RHEOLOGICA ACTA

AN INTERNATIONAL JOURNAL OF RHEOLOGY

Band 11 September/Dezember 1972 Heft 3/4

.From the Department o/Aeronautical Engineering, Technion - Israel Institute o/Technology, Hai/a (Israel)

On viscous flow and effective viscosity of concentrated suspensions and emulsions

Effect of Particle Concentrationand SurfactantImpurities
By I. Yaron and B. G a l - O r

With I figure and 4 tables

( R e c e i v e d N o v e m b e r 26, 1971)

Notation
a ~ r a d i u s of particle.
A m, A m, B m, B n . . . . . . In, I n = g e n e r a l coefficients defined b y [A 1] to [A9].
c -~ c o n c e n t r a t i o n o f s u r f a c t a n t s in c o n t i n u o u s p h a s e .
C1, C~, C3, C4, Cs ~ coefficients defined b y [A14] to [A18].
D~ -~ diffusivity o f s u r f a c t a n t s in c o n t i n u o u s p h a s e .
D~ ~- surface diffusivity of surfactants.
E ~ r a t e of e n e r g y d i s s i p a t i o n p e r u n i t v o l u m e .
F ~ frictional force.
g ~ acceleration d u e to g r a v i t y .
G ~ shear.
h ~ d i s t a n c e f r o m c e n t e r of particle to p o i n t of zero velocity.
i, j, k = Cartesian u n i t vectors.
Jn ~ s u r f a c e flux of s u r f a c t a n t s .
/( ~ c o n s t a n t defined b y [27].
Lm n' /~m m Mn'
n' Mn, - ~ Nn,
~ Nn
^~ ~ p a r a m e t e r s defined b y [A 11] to [A 13].
m, n ~ integers.
p ~ pressure.
Pn = solid spherical h a r m o n i c of o r d e r n.
r ~ r a d i u s vector.
R1, R~ ~ radii of c u r v a t u r e .
s ~- surface area,
Sn {0, ~ } ~ s u r f a c e spherical h a r m o n i c of o r d e r n.
tr ~ u n i t v e c t o r in radial direction.
To ~ t o r q u e a b o u t c e n t e r of particle.
U ~ v e l o c i t y of u n i f o r m i m p o s e d field.
Us ~ Stokes velocity o f particle.
v = v e l o c i t y vector.
m ^m m ^m m ~m m ^m
Vn, Vn' Xn' Xa' Yn' Yn' Zn' Zn = p a r a m e t e r s defined b y [66] to [69].
W1, W~, Y1, Y~ = p a r a m e t e r s defined b y [52] to [55].
x, y, z ~- Cartesian coordinates, z a l i g n e d w i t h axis of particle.
Greek letters
a* ~ overall a d s o r p t i o n r a t e c o n s t a n t .
fin = v i s c o s i t y p a r a m e t e r defined b y [A 19].
= r a t i o of radii o f particle a n d cell.
~n = interfacial r e t a r d a t i o n v i s c o s i t y defined b y [A 20].
T' ~ s u r f a c e c o n c e n t r a t i o n of s u r f a c t a n t s .
!' 0 ~ e q u i l i b r i u m s u r f a c e c o n c e n t r a t i o n of s u r f a c t a n t s .
/" -~ d e v i a t i o n of F f r o m / % .
/~nm, I nm ~ coefficients defined b y [31].
(~ = t h i c k n e s s o f Nernst diffusional layer.
An : p a r a m e t e r defined b y [A 10].
e = p a r a m e t e r defined b y [32]
~n = g e n e r a l coefficient defined b y [23].
~] = d i m e n s i o n l e s s r a d i u s , ~/ = r/a.
0 : cone angle.
16
242 Rheologica Acta, Band 11, Heft 3/4 (1972)

= viscosity ratio defined by [A21].

= viscosity.
/~eff effective viscosity.
~n(O, qJ) = deviation from sphericity function.
= deviation parameters, defined by [61]
= density.
o = surface tension.
7:r surface shear force.
= components of stress tensor.
= polar angle.
q)n = solid spherical harmonic of order n.
Zn solid spherical harmonic of order n.
= parameter defined by [71].
= components of vorticity.
Superscripts
= pertains to phase in general.
C = pertains to continuous phase.
d pertains to dispersed phase.
o = pertains to imposed field.
Subscripts
a at interface.
o equilibrium value.
r = radial value.
0 tangential value.
q~ azimuthal value.
Special signs
() expected value.

Introduction
In many practical situations one has to consider the
motion of two-phase particulate systems within shear
fields imposed by stationary or moving solid boundaries.
In such cases the motion around spherical particles is
not axi-symmetrical and the imposed shear fields may
also cause deformation of fluid particles. This work
deals with a general analysis of the motion around
uniformly-sized particles of ensembles of both rigid
and deformable particles moving at low particle
Reynolds numbers in arbitrary imposed shear fields.
Effects of surfactant impurities and volume concentra-
tion of fluid particles upon the motion and deformation
are also considered. The general expressions derived
here are employed to obtain specific relations for uni-
form, Couette and hyperbolic imposed flow fields. The
velocity fields obtained here for both fluid phases can
be used to evaluate interracial convective rates of heat
and mass transfer. For such applications one cannot
treat the multiphase system as if composed of one
equivalent phase.
Cell models and their statistical nature
W h e n e v e r a p a r t i c u l a t e s y s t e m is c o m -
posed of a very limited number of particles
(dilute s y s t e m ) a r r a n g e d in s o m e fixed k n o w n
g e o m e t r i c a l a r r a y one m a y t r y t o s a t i s f y
s i m u l t a n e o u s l y all b o u n d a r y c o n d i t i o n s a t
t h e i n t e r f a c e s o f all t h e particles, or a t least
s o m e c o n d i t i o n s a l t e r n a t i n g l y a t t h e surfaces
o f t h e particles (e.g. m e t h o d o f reflection).
H o w e v e r , for concentrated s y s t e m s in w h i c h
t h e p a r t i c l e s positions c a n n o t be prescribed,
the complexity of the system dictates
s t a t i s t i c a l a p p r o a c h e s , one o f w h i c h m a y be
t h e cell m o d e l (2)1). This m e t h o d is b a s e d on
t h e a s s u m p t i o n t h a t t h e field p r o p e r t i e s
around an arbitrary typical particle of the
s y s t e m (e.g. v e l o c i t y c o m p o n e n t s , s h e a r
stresses, t e m p e r a t u r e , h e a t fluxes, con-
c e n t r a t i o n s , m a s s fluxes, etc.) m u s t a t t a i n
e x t r e m a l ( m a x i m u m or m i n i m u m ) v a l u e s a t
s o m e d i s t a n c e f r o m t h e particle, b e c a u s e o f
the presence and mutual interactions of the
n e i g h b o u r i n g particles. W e c a n t h u s en-
visage e a c h p a r t i c l e t o be e n c l o s e d b y a n
i m a g i n a r y e n v e l o p i n g surface, o n w h i c h t h e
field p r o p e r t i e s b e c o m e e x t r e m a l . M o s t
p a r t i c u l a t e s y s t e m s are c o m p o s e d o f randomly
dispersed particles. T h e r e f o r e , t h e cell en-
velopes a s s o c i a t e d w i t h t h e v a r i o u s particles
are o f different s h a p e s a n d sizes. H o w e v e r
in a c o n c e n t r a t e d s y s t e m one e x p e c t s a n y
g i v e n p a r t i c l e t o be, in a statistical sense,
s u r r o u n d e d b y a m o r e or less unfixed, y e t
s y m m e t r i c a l cluster o f particles. U p o n super-
p o s i t i o n o f t h e n u m e r o u s cell e n v e l o p e s o f this
cluster 2) t h e i r s t a t i s t i c a l l y e x p e c t e d f o r m
t e n d s t o a p p r o a c h a spherical s h a p e [in a n
e n s e m b l e o f r a n d o m l y m o v i n g particles (2)].
1) Cell models (of various shapes) have, so far, pro-
vided the only useful solutions, which agree with all
experimental data for concentrated system (2, 10, 12,
19, 22) [but not necessarily for dilute ones as incor-
rectly implied in a recent paper (24)].
2) On a single center of a typical particle, whose
size and shape represent the entire ensemble.
 Yaron and Gal-Or, On viscous flow and e~ective viscosity o/ concentrated suspensions and emulsions 243

One must emphasize now t h a t the velocity

field determined by any boundary condition = "~ l.Vx(rZn) -t- Vcf n + 21ae(n -4- 1) (2n + 3)
n= -r
specified on this cell envelope is n o t the one
t h a t one can measure around a givenipar-
ticle, since it represents the expected statis- • r VPn-- #c(n+ 1)(2n+3) rPn~ [3]
tical average velocity field of the entire and
assemblage. Therefore, the expressions deri-
ved in the present work become p r o p e r t i e s of p~= ~ Pn" [4]
the entire assemblage of particles. Similar
assumptions are used frequently in statistical Placing the origin of the coordinate
thermodynamics (20, 25). system at the center of a typical particle,
The radius of the cell envelope is derived the requirement t h a t the velocity at the
from the assumption that m randomly origin be finite restricts solid spherical
dispersed systems the ratio of the particle- harmonics in the dispersed phase ( ~ - d)
to-cell volume must be equal to the ratio of to positive values. The general solutions [3]
the volume of the dispersed phase to the and [4] are also applicable to the arbitrary
volume of the whole system. Accordingly, imposed shear field (~ = 0) in the absence
for a system composed of uniformly-sized of thedispersed particles.
spherical particles of radius a, the radius of To evaluate the various solid spherical
the cell envelope is aq ~-l/a = a y -3, where ~b harmonics involved, the following boundary
is the volume concentration of the dispersed conditions are employed:
phase (2). At the surface of a particle
Since the cell represents the bounds of va = vC, [5]
"influence" or "perturbation" due to a a c = 0, [6]
V r = Vr
typical particle on the field around it, it is
evident that the extremum field values which v r = v r -- + tr + V s a ( F ) . [7]
must be specified on the envelope must be
those of the "unperturbed" field, i.e. to At the spherical cell envelope (i.e. at
those field values of the continuous phase r : 7 -i)
which would have been encountered, had = v~ , is]
one not introduced into it the particles of c 0
the dispersed phase. In the present analysis ~r0 = Tr0' [9]
we adopt the "free surface spherical cell" vrc = z~. [10]
model, which assumes t h a t on the envelope
Condition [7] states t h a t the surface shear
the radial velocity component and the tan-
forces in both phases, when taken in com-
gential shear stresses have the values of the
ponents, show a difference due to the cur-
unperturbed shear field, i.e. t h a t tangential
vature of the surface (capillary effect on the
shear stresses cannot be transferred across
normal component) and to the interfacial
the cell envelope. This model differs some-
tension gradients set up by adsorbed sur-
what from the "zero-vorticity" model (2),
factant impurities (1).
which assumes t h a t no vorticity diffuses from
Using the approximate relation
one cell to another.
a(I') = a ( l ' o + F')_~ a ( F o ) + _ _(~)oF"F'~ Fo, [11]
Expected velocity and pressure fields
whereby
For steady motion with negligible inertia Oa
Vs a (F) _~ ( ~ f i - ) o Vs F ", [12]
(i. e. Re ~ 1), the equations of motion and
continuity for the expected velocity and we transform, following B r e n n e r (8), boundary
pressure fields around and inside the fluid conditions [5] to [10] as follows :
particles in the assemblage are At r : a: v c" tr = 0, [13]
#~v~<v~> = tT<p~>, [1] v d" t r = 0, [14]
and
v'. <v~> = o. [2] r~=r ar ' [15]
Dropping for simplicity the expected value r" V x v d = r" V x v c, [16]
sign(<>), the general solutions to these
equations in terms of solid spherical har- r" Vx(rxzdr) : r" V x ( r x v C r ) - (~)0[r" Vx(rxVs_r")],
monics (5) is [17]
16"
244 Rheologica Acta, JBand 11, Heft 3/4 (1972)

v~. tr - z a. r = a ( r ) ( i / R , + ]IR,), [18] Introducing expressions [27] into [24],

and expressing V~ " (V)a in terms of solid spherical
r. Vxz d = r- I V x l r rc [19] harmonics, expanding the latter according
to Eqn. [23], assuming that / " is also ex-
At r = ~-~: v c" tr --~ v ~ tr, [20] pandable in the form
c 0 co
r , V x v r = r" V x vr , [21]
P' = ~ r~'s^(o
n , ~), [28]
r .VxCrxzCr) = r . Vx(rxv~ [22]

To employ the transformed boundary whereby

co
conditions [13] to [22], one must specify 8 2 ," $ ,' 2
the shape of the particle, which m a y be n=l
deformed b y the external shear field. This
shape is not a p r i o r i known. It is expedient and noting, that from the theory of surface
to first approximate the particle b y spherical spherical harmonics (7),
shape, and later calculate the deviation of its
shape from sphericity. This calculated V2sSn(O, q)) = - - n ( n + :l)Sn(O, ~) [30]
deviation can then be utilized to initiate an
we find, applying orthogonality properties
iterative procedure for reformulation of the
of spherical harmonics and L e g e n d r e ' s poly-
aforementioned boundary conditions.
nomials, that
We now express the boundary conditions
in terms of the general solution [3], in which m aFo 1
r n =
the solid spherical harmonics have been D~ (n*+n+e)
further expanded in terms of solid surface
harmonics, and the latter in turn resolved [ n ( n § 2) m T]
• 2 ( 2 n - t - 3) A n + n ( n - - 1)B , [31]
in the general form
where
/~a 2
~n Sn(O, ~o) = ~ (~T cos m~o + ~nm sin m,q~)Pm (cosO)
[32]
[23]
where Note, that an expression similar to [31] is
m m in obtained for f T in which A~ and B~ exchange
~T= AT, BT ..... s:, %, ~ - 1 ..... ~-.-~
AT and BT, respectively.
and
~m Am -m m .m . .
n n ' B n '" 9 ", f n ' COn,CO-n-1 " ' ' , ~ - - n - 1
General expressions
Surfactant impurities Introduction of relation [31] into boundary
condition [17], and utilization of the ortho-
The surface flux of surfactant impurities gonality properties of solid surface harmonics
at steady state, neglecting coupling effects and L e g e n d r e polynomials, gives a set of
due to surface shear forces, is given by nine equations, the simultaneous solution of
which results in a set of nine coefficients
A = v~ 9 [ r ( v h - D ~ r ) ~ roV~-(,,).- 1) i~ V ~
s 1".'
AT, B T , . . . , IT, listed in the Appendix.
[24] With their aid one m a y describe the flow
Relating this flux to the kinetics of dif- fields in the dispersed and continuous
fusion from the continuous phase to the phases of the ensemble in terms of the given
interface (6) coefficients ~ a-~-l,...,y-n-1
an, ~ m of the
unperturbed field. The latter can be derived
].' ~(ro - r~) f t'at"
w),~' E25] from the examination of suitable expressions
for specific flow conditions. Note that another
and the kinetics of adsorption-desorption set of nine coefficients AT, B T , . . . , iT is
mechanism on the interface obtained in terms of the coefficients
a^m am
, , a-~-I Am
. . . . , ~-~-1 of the unperturbed
Jn = -- a* (F --/'i), [26] field. The two sets of coefficients are identical,
we obtain
except for the supersign ^.
[ ~,__~ (~r~ ]-'r'=-~:r'. [27] General expressions for velocity compo-
Jn = -- ~* /1 "[-
L D~ ] eqJ nents, pressure distributions, shear stresses
 Yaron and Gal-Or, On viscous flow and e#ective viscosity o/concentrated suspensions and emulsions 245

a n d v o r t i c i t y d i s t r i b u t i o n in b o t h p h a s e s Ga
v ~ tr =--~-" ~ cos2~P~(cos0) -- Ux cos ~P~ (cos0)
of t h e a s s e m b l a g e h a v e been d e r i v e d f r o m
E q n s . [3] a n d [4] a n d are r e p o r t e d elsewhere -- Uy sinCP~ (cos0). [44]
(19). F o r t h e sake of b r e v i t y we p r e s e n t in
this w o r k only expressions for specific im- and
p o s e d shear fields. r . V x v ~ = O. [45]
Using these relations one obtains
Characteristic parameters o f i m p o s e d
flow fields fl~ = - vx, [46]
t~ = - ~ , [47]
a) Uni/orm flow and
U n i f o r m i m p o s e d flow fields m a y be Ga
#~ = - ~ - . [48]
e n c o u n t e r e d in n a t u r e , e.g. a t m o s p h e r i c
s e d i m e n t a t i o n of dust or fallout, aerosols, fog,
etc., a n d in s e d i m e n t a t i o n of suspensions Frictional force, torque and force b a l a n c e
a n d the like in large d i a m e t e r vessels. F o r o n particles o f e n s e m b l e
such a flow 1)
v ~ = -- U k, [33] Using B r e n n e r ' s (8) expression for the
frictional force acting u p o n a particle of t h e
v ~ tr = -- U cos 0 = -- UP1 (cos 0), [34] ensemble
and F = -- 4 z V ( r 3 P-e),
r 9 Vx v ~ = O. [35]
we o b t a i n in t e r m s of the coefficient G~
I t follows f r o m t h e general solution [3]
a n d the e x p a n s i o n s of the solid spherical F=--4~ttCa(G~ G1j
1 9 + G~i). [49]
h a r m o n i c s t h a t for this case Similarly, f r o m the expression for the
fl0 = _ U, [36] t o r q u e (8), e x p e r i e n c e d b y a particle of t h e
ensemble a b o u t its origin
a n d t h a t all o t h e r coefficients are equal to
zero. To = -- 8~ / V(r~z=2) [50]
we find
b) Couette flow To=-8~/,ca(I ok§ I~i).
This u n i f o r m shear field is e n c o u n t e r e d in A force b a l a n c e on a particle gives
coaxial cylinders r o t a t i o n a l v i s c o m e t r y . H e r e
v~ i- Ui, [37] F + ~4- ~ a 3.tqd - - q c ) ( 1 - - y ~ ) g = 0 . [51]

v~ tr : ( G h - U) cos~P~(cos0) W h e n directions of vectors k a n d g co-

incide, using t h e characteristic p a r a m e t e r s
Ga
+ ~ ~ sin2~P~ (cos0) [38] of the i m p o s e d flow fields~derived in t h e
p r e v i o u s section, a n d t h e general expression
r . V x v ~ = - - G a ~ cos0, [39] for the coefficients (A1) to (A9), we o b t a i n
the following specific expressions for frictional
w h e r e b y we find force a n d t o r q u e on particles of e n s e m b l e s in
~ = ah- U, [40] uniform, C o u e t t e , a n d h y p e r b o l i c i m p o s e d
fields :
Ga
~i= 6 ' [41]
and Frictional force Torque
y0 = _ Ga. [42]
Uniform 6z #c a Us k 0
c) Hyperbolic flow Couette 0(1) 0
Hyperbolic 0(3) 0
A hyperbolic flow field is set u p b y t h e
m o t i o n of four r o t a t i n g cylinders. F o r such a Note: (1) A force balance for this case gives U = Gh,
whereby fl~ = 0.
field (2) A force balance for this case gives Ux = Uy = 0,
v~ Uxi-- Uyj [43] whereby fll = ~ = 0.

~) In the Cartesian coordinate system the direction The s a m e results are o b t a i n e d for n e u t r a l l y
of unit vector k coincides with the axis 0 : 0, 0 : z. b u o y a n t particles.
246 Rheologica Acta, Band 11, HeJt 3/4 (1972)
Velocity profiles in the dispersed
and continuous phases
Employing the general expressions from
reference (19), the velocity components for
some specific imposed fields are summarized
in table 1, where the following parameters
are defined:
Wl = 3(1 + 2/3~1) + 2r - #1),
Y1 = 2(1 + fl~)+ 3~5(1 - 2/3fil),
W2= 5(1 + 2/5fl~)+ 2y'(1 -fl~),
y, = 2(1 + ~) + 5~(1 - 2/5#3).
Pressure distribution
The general expressions of reference (19)
are also employed to arrive at specific ex-
pressions for pressure distributions in various
imposed fields as given in table 2. The total
pressure distribution should include, in
addition to the terms of table 2, the re-
ference Po and the static pressure @grcosO
terms.
Distribution o/shear stress components
The specific expressions for stress tensor
components in the dispersed and continuous
phases of two-phase particulate systems in
uniform, Couette and hyperbolic imposed
fields are presented in table 3. (General ex-
pressions are given in reference [(19)].
Distribution o/vorticity components
The general vorticity components can be
reduced (19) to specific cases which are
presented in table 4.
Deviation of shape of a particle from sphericity
Boundary condition [18] is now utilized
to find the deviation of shape of a typical
particle from sphericity.
I t is assumed t h a t the shape of a typical
particle's interface can be represented by
r = a[1 + 5(0, ~)],
such t h a t
15(0, ~)1 < 1.
According to Landau and Lilshitz (14)
1 + 1 2 25
R, R2 a a
1 [ I 02~
a [~
1 0 sin0-~-
a~ + sin0 O0 ( +0(5) 3.
Assuming t h a t the deviation ~(0, W) from
sphericity can be expanded into surface
spherical harmonics according to
~(o, ~) = ~ ~n:Sn(O,~),
n=0
t h a t the volume of the deformed particle
remains constant and t h a t the origin of
[52]
the coordinate system remains always
[53] coincident with the center of gravity of the
particle, Hetsroni et al. (9) have shown,
[54] using the properties of surface spherical
[55] harmonics, and neglecting the term of 0 (~)2,
that
-~[+-~-~ = - E 2+ (n'+~-2)~nS~(O,~o) .
[59]
Introducing this expression into boundary
condition [18], expressing the radial com-
ponents of the surface shear force in terms
of spherical harmonics, eliminating har-
monics of order zero and one, which re,
present the reference pressure and force
balance terms, one obtains, after some
manipulation, for the shape of the particle's
interface
n=Om=O
[60]
where
1 t
(n~+ n + 2 ) ~ 2n(n--1)(B~--flnE~n)
+ ~ (A~-- ~nD~)-- 2~.(~ + i)
x ('~ + 2)H'2"--/~* -(n20-,;--
+ 3n ~ I) G~n} [61]
Expression [61] can be used to reformulate
boundary conditions [13] to [22]. Such a
reformulation has been recently employed
by Haber and Hetsroni (13) for the case of
a single particle in an unbounded infinite
[56] fluid. However, because of the complexity
of the expressions involved, the reformulative
procedure was not carried beyond the second
[57] iteration.
In the present analysis we have restricted
ourselves to the first iteration. The deviations
of the shape of a typical particle from
sphericity for the various imposed fields
considered are given as follows
Uniform
[5S] ~'~a.
 Table 1. Velocity components in dispersed and continuous phases of ensembles in various imposed fields

Velo-
city Uniform Couette Hyperbolic
compo-
nents

Vdr 32 W~
Us fl~(1 -- ys) (I -- ~z) cos0 3 Ga
2-
3 (Y, --GaW 2 ~ f12~](77 _ 1) (1 -- ,~2)sin 2~v sin20 ( Y~ -- W~ 73) f12 q (y7 _ 1) ( 1 -- ~) cos 2 q~sin20

V~~ 32 W~
Us f l i ( 1 - ~ 5 ) ( 2 ~ - l ) s i n 0 3 Ga --1)(1 - - ~-
5 v/)
2 sin 2c~ sin0 cos0
30a
(Y2__ W~7~) fi~V(y7 - 1 )
(1--~-~f cos2~0sin0cos0 ~5

d
VcP
0 32 (Yz - -GaW~y3) flz ~](y7 - 1) (1 - - ~5- ~ 2) cos2q0sin0 (y, _3Ga 5 ,2)sin 2~0 sin0
W~Ta) fl,~?(y7 -- 1) (1 -- ~-

VCr "3~ (Us

,fyn-- Y~"t W~
~ 1)cos0 ~1- ( y Ga
=~V~ya)-(-- 3"~aYT+ ~IY~- +~)sin2~ ~ (Y2 -- W~ya) -- 3~13~7 q- ~/Y~ -- W-L
( v~ q- ~z c~
Ga ( 2)
VC0 2"~3Us[ 2~1 W~2~+ Y~--~f75) 2(Y~--W~) (-5~ayv+~Y~- sin2q0sin0eos0 (Y2 ~[/V2~ )3) ~]Y2 - - 5T~3~)7 - - ~ COS 2~9 s i n 0 cos0
• sin0
V~ 0 -- 2
~ 2 ( Y ~Ga}V~?z) ( -- 5 ~ y 7 + ~ I Y 2 - - ~2 ) cos2~sin0 Ga ( , y ~ _ _ 5 v / 3 ~7 _~_7) sin2tpsin0

Table 2. Pressure distribution in ensembles of particles in various imposed fields

Flow Field pd pC
r
#d 3 Us 3 c Us W~ ~ 5 ) cos0
Uniform 10 - - ~fll (1 -- 75) 9- - - cos tl 2 11(7 +1~ co
a 2 W~
21 /~d G g~
Couette ~ (Y~ -- W2 V3) ~12fl2(1-- y7) sin2~o sin20 2 (Y~ ----W2yz) ~ U sin2q ~sin20

Hyper- 21/z d G vl2fl~(1 --yT) cos 2~0sin20 _/~e (Y2 :IY,~)G (21 ~2~,~ q_ ~ ) cos2~0sin20
bolic (Y~ -- W~ ?z)

t~
 Table 3. Stress tensor components in dispersed and continuous phases of ensembles of particles in various imposed fields

Stress
tensor Uniform Couette Hyperbolic
compo-
nent

_ 91~ a Us 3 #a Gfl2(77__ 1) 3 Iza Gfl3 (77 -- 1) (2 + ~3) cos 2~0 sin20

- 7 - w T fl~(1 - 7 5) n ~ cos0 ( Y2 -- W, 73)
9 t, a Us 2/z d Gfl3 (77 -- l) (3 -- 8 ~/~)cos 2 cp sin 0 cos 0
2 r W, */3fix(1--7~)sin0 #d Gfl~ .(y~__ ~lr~ra ) (3 -- 8,/2) sin 2~o sin0 cos0
( Y~ - ~ T ~ )

0 @7 _ 1) (3 -- 8~ 2) cos 29 sin0 -- 2tflGfl2 ( Y (77

, - - --W1)
3 ~ ) (3 -- 8~3) sin 2~ sin 0
# a~2 ( r ~ - - ~ T 7 ~)
9 tz_c Us ,uea ( 3 7 1 ) 21acG (Y2_3770, 12,-5+ 1 W,??-3)
2 r Wx ( - - 2 r l ~75+ 2rl-a (Y3-- W373) Y 3 - - ~ - 7 ~/2_12~-a+_~_W~-3 {r,-~-w~r ~) ~ - y
+ rUx W~) cos 0 • sin 2 ~0sin~0 • cos 2(p sin* 0
9 p e Us G G
2 r W~ ( ~ r s - - n - ~ ) s i n O Pe ( Y . - W . ~ ) (Y* -- 877 ~/3+ 8r/-n _ W3 ~7-a) 2~c ( Y . - W . ~ ) (Y* --87~*/* + 8r/-5 -- W'n-3)
• sin 2q9 sin0 cos0 • cos 2 ~o. sin 0 cos 0
G G
0 /zci (Y. _ WzTa) (Y. -- 877 ./~ + 8~ -~ - - W . ~ -a) cos29sin0 --2/~c (Y2 -- W2~) (Y~-- 877 ~/3q_8~-5 _ Warua)sin2~0sin0

Table 4. Vorticity components in dispersed and continuous phases of ensembles of particles in various imposed flow fields

Vorti-
city Uniform Couette Hyperbolic
compo-
nents

0 7 Gfl *r12 @7 __ 1)cos2 ~osin0 7Gf12r12 (77 -- 1)sin2 q0sin0

2 ( Y~ -- W~ 73) (Y~ -- W273)

d 15 Us 7 _Gfl, rt2 ( a 1) sin2 ~osin0 cos0 7 G f127/2 (77 -- 1)cos2 q0sin0 cos0
4 WI fll ~2 (Ts __ 1)sin0 2 (Y~--W273 ) ~ -- (Y. -- W~ 73)

0 1 G W . rl-" (7 77 ,~ 1) cos2 ~osin0 GWzrl (7 77~5 _ l ) sin2 sin0

2 (Y~ -- W~ 7 ~)
c 3 Us 7 -1 1 aW.,-a ( 77, 5 ) G W,• (7 77~5 -- 1) cos2 q~sin0cos0
0)~0 -4 W~ r (57 5 ~ / 3 - W 0 s i n 0 2 ( Y . - - W.73 ) 7 ~ - - 1 sin2tpsin0cos0
 Yaron and Gal-Or, On viscous flow and effective viscosity o/concentrated suspensions and emulsions 249

Gouette dcosm~0 ^m d s i n ~ Pnn (cos0) ]

3 Gafl~ tzd 4- M~n ~ 4- M n d~ ] sin0
r=a 1 + 16 a ( Y ~ - - W ~ )

2 Yz + 2 W~ + 5) sin 2~ sin~O]
X (2 y: -- -~-
n=l m=0
Hyperbolic (cos0)
r=a[1 4-3 Gaflzffd . ] sin 0 dO dq. [65]
x sin 0
8 a ( Y = - - W~y")
where
X ( 2 7 7 - ~ Y2~ + 2 W ~ + 5) cos 2~ sin~O]
Vn = - n an + 2(n -- 1)7 Pn
E f f e c t i v e v i s c o s i t y of t w o - p h a s e 4- 2(n~4- 3 n - - 1)
multiparticle systems (n 4- 1) Vn ~-~-1 -- 2(n 4- 2)y n+2 V-n-1
/r
Happel (3), and more extensively Happel [66]
and Brenner (10), have shown on the basis and
o f energy dissipation considerations, and the .~ 1 [(n + 3 ) / ~ - ~ ~ + (n + , w ~
spherical cell concept, that the effective Zn -- n(n + 1) ~n
viscosity of an ensemble of particles in slow (n 2) V nam- n - 1 -- nv n+2Rm q [67]
-- -- ~'-n-1J 9
viscous motion can be expressed by
Ec An expression for E c, similar to [65], is
ffeff = ~ - . [62] obtained if Y~ and Y~ are substituted for
^ra 9
Here the rate of energy dissipation per V~ and V~, respectively, and X~m and ~ ,m
for Z~m and Zn,
^m respectively, where
9
unit vo]ume of the fluid, in the continuous
phase, on a spherical surface of radius b = a y - a ](nm=2n(n.,-n+lt~m ( n ~ : - - : ~ } 3) -n-1 r~m
9)Y ~ + --(2n Y Jan
in the absence of the dispersed phase, is
E ~= ; ds.r ~ ~ [63] ~, n+2 r,m (n ~ 4- n -- 1) yn m
4- 2(n + l) (n + z)y nn + ( 2 n - - 1) Gn
Sb
[68]
and when the dispersed particles are present 500~
Ec = I d s " re. v c . [64]
*gb
Utilizing boundary conditions [8] to [10],
and the expressions for velocity components, o,I
and for radial component of the stress force, 100
we obtain A
o
2n n co n
50
EO=ftcbf I{Z ~,, [(V~~c~176 l~'sinm(p) ~,,I
0 0 n=l m=0

X PnnlcosO)~'s ~ [(Lmncosmr
n=lm=O
27t Jr oo i Io 4 /,4. Y //1ooo
X pm(cosO)J}sinOdOd~v + ffeb I f 2
o on=lm=O
1 [(Nnm deosmq~__+ ^ m d s i n m ~ )
X {n + 1) n dq~ Nn ..... dg~
Pnm (cos O)
X- sinO 4- (Mnm cos mq)4- M~msinm~)
n

• d0 Z,':' cos m~ + 2~sinmv)

n=l m=O 0 0,1 0,2 0,3 0,0 0,5 0,6 0,7 0,By ~
dp m 2~ ~ co s Fig. 1. Effective viscosity of emulsion. (Data: O =
(c~ sinOdOdq~+ ~cb f I Neogy and Ghosh (18) (xylene-in-water and water-in-
x- dO
0 0n=l m=0 benzene emulsions); A = Sibree (15) (limpid and vis-
( dpm cous p~raffin in water); ~ = Sherman (17) (water-in-
X 1n ( n + 1) N n~ cosm~4- 37~m sm
" m qU~ n(C~ oil emulsion) ; [~ = Broughton and Windebank (16) (model
emulsion). Solid lines represent our model (Eq. 70).
250 Rheologica Acta, Band 11, Heft 3/d (1972)
and
Xnm = (n + 3) -n-1 ~m -n+l m
2 ( n + 1 ) ( 2 n + 3) ? l)n + ? En
(n--2) • n G~n + .n+2 ~ m
-- 2 n ( 2 n - - 1) Y ~ln -
On the basis of the above expressions we
find that for two-phase multiparticle systems,
in a uniform imposed field, the effective
viscosity of the ensemble /~e~f---- 0, whereas
for both the Couette and the hyperbolic
imposed fields
~eff ~ 1 -~ 5" 5~Va~
where
4y 7 + 1 0 - - 84/11~ 2 + 4fl2(1 -- ~7)
10(1 - yl0) _ 25y~(1 - y~) + lOfl~(1 - 7 ~) (1 -~7)-
Discussion
The formulations which have been derived
here reflect the effect of the volume con-
centration of the dispersed phase through
the parameter y, and of the presence of
surfactant contaminations through the "in-
terracial retardation viscosity" ~n. The
latter does not have a unique value, but
depends on the character of the imposed
field, as shown b y eq. [A21]. Thus, when the
imposed field is represented b y spherical
harmonics of several orders, we find here
that there will be more than one "retardation
viscosity":
a) Reduction o] theory to specific solutions
The specific expressions derived from the
general theory for the case of a uniform
imposed field are identical with those
previously derived b y Gal-Or and Waslo (1)
from different considerations. The expressions
for Couette and hyperbolic imposed fields
reduce in the limit ~ - > 0 and f12-> co to
those of Taylor (11). The present results
indicate clearly that contamination of the
interface b y surfactant impurities retards the
circulatory motion within fluid particles
and reduces their deformability. This effect
is even more pronounced in concentrated
systems (large ~ value), as compared to
infinitely diluted ones (~ -~ 0).
b) Comparison with experiment
The representation of the behavior of
two-phase multiparticle systems b y "spher-
oid cell" models, even bearing in mind their
statistical nature, has been open to criticism.
It is, therefore, instructive to analyse the
predictions of theories, based on these
models, in relation to empirical data. Yaron
and Gal-Or (12) 1) have already demonstrated
the satisfactory agreement between relative
velocities of ensembles in uniform fields,
[69] predicted from the "free-surface spherical
cell" model, and experimental values. In the
present work we evaluate the realism of
predictions of the cell model in the case of
effective viscosities of both suspensions of
solid particles and of liquid emulsions. It
should be noted, that expressions [70] and
[71] for coaxial cylinders rotational visco-
[70] metry (Couette field) reduce to those of
Wacholder and Hetsroni (4) 2) for emulsions
of absolutely pure systems (yn ---- 0) and of
Happel (3) for a dispersion of solid particles
[71]
(Pn -> ~ ) . For the latter case the predicted
effective viscosity as a function of volume
concentration of the dispersed phase in the
range 0 < 7 a < 0.5 was already compared
with the experimental data b y Happel and
Brenner (10). In view of the familiar large
scatter of experimental results in rotational
viscosimetry, due to a variety of factors not
all of which are directly accountable for b y
simple theory based on energy dissipation
considerations, one may consider the extent
of agreement to be at least fair3).
I t is even more difficult to obtain reliable
data for effective viscosity of liquid emul-
sions, since surfactant contamination b y
even minute, undetectable quantities of
surfactant impurities, can substantially effect
the measurements. In fig. 1 we compare some
experimental results with theoretical curves
derived from eq. [70]. It is shown that the
theoretical lines and the empirical data both
follow the same trend.
Apparently, a considerable amount of
very careful viscometric measurements
with controlled levels of contamination is yet
necessary before one can definitely derive
conclusions regarding the relative merits of
cell models for predicting effective viscosities.
Acknowledgement
This work is supported b y G r a n t No. 11-1196 from
Stiftung Volkswagenwerk, Hannover, Germany. Com-
putational help given by M. Boazon is gratefully
acknowledged.
1) I n a most recent study, Barnea (22) has demon-
strated, t h a t our model gives the best agreement with
experimental data for a b o u t one h u n d r e d different
two-phase systems.
2) Their solution, however, erroneously contains a
slightly different numerical coefficient as compared to
our Eqn. [71].
a) q. v. also, a recent paper b y Sather a n d Lee (21).
 Yaron and Gal-Or, On viscous flow and effective viscosity o/ concentrated suspensions and emulsions 251

Summary 8) Brenner, H., Chem. Eng. Sei. 19, 519 (1964).

Previous analysis by Happel (3) of viscous flow in
concentrated solid suspensions has been extended to
include concentrated emulsions of slightly deformable
fluid particles in the presence or absence of surfactant
impurities.
General expressions were obtained for viscous flow
in multi-particle systems when arbitrary shear fields are
imposed. Specific relations were then derived for uni-
form, Couette and hyperbolic fields. The behavior is
found to be strongly dependent upon particle con-
centration and surfactant concentration. The theoretical
expressions obtained for effective viscosity of emulsions
compare favorably with experimental data of Neogy
and Ghosh (18), Sibree (15), Sherman (17), and Brough-
ton and Windebank (16). These results support other
studies on ensemble velocities [(10), (12), and in part-
icular (22)], which strongly indicate the practical value
and factual reliability of cell models in predicting the
behavior of suspensions and emulsions.
Re/erences
1) Gal-Or, B. and S. Waslo, Chem. Eng. Sci. 23,
1431 (1968).
2) Gal-Or, B., Canad. J. Chem. Eng. 48, 526 (1970).
3) Happel, J., J. Appl. Phys. 28, 1288 (1957).
4) Wacholder, E. and G. Hetsroni, Isr. J. Techno-
logy 8, 271 (1970).
5) Lamb, H., Hydrodynamics, 6th Ed. (New York
1945).
6) Newman, J., Chem. Eng. Sci. 22, 83 (1967).
7) Hobson, E. W., The Theory of Spherical and
Ellipsoidal Harmonics (Cambridge 1931).
9) Hetsroni, G., S. Haber, and E. Wacholder, J.
Fluid Mech. 41, 689 (1970).
10) Happel, J. and H. Brenner, Low l~eynolds
Number Hydrodynamics (Englewood Cliffs, N . J .
1965).
11) Taylor, G. L , Proc. Roy. Soc. 138A, 41 (1932);
ibid. 146A, 501 (1934).
12) Yaron, I. and B. Gal-Or, Amer. Inst. Chem.
Eng. J. 17, 1064 (1971).
13) Haber, S. and G. Hetsroni, l~eport GH/12, Tech-
nion-Israel Inst. of Technology, Haifa, Aug. 1970.
14) Landau, L. D. and E. M. Li/shitz, Fluid Me-
chanics (Wesley, Mass 1959).
15) Sibree, J. 0., Trans. Far. Soc. 26, (1930).
16) Broughton, G. and C. S. Windebank, Ind. Eng.
Chem. 30, 407 (1936).
17) Sherman, P., J, Soc. Chem. Ind. (London) 69,
Suppl. 2, $70 (1950).
18) Neogy, R. K. and B. N. Ghosh, J. Ind. Chem.
Soc. 29, 573 (1952).
19) Yaron, I., D. Se. Thesis, Technion-Israel Insti-
tute of Technology, Haifa 1971.
20) Hirsch/elder, J. 0., C. F. Curtiss, and /L B.
Bird, Molecular Theory of Gases and Liquids (New York
1954).
21) Sather, N. F. and K. J. Lee, Viscosity of Con-
centrated Suspensions of Spheres, paper 5 6, Int.
Symp. Two-Phase Systems, Haifa, Aug. 1971.
22) Barnea, E., D. Sc. Thesis, Technion-Israel In-
stitute of Technology, Haifa 1972.
23) Batchelor, G. K., J. Fluid Mech. 46, 823 (1972).
24) Batchelor, G. K., J. Fluid Mech. 52, 245 (1972).
25) Gal-Or, B., Modern Developments in Thermo-
dynamics (Israel Program for Scientific Translations,
Jerusalem, 1973).

Appendix
Characteristic general coefficients of the flow fields in the dispersed and continuous phase of the ensemble are:

m 2 ( 2 n + 3) / ( n + 1) m ( n - - 1) m ( n + 1) ( n + 1)(n + 2) H~] " [All

An = ( 4-(2nn~+3) Dn + ~ En 4(2n -- 1) G~ + 2n
1
Bnm m [A2]
2(2n + 3) An
Cnm = (2n + 1)2C~ Nnm [A3]

1 2(2n
Dnm = A~- (n + --1)1)
2 [(n -- 1) C 2 { M m
n (y.n+2 -- y.n\] -- 2L m
n [(n + 2) nTn+2 -- (n -- 1) (n q- 1)~n]}

+ n C,{M: ~(Vn+2 -- , - n + l ) __ 2Lnm [(n + 2) n v n+2 -- (n -- 1) (n + 1)~,-n+l]}

+ n(n + 2)C,[M:n -- 2 (n -- 1)(n + 1) Lnm] (r - n + l - rn)]. [A4]

E ~ : A--n-
" 1 4(2n +(n3)
+ (2n
1)2 -- 1) [C5 {Mr~ (yn __yn+2) __ 2 Lnm [(n l) (n + 1)y n -- (n + 2)nyn+21}

+ n(n + 2)C,{Mnm (Vn -- ~,-n-1) _ 2 L[n [(n -- 1)(n + I)Vn -- (n + 2)ny-n-I]}

J- nCa[M~n ~ -- 2(n J- 2)nL m] (~-n-x __ vnA-2)], [A5]

F m : [ ( n - 1 ) + ~(n + 2)]C~N~, [A6]

Gnm_ Anl 2(2nn(n+1)+3) [ C s { ~ I ~ n ( v n + 2 - - v - n + l ) - - 2 L ~ n n [ n ( n ' } - 2 ) T n + 2 -- (n -- 1) (n -}- 1)7-n+1]}

+ n(n+ 2)C, {Mm (y-n-I -- y-n+1)_ 2L[~ In (n+ 2)~-n-' --(n-- i)(n+ l)y-n+l]}
+ (n -- 1)C, [M~n -- 2n(n + 2) L[ ~] (7-n-1 -- yn+2)] , [A7]
252 Rheologica Acta, Band 11, Heft 3/4 (1972)

1 n(n + 1)
Hnm = An 4(2n + 3) (2n -- 1) [ ( n . 1)C2 {M m (y-n-1 __ yn) __ 2 L m [~t (n + 2)7 -n-1 -- (n -- 1) (n + 1)7n]}

+ (7 - - + - +

-}- (75 [Mnm -- 2(w, -- l) (~t § 1)Lnm] (yn __ y-n-l)] , [A8]

Inm = (n -- i)(i _ I)C~Nnm, [A9]

where

An - n ( n + 1 ) ' ( 2 n + l) {Cs(?a y2n+2)

2(2n 4- 3) (2n -- 1) -- -5 (n -- 1)C~ (y2n+2 __ 7-1) + nOa(Z3 __ ~{-2n)

+ ~(~ + ~)c, (r -2n - ~-1)}, [AI0]

Lm -n-1 m - n + l m ~,n ~nT2~m
=Y an + Y fin "~- ~m-n-1 -- ~ t~_n_l, [All]
m = (U -- I) 7-n Yn
7Vn m -- ( n § 2) 7 n+2 ]/m
-n-l' [A12]

M nm= 2 n ( n + 2 ) 7 - n - l c d n , + 2 ( n _ l ) ( n + l ) r --n-i-1 f lmn + 2 ( n _ l ) ( n + l ) y n a n _ + 2 n ( n + 2 ) r n + 2 f l f nm_ 1" [A13]

I/C~ = (n-- l)n(n + l){[(n- i) + l(n + 2)]y- n - (A- I)(n + 2)yn+l}. [A14]

C2 = 2 (2n + ' [A 15]

C~= [I+ fin(n+ 1)(n--l)]

[A16]
n(2n + 1)
1 fin ] [A17]
C, = ~ - + (2~+ 1 ~ '
c5= [(~+ 1 ) f n ~ ( n + 2)] [AlS]
(2n + 1) J '
tec
fin-- te4 + ~n ' [A 19J

7n ( 2 n + 1) -~ o ( n i T n T el Di s ( 2 n + 1) Kn - ~ - o"
and
= tee/ttd . [A21]
Note that 7n has dimensions of viscosity. I t may be regarded as a sort of "interfacial retardation viscosity" factor'
and represents the effects due to adsorbed surfactant impurities.
A set of coefficients, identical to those given by expression [A 1] to [A9] but bearing the supersign A, can also be
obtained.

Authors' address:
I. Yaron* and B. Gal-Or
Dept. of Aeronautical Engineering
Technion - Israel Institute of Technology
Haifa (Israel)

*) Present address: Division of Fluid, Energy and Aerospace Sciences, Case Western Reserve University
Cleveland (USA).