Wall Slip Effects On Dynamic Oscillatory Measurements

Wall Slip Effects on Dynamic Oscillatory Measurements
Ann S. Yoshimura and Robert K. Prud'homme
Citation: Journal of Rheology (1978-present) 32, 575 (1988); doi: 10.1122/1.549982

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16:21:06
Wall Slip Effects on Dynamic
Oscillatory Measurements
ANN S. YOSHIMURA and ROBERT K. PRUD'HOMME

Department of Chemical Engineering, Princeton
University, Princeton, New Jersey 08544
INTRODUCTION
Concentrated emulsions, suspensions, foams, and polymer so-
lutions often appear to slip along confining walls. This apparent
slip is usually caused by large velocity gradients in a thin region
adjacent to the wall, where the viscosity is low because of a re-
duced concentration of the suspended phase. It has been shown
that wall slip phenomena can have large effects on steady shear
rheological measurements.v" If slip occurs, the apparent viscosity
can be significantly lower than the actual viscosity.
Effects of wall slip on dynamic oscillatory shear measurements
are less well understood. The stress waveforms obtained from
dynamic oscillatory experiments on emulsions and dispersions,
which one might suspect to slip at boundaries, are often quite
complex. Our initial goal in this work was to see whether it was
possible to determine from the shape of the waveform whether
slip was occurring. To understand what characteristics are re-
quired of a slipping layer to produce nonlinear waveforms, we
propose a simple model of slip. The governing equations of mo-
tion are derived and three special cases are considered: (1) the
fluidity of the slip layer (i.e., the proportionality constant be-
tween stress and slip velocity) is constant, (2) the fluidity depends
on stress, and (3) the fluidity has a time dependence. A linear
viscoelastic model is chosen to represent the bulk fluid rheology,
so that nonlinearities arise from slip effects alone. To perform
calculations, parameters describing the bulk fluid and slip flu-
idity have been obtained from independent measurements on a
model emulsion we have described elsewhere.v'
The results show that the constant fluidity model predicts
linear waveforms with phase shifts related to the fluidity and
© 1988 by The Society of Rheology, Inc. Published by John Wiley & Sons, Inc.
Journal of Rheology, 32(6), 575-584 (1988) eee 0148-6055/88/060575-10$04.00
16:21:06
576 YOSHIMURA AND PRUD'HOMME
viscoelastic properties of the fluid; the stress-dependent fluidity

results in nonlinear but symmetric stress waveforms; and the
dynamic fluidity model can mimic the nonlinear, nonsymmetric
waveforms observed experimentally.
In work done in parallel with this study we have investigated
the effect of yield stresses on dynamic oscillatory measurements"
in the absence of slip. Materials that are prone to slip are also
prone to display yield behavior. Nonlinear, non symmetric wave-
forms of similar shape can result from slip (as shown by this
study) or yielding (as shown in ref. 4) even for materials with
linear bulk rheological properties. The shape of the stress wave-
form is, therefore, not a definitive indicator of the presence or
absence of slip. Measurements with two-gap separations at the
same frequency and strain can determine whether slip occurs.
If stress waveforms from both measurements are identical, then
slip is not occurring, and nonlinearities or phase shifts are due to
the bulk fluid properties. If the waveforms differ then slip is
occurring. Because slip may depend on both stress and time, it is
not possible to extract bulk fluid properties from measurements
using two-gap separations as can be done for steady shear in
capillary" or parallel plate geometries. 5
EQUATIONS OF MOTION FOR SLIP

We assume that the slip layer (the high velocity gradient re-
gion) is very thin so that we may represent wall slip as an actual
discontinuity in velocity at the wall. The difference between the
velocity of the wall and of the fluid at the wall is the slip velocity,
US' The fluidity of the slip layer, tp, is defined as the ratio of the
slip velocity to stress at the wall,
Us
ip =-. (1)
T
The fluidity can be thought of as an effective thickness of the slip

layer, divided by the slip layer viscosity.
Because we were interested in viscoelastic foams and emul-
sions, we chose a constitutive equation for the bulk material that
includes viscous and elastic effects. A simple Kelvin-Voigt mate-
rial has a constitutive relationship given by
dy
T = T/ dt + Gy (2)
16:21:06
EFFECTS OF SLIP ON DYNAMIC DATA 577
where
T = shear stress
TJ = viscosity
y = shear strain
t = time
G = modulus.
The dynamic moduli for this material are
G' = G
G" = WTJ
where W is the frequency of the oscillatory strain. The loss tan-
gent is then
tan () = G "/0' = WTJ

0'
The fluid is contained between infinite parallel plates sepa-
rated by a distance H (Fig. 1). The bottom plate is stationary
while the top plate oscillates with frequency wand displacement
amplitude x o ,
X p = x, sin wt. (3)
From Figure 1, we see that
dx; dy
-;It = Us + H dt + us' (4)
I--l
Us
I---l
Us
Fig. 1. Velocity profile for a fluid confined between parallel plates in the
presence of wall slip.
16:21:06
Combining with Eq. (3) and the definition of the slip layer fluid-
ity [Eq. (1)J leads to
dv lUXo cos wt - 2ipT
(5)
dt H
This equation is then combined with the Kelvin-Voigt model
[Eq. (2)J to obtain
1]
T= H [lUX o cos wt - 2ipT] + Gy. (6)
Differentiating this result with respect to time gives
dr
dt = - H
1] [2' dip dT] dy
w x, sm wt + 2T dt + 2ip dt + G dt (7)
and combining once again with Eq. (5) yields
-dr = - - 1] [
w2x .SIn
dip + 2ip-
wt + 2T- dT]
dt H 0 dt dt
G
+ H [lUX o cos wt - 2ipT]. (8)
We now introduce dimensionless variables for time, fluidity,

and stress,
T = wt (time)
<P = --'t (fluidity)

ipo
1 = Tipo (stress)
lUX o
and define two dimensionless parameters,

V = 1]ipo
H
E = Gipo
wH
where ipo is a characteristic value of the fluidity. The parameter
V is the dimensionless viscous component and E is the dimen-
sionless elastic component of the fluid. Using these dimensionless
variables and parameters, Eq. (8) can be written as
16:21:06
d'i.
dT = - V [ sm
. T + 2~ d¢ d'i.] + E[cos T - 2cI>~].
dT + 2cI> dT
(9)
Ifwe assume a functional form for the fluidity function, cI>, we can
use Eq. (9) to solve for the stress as a function of time.
Constant Fluidity
We first consider the case where the fluidity is constant,
'P = 'Po·
This is equivalent to assuming the effective thickness of the slip
layer is independent of stress. Equation (9) then becomes
d'i.
dT = - V [ sin
. T + 2 dT
d'i.] + E[cos T - 2'i.] (10)
and its steady-state solution is found to be

E V + 2V 2 + 2E 2
'i. = 1 + 4V + 4V 2 + 4E 2 sin T + 1 + 4V + 4V2 + 4E2 cos T.
(11)
The stress is linear (sinusoidal) and is shown in Figure 2 for

parameter values V = 0.24 and E = 0.6, corresponding to
0.5
w
ui 0
-
til
~
en
- 0.5
0 1t 271: 31t
Time, T
Fig. 2. Calculated stress response for slip layers with constant fluidity, <P = 1.
Parameters are V = 0.24 (fluid viscous component) and E = 0.6 (fluid elastic
component).
16:21:06
TJ = 80 poise
G = 4000 dyn/em"
!Po = 1.5 X 10- 4 em/poise
W = 20 S-1
H = 0.05 em.
The values for TJ and G were chosen as reasonable values for an
oil-in-water emulsion," while wand H are typical for dynamic
experiments. The parameter !Po is the zero-stress fluidity obtained
from steady-shear experiments on an oil-in-water emulsion."
The loss tangent can be calculated from Eq. (11),
{) _ Y + 2y 2 + 2E 2 _ WTJ 2WTJ2!po 2G!po (12)
tan - E - G + GH + wH'
Note that as the slip layer fluidity goes to zero (no slip), the loss
tangent approaches the actual loss tangent for the fluid,
WTJ
tano-C'
When the fluidity is non-zero, the loss tangent is larger than the
actual loss tangent. Thus the presence of slip makes the fluid
appear to be less elastic than it really is.
Stress-Dependent Fluidity
Steady-shear experiments on an oil-in-water emulsion' have
shown that the fluidity of the slip layer increases nearly linearly
with stress, but has a non-zero intercept at stress equal to zero.
Accordingly, we now assume that the fluidity varies with stress as
In dimensionless form,
<t> = 1 + MI!I
where
= mwx: o
M 2 •
!Po
16:21:06
This expression is inserted into Eq. (9) to obtain
~ = -v [sin T + 2~ ± 4M!~] + E[cos T - 2!::;: 2M!2]

(13)
where the upper signs apply when ! > 0 and the lower signs
apply when! < O. This equation was solved using a fourth-order
Runge-Kutta scheme for the parameter values
v= 0.24
E = 0.6
M = 133.
The value for M corresponds to the parameters

m = 10-6 em/poise . dyn
w = 20 s"
x, = 0.15 em
'Po = 1.5 X 10- 4 em/poise.
Steady-shear experimental values were used for m and 'Po, while

x, and ware typical experimental parameters. The resulting
stress waveforms (Fig. 3) are nonlinear (nonsinusoidal) and
symmetric.
0.1
u>
so 0
...
Q)
Ci5
- 0.1
0 n 21t 3n
Time, T
Fig. 3. Calculated stress response for slip layers with stress-dependent fluidity,
<P = 1 + MI~I. Parameters are V = 0.24 (fluid viscous component), E = 0.6 (fluid
elastic component), and M = 133 (slope of the fluidity vs. stress relationship).
16:21:06
Dynamic Fluidity
The relationship between fluidity and stress, which we used in
the previous analysis, was measured during steady-shear experi-
ments. Therefore, it can be considered an equilibrium relation-
ship. In dynamic experiments, where the stress is continuously
changing with time, the fluidity may not be able to adjust instan-
taneously to the current stress. Assuming first-order kinetics, we
can represent the rate of change of fluidity as
drp
dt = K[rpeq - rp]
where K is a growth constant and rpeq is the equilibrium fluidity

given by
rpeq = rpo + mlTI·
Converting to dimensionless variables and solving for stress gives
I~I = - 1 [ - 1 -d<f> + <f> - 1 ] (14)

M NdT
where
N=~.
w
Inserting this expression into Eq. (9) results in

2<f> 2<f>
2V d 1 d 2V d d [ 2E] d
N dT 2 + N dT 2 + N dT dT + 4V + N <f> dT +
(1 - 2V) ~~ + 2E2 - 2E<f> ± (VM sin T - EM cos T) = 0

(15)
where the positive sign on the last term applies when ~ > 0 and
the negative sign applies when ~ < O.
Equations (14) and (15) were solved using a fourth-order
Runge-Kutta scheme for the conditions
V = 0.24
E = 0.6
M = 133
N = 2.
16:21:06
0.1
uf
CI) 0
a.>
....
tf;
- 0.1
0 n 2rr 3rr
Time, T
Fig. 4. Calculated stress response for slip layers with dynamic fluidity,
d<P/dT N[ - <P,q] where ,q = 1 + MI~l Parameters are V = 0.24 (fluid vis-
=
cous component), E = 0.6 (fluid elastic component), M = 133 (slope of the fluidity
vs. stress relationship), and N = 2 (fluidity growth rate constant).
The value of N corresponds to an experiment frequency of w =

20 S-1 and a fluidity growth constant of K = 40 S-1. The resulting
stress waveforms (Fig. 4) are nonlinear and nonsymmetric.
Since we have assumed linear behavior for the fluid, the non-
linear nature of the calculated stress response is caused by slip
effects alone. If the fluidity is in equilibrium with the stress, then
the resultant stress waveforms will not be linear (i.e., simple sine
waves containing only the first harmonic) but they will be sym-
metric. Nonequilibrium (i.e., time-dependent) fluidity relations
are necessary to produce nonlinear and non symmetric wave-
forms. In another study;' we have shown that the same type of
stress response can result from nonlinear properties of the fluid,
therefore, we cannot easily distinguish between the effects of slip
and of fluid rheology. Consequently, wall slip must be eliminated
before dynamic oscillatory data can be interpreted properly.
References
1. Y. Cohen and A. B. Metzner, J. Rheal., 29, 67 (1985).
2. R.J. Mannheimer, "Rheological Evaluation of Cement Slurries," Final Re-
port No. SWR·6836, Southwest Research Institute, San Antonio, TX (1982).
3. A. S. Yoshimura and R. K. Prud'homme, "Wall Slip Corrections for Couette
and Parallel Disk Viscometers," J. Rheal. 32, 53-67 (1988).
4. A. S. Yoshimura and R. K. Prud'homme, "Response of an Elastic Bingham
Fluid to Oscillatory Shear," Rheol. Acta 26,428-436 (1987).
16:21:06
5. A. S. Yoshimura, Foam and Emulsion Rheology, Ph.D. thesis, Department of

Chemical Engineering, Princeton University, 1987.
6. M. Mooney, J. Rheol., 2, 210 (1931).
Received September 14,1987

Accepted January 12, 1988
16:21:06

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Wall Slip Effects on Dynamic Oscillatory Measurements

Ann S. Yoshimura and Robert K. Prud'homme

Citation: Journal of Rheology (1978-present) 32, 575 (1988); doi: 10.1122/1.549982

Articles you may be interested in

Wall Slip of Narrow Molecular Weight Distribution Polybutadienes

A Comparison of Techniques for Measuring Yield Stresses

Wall Slip in Viscous Fluids and Influence of Materials of Construction

ANN S. YOSHIMURA and ROBERT K. PRUD'HOMME

viscoelastic properties of the fluid; the stress-dependent fluidity

EQUATIONS OF MOTION FOR SLIP

The fluidity can be thought of as an effective thickness of the slip

tan () = G "/0' = WTJ

Differentiating this result with respect to time gives

and combining once again with Eq. (5) yields

We now introduce dimensionless variables for time, fluidity,

<P = --'t (fluidity)

and define two dimensionless parameters,

and its steady-state solution is found to be

The stress is linear (sinusoidal) and is shown in Figure 2 for

This expression is inserted into Eq. (9) to obtain

~ = -v [sin T + 2~ ± 4M!~] + E[cos T - 2!::;: 2M!2]

The value for M corresponds to the parameters

Steady-shear experimental values were used for m and 'Po, while

where K is a growth constant and rpeq is the equilibrium fluidity

I~I = - 1 [ - 1 -d<f> + <f> - 1 ] (14)

Inserting this expression into Eq. (9) results in

(1 - 2V) ~~ + 2E<I>2 - 2E<f> ± (VM sin T - EM cos T) = 0

The value of N corresponds to an experiment frequency of w =

5. A. S. Yoshimura, Foam and Emulsion Rheology, Ph.D. thesis, Department of

Received September 14,1987

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