1 285.

852
 On the viscosity of a concentrated suspension of solid spheres

APPENDIX Each of these series has been summed, the results

being available in JOLLEY[12]. In particular, we
In order to sum the expression in Eq. (6), it is
find that
convenient to make the partial fraction reduction:

SE f
n(n + 1)
n= 1(4n2- 1)(2n - 1)(2n + 3)2

1
-3/g l/64
=J (2n - 1)2(2n + 3)2 - (2n - 1)(2n + 3)
?(2n+l)-‘(2n+3)-‘=1/6
1

l/32 3164 f(2n-1)-2=; 64.2)

-(2n+3)(2~+1)+(2n-1)2 1

Therefore,

(A.11 S= l/32 (A.3)

R&n&-Une technique asymptotique est employee pour deduire la dependence fonctionnelle de la

viscosite effective de la concentration pour une suspension de spheres uniformes solides a la limite
quand la concentration se rapproche de sa valeur maximum. Ce resultat, ne contenant aucune con-
stante enpirique, est compris comme complement de la formule classique d’Einstein qui est seulement
valable pour une dilution infinie. On trouve un accord satisfaisant entre la solution asymptotique et
les don&es disponibles a condition que la concentration maximum soit determinee a partir des
donnees elles-memes.

Zusannnenfassnng-Zum Ableiten der funktionellen Abhlngigkeit der effektiven Viskositat von der
Konzentration in einer Suspension gleichformiger, fester Kugeln-innerhalb des Bereiches, in dem sich
die Konzentration ihrem Hiichstwert nahert-wird eine asymptotische Technik angewandt. Das
Ergebnis, das keine empirischen Konstanten enthllt, sol1 die klassische Einsteinformel erganzen, die
nur in unendlicher Verdtinnung gilt. Zwischen der asymptotischen Losung und den zur Verftigung
stehenden Daten wurde gute Ubereinstimmung gefunden, vorausgesetzt, dass die Hochstkonzentration
aus diesen Daten selbst bestimmt wird.

853