DEVELOPMENT OF A PREDICTIVE POWER LAW RELATIONSHIP FOR

CONCENTRATED SLURRIES, PART 1: THEORY

Gregory A. Campbell, Castle Associates, Jonesport, Maine 04649
Michael E. Zak, Xerox, Webster, New York
Jayaprakash. S. Radhakrishnan, General Electric Power and Water, India
Mark D. Wetzel, DuPont, Wilmington, Delaware 19803

Abstract viscosity is positive definite) and n is the power law

constant. If n=1, then k is the shear rate independent
All polymer slurries that have a high concentration of viscosity.
filler are shear thinning. This can include the starting
materials for sheet molding compound, polymer based
inks, many reactive extrusions systems, and polymer
concentrates that are let down in extrusion systems as
color concentrates or opacifiers. Several sizes of calcium
carbonate were initially investigated because of their
extensive use in the polymer industry as fillers. The
investigation focused on developing an analytical tool that
would lead to understanding and the prediction of the
flow characteristics of slurries that have a Newtonian
continuous phase but have high enough filler
concentration to exhibit shear thinning or power law
characteristics. This works focuses on concentrations
where the initial yield behavior is not dominant A new
function was found that linearly correlates the power law Figure 1. Polymer viscosity vs. shear rate response.
constant, n, to the concentration of the filler. The A capillary rheometer is an instrument often used for
behavior of this function suggests that the Newtonian to measuring the rheological properties of a fluid. The
Power-law behavior may be dominated by percolation Instron capillary rheometer used in this project for the
processes. We present here a theory that predicts the calcium carbonate slurries was operated at pre-selected
characteristic of the power law constant, n, as a function rates. A load cell was used to measure the force required
of filler concentration and is based on observing and to push the fluid through the capillary. A capillary, with a
modeling the well-known plug formation in the center of known length and inside diameter, was secured in the
a tube as the material flows down the tube. The plug was bottom of the barrel. The barrel was a thick, steel pipe
experimentally shown to be a non-dissipating volume in that rested in a ball and socket joint. Four band heaters
the flowing slurry. This percolation based rheological encircled the barrel for temperature control. The fluid
analysis was then extended to a highly filled Polyethylene that was to be tested was placed in the barrel. The
resin. plunger, fixed into the load cell that was at the end of a
ram, was driven at the desired rate.
Introduction
Four grades of calcium carbonate were used and the
The general relationship for the viscosity of slurries
percolation concentration, c, and the maximum
is diagramed in Figure 1. At very low shear rates the
concentration, m, were found to be:
viscosity acts in a Newtonian manner and the viscosity is
independent of the shear rate. As the shear rate is Particle Type Nominal Avg. c m
increased the apparent viscosity often decreased as the Particle Size
shear rate is increased. The power law region found in Omyacarb 21 21 m 0.1726 0.5930
Figure 1 is indicative of this rheological response. As the Omyacarb 10 0.1732 0.6061
10 m
shear rate continues to increase the slurry often becomes
Newtonian again but at a much lower value, infinite Camel-WITE 3 m 0.2006 0.5360
shear viscosity, than in the low shear rate Newtonian CAL-ST 0.7 m 0.2327 0.6732
plateau. For simple, one-velocity component flow, the
viscosity-power law relationship is: The percolation concentration and maximum
concentration for these systems were determined using
n 1
= k ! (1) the viscosity data. Best fit line as seen in Figure 2 and the
function in equation 11 yield both c, and the maximum
where is the viscosity, ! is the one component shear concentration, m.
rate (the absolute value brackets are used because

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 The percolation threshold concentration changed with
particle size. The largest two particle sizes showed
essentially the same threshold volume fraction, 0.173.
This value was close to the theoretical value of 0.16. For
the 3.0 m Camel-WITE particles, and then again for the
0.7 m CAL-ST particles, the threshold concentration
shifted to a higher concentration with a decrease in
particle size. The size of the Omyacarb 10 and 21
particles was such that hydrodynamical interactions
dominated colloidal forces. However, the Camel-WITE
and CAL-ST particles were influenced by colloidal
forces. Brownian motion, which tends to randomize the
location of particles in a suspension, was the greatest
colloidal interaction since the other colloidal forces had
been minimized. The stearic acid treatment of the CAL-
ST particles played an additional role in delaying the start
of shear-thinning behavior. This increase in threshold
concentration as the particle size went below one micron
could also be modelled by directed percolation. In
directed percolation, the lattice is sensitive to particle
properties and the probability of connectedness is
adjusted.
The results were previously reported in an ANTEC
paper in 2001 [1]. A typical result for the power law
function of calcium slurry in a polyol is found in Figure 2.
The data indicate that there was a linear relationship
between the power law and the concentration to the 2/3
power. This may imply that the power law is a function
of some surface area related to the particles.
These results led to work on the development of a
theory that would relate the power law to the
concentration of the filler in the slurry. What follows in
the next section is a proposed mechanism for the
development of the power law and a mathematical model
based on that theory.
Figure 2. Power law vs. calcium carbonate filler
concentration, from Zak Thesis [2].
Theory Development
Power-Law Index, n
The following mechanism is proposed as a physical
model for the shear-thinning behavior of concentrated
suspensions under laminar flow conditions. What follows
is the theoretical development. A more complete
description can be found in [2,3]. In sufficiently
concentrated suspensions, it has been shown
[4,5,6,7,8,9,10,11-22] that macroscopic structures were
present as the suspension was deformed. These
macroscopic clusters of agglomerated particles had a
significant effect on the behavior of the suspension.
Experimental evidence [4,5,8,10,16] showed that there
was no motion amongst the particles within these clusters.
This led to the hypothesis that the power law region of the
viscosity curve reflected the change in volumetric energy
dissipation related to the concentration of the filler and
the shear rate.
Brenner [23] calculated the relative zero-shear
viscosity of a suspension from the amount of work done
by the suspension on the available particle surfaces. The
relative viscosity as a function of filler surface area is
thus:
p ni ui dS
s0 + Si
r = (2)
(0 ) (0 )
p
s0
ni u dS i
where pn was the outer normal traction on the surface and
ui was the velocity vector. The super script (0) indicates
the calculation for the pure fluid. When particles were
added to the suspending fluid, the surface area upon
which the fluid could act increased. This led to an
increase in the dissipation rate. The new dissipation rate
for the filled system is in the numerator of the relative
viscosity function, r.
For pure suspending fluid, the fluid can only perform
work on the container surfaces, So. For this case of pure
suspending fluid, the dissipation rate is the denominator.
At low shear rates, when particles were added to the
suspending fluid, the surface upon which the fluid could
act was increased because the clusters could reorganize.
This led to an increase in dissipation rate. The numerator
in the previous equation reflects this change; where the
effect of the particle surfaces, Si, was summed in addition
to the pure fluid as a result of the cluster/floc
reorganizing with the resulting increase in energy
dissipation.
Suspensions at moderate concentrations show
Newtonian behavior at low shear rates and then exhibit
shear-thinning behavior at higher shear rates. It was
previously proposed by Campbell and Forgacs [24] that at
low shear rates, particles in a cluster had time to
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rearrange, allowing the cluster to deform as a result of the
imposed flow field. The particles rearranged themselves
by moving into existing holes within a cluster [24] or past
neighbors. This allowed for stress to be transferred
throughout the suspension and for the fluid to perform
work on all of the particle surfaces, thus yielding a
Newtonian viscosity.
m c characteristics of the suspension. Even though the power-
law index changes with shear, a gradual transition from
m Newtonian to fully developed power law, there is a
0 = e
1 (3)
where 0 = Newtonian viscosity
m = Maximum packing concentration
c = Percolation concentration
= Filler concentration
This was similar to the idea of a characteristic time for a
material put forth by Heyes and Melrose [25]. Their
characteristic time was a measure of the time required for
significant local structure change to occur in the
unsheared material.
As the shear rate increases within the flow field, it is
proposed here that large fractions of a cluster must
cooperatively rearrange. At some point, the stress
required for the particles in a cluster to locate and move
into the existing holes as a group, is larger than the locally
applied stress on the cluster. When this occurs, that part
of the cluster, where the particles cannot move into holes,
flows without rearranging. Eventually, the whole cluster
cannot deform. In the flow regions where there is no
rearrangement of clusters, particle surface area is
excluded from the shear rate in the fluid. Thus the fluid
cannot perform work on those particulate surfaces in the
non-deforming cluster. This leads to an analysis of the
thermodynamics of the viscous dissipation of energy in
suspension flow in the manner described below.
No relative motion within a cluster suggests that
there is no viscous dissipation of energy within that
cluster. Thus, all of the dissipation of energy must take
place in the regions surrounding the non-dissipative
clusters. These regions can consist of pure suspending
fluid, individual particles, and smaller sized particle
agglomerates that deform. The container surface, the
individual particles and the surface of the particles within
the deformable clusters, and the outer surfaces of the
macroscopic non-deforming clusters are the only surfaces
upon which the fluid can act. Therefore, it is proposed
that it is the loss in surface area upon which the fluid can
perform work that is responsible for the apparent decrease
in the viscosity. Using Green's theorem, one can look at it
as a loss in volume that is capable of viscous energy
dissipation. This hypothesis is an alternative to past
analyses [26,27-32,33,34] where the whole volume of the
suspension was taken to be dissipative and was usually
analyzed as a Newtonian system.
In this analysis, as the shear rate increases above the
critical shear rate, clusters and parts of clusters cease to
dissipate energy. The viscosity drops below the zero-
shear Newtonian value and continues to decrease as more
and more particle surface area is excluded from doing
work. This continues to a certain point, determined by the
volume fraction of solids and other physical
central region in shear rates of constant slope that can be
described with a single value. It is proposed that this
value depends directly upon the final size of the non-
dissipative structure and it is the development of this non-
dissipative volume that is being modeled here. For
concentrated suspensions, the power-law index appears to
be a log normal distribution depending on shear rate.
This log normal distribution has been shown to be true for
polymer melts; suspension data suggests the same.
When the whole suspension can dissipate energy, the
behavior is Newtonian. As the concentration increases
above some critical concentration for cluster formation,
macroscopic clusters form and the volume of these
clusters increases with the concentration. This, in turn,
increases the shear-thinning behavior at those shear rates
that do not allow time for structure rearrangement. It
follows that the power-law index, which indicates the
amount of shear-thinning, decreases from its Newtonian
value of unity towards zero as the clusters grow and the
maximum packing fraction is approached; see the
experimental data for calcium carbonate presented in
Figure 2. As the maximum packing fraction is
approached, the volume available for energy dissipation
decreases toward 0. This analysis only applies when the
concentration and the shear rate combine to produce
pseudo-plastic behavior that can be described by a single
power-law index.
The proposed definition of the power-law index
based upon this model is the ratio of (1) the viscous
dissipation of energy in the volume of the suspension
minus that volume occupied by the non-dissipative
clusters, to (2) the dissipation that would occur if the fluid
that is dissipating energy could occupy the total volume
available. The power-law index definition in terms of
surface areas is then:
d ij dV
v vc
ij
n= (4)
ij d ij dV
v
This general model for the power-law index predicts n = 1
when the volume of the non-deformable cluster Vc = 0,
and it predicts that n will approach zero in the limit when
Vc reaches V. All models are correct based on the
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assumptions used to develop the model. However, to
determine the potential utility of a model in predicting
outcomes, it is necessary to validate the model using
quantitative data relating to the system that it will be
applied. In order to evaluate the utility of this model for
prediction of the power-law index, one must quantify the
non-dissipative volume and evaluate the integrals.
The original analysis for dilute slurries was proposed
by Einstein [26]. The approach developed here is an
extension of the approach of those analyses that take the
interstitial fluid in flocs into account when calculating the
zero-shear suspension viscosity [35,36,37,38]. In those
analyses, the fluid inside of the flocs is said to be
effectively excluded since it does not interact with the
remaining suspension. Thus the volume fraction of solids
is raised, causing the increase in the viscosity. In the
present analysis, the fluid associated with the non-
deforming clusters is removed from the dissipation zone
of the slurry and is incapable of dissipating energy as
well. It is this volume of the fluid not dissipating energy
that is responsible for the shear-thinning behavior.
Graham et al. [37] on the other hand, attribute it to the
shape of the flocs.
Application of Power-Law Index Model
Due to the current lack of quantitative data for the
location and amount of structure formation in Couette,
cone and plate, and other linear flow viscometers, it was
not possible to experimentally relate the power-law index
for those cases to the non-deformable clusters. However,
the results of the experiments by Karnis et al. [5,6]
provided information concerning the shape of the velocity
profile, and the size and location of the non-dissipative
structure (that being the core cluster) in Poiseuille flow.
Similar information was obtained more recently by
Altobelli et al. [39] with nuclear magnetic resonance
imaging that supported the results of Karnis et al.
Therefore, an expression for the power-law index was
developed by using this information from capillary flow.
Capillary geometry was used to test this hypothesis
because all of the structure was centrally located and thus
the respective volumes could be quantified. Also, it was
relatively straight forward to measure the pressure drop
across the tube as the structure was being measured thus
providing a classical approach to evaluate the power law
constant, n.
From a visual inspection of the velocity profiles of
Karnis et al. [5] a Bingham model of the stress tensor was
chosen for modeling the flow field in the dissipative
region. This choice assumed that the behavior was
Newtonian in the dissipative region. The Bingham model
allowed the diameter of the core cluster to be specified.
The stress was given as:
y 1
ij = 2 b + d ij for ( ij ij ) > y2
4 II d 2
(5)
1
ij = y for ( ij ij ) < y2
2
where the yield stress, y, governed the size of the central
core. The use of a yield stress model was similar to the
idea put forth by De Gennes [40]. This idea was that
partial plug suspension flow can be examined as a flow
containing two unique velocity fields. De Gennes also
suggested that the central core was assumed to be more
like a solid. For Poiseuille flow, the stress was given by:
dU
rz = b Z
+ y for R > Rc (6)
dZ
rz = y for R Rc (7)
This Bingham model predicted the blunted velocity
profiles reported by Karnis et al. for the experimental
observations listed [6]; (1) The ratio of the centerline
velocity of the suspension to the centerline velocity of a
Newtonian fluid, flowing at the same flow rate, was less
than one. (2) The ratio of the velocity of the suspension
at some radial position to the velocity of a Newtonian
fluid at the same position, flowing at the same flow rate,
was greater than one. (3) The shear rate of the suspension
was greater than the shear rate for a Newtonian fluid near
the tube wall and less than the shear rate of a Newtonian
fluid away from the wall. (4) A linear relationship existed
between the pressure drop and the flow rate.
The denominator of expression Equation 8 for the
power-law index was defined for a suspension flowing
through a tube without a central core. This corresponded
to a Bingham fluid flowing with a yield value of zero, for
which the velocity profile simplified to the Newtonian
expression. The pressure drop for both flow cases (i.e.,
that with a central core and that without a central core)
and the tube geometry were assumed to be equal. Now
the defining expression for the power-law index was
written as:
R
d ij rdr
Rc
ij
n= R
(8)
* *
ij d ij rdr
0
The * indicates that these terms represent the zero
core size expression and the corresponding flow field.
The results of the and z direction integrals cancelled out.
The upper integral in this analysis was over the annulus
where there was enough shear stress to deform the local
clusters. The integration was thus carried out only over
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 the volumes that were dissipating energy. After value as the average flow rate was increased. A stylized
evaluating the integrals using the viscosity model and representation of flow characters of the data found by
cancelling like terms, the expression for the power-law video analysis is presented in Figure 5. There is a blunted
index was: velocity profile typical found in the experiments when the
fluid presented power law characteristics using the
4 1 pressure drop across the tube. Flow visualization
n =1 + 4 (9)
3 3 indicated the particles in the core did not have any relative
where motion; they acted as a large non-dissipating cluster while
the particles toward the walls moved relative to one
Rc y
another deforming the clusters and thus dissipating
= = (10)
R rz (r = R) energy. This is consistent with the theory developed in
the preceding paragraphs.
The upper and lower limits of n were correct. When
there was no plug present, = 0. Newtonian flow was
predicted, n = 1. As the core size approached the size of
the tube, 1, the volume for dissipation went to zero
and n approached zero as well. The validity of equation
for n was substantiated by the fact that = 1 was the only
real root. Perhaps the most common and widely used
non-Newtonian model for pseudoplastic fluids is the
Ostwald and de Waele's power law [41]. This has since
the late 1920s been considered to represents an apparent
or effective viscosity as a function of the shear rate for
many types of shear thinning data. In contrast, what we
propose here is physics based theory for shear thinning of
at least Newtonian fluid based slurries.
Experimental
Data on the core to capillary ratio and the corresponding Figure 3. Experimental system for power law - structure
values of the power-law index were needed in order to verify correlation.
this expression. No literature data providing both pieces of
information were found. Therefore, it was necessary to run
the appropriate experiments to obtain the data required to test
the expression for n. A laboratory set up of the necessary
equipment, as seen in Figure 3, was developed and used to
gather the data needed to correlate the core structure and the
power law calculated using pressure drop in the capillary.
The complete experimental procedure may be found in the
Zak or Radhakrishnan theses [2,3]. A fluid with matched
refractive index to the PMMA particles was developed. A
small quantity of polystyrene latex was added to give
markers that would be visible using ultra violet light. Video
was taken during the experiments and used to determine the
local velocity in the tube as a function of both position away
from the wall and the average fluid flow rate. Using the
video the local velocity was calculated after calibration of the
pixel position with the tube characteristics.
Application of Theory to Data
Figure 4. Slurry Velocity Profile as a function of filler
Figure 4 shows typical velocity profiles when the concentration (concentrations: 1 less than
fluid changes from acting in a Newtonian manner to percolation, 2 and 3 concentrations increasing
having more structured characteristics. The radius of the above percolation).
non-dissipating core, Rc, was found to increase with both
The next question is does the size of the non-
filler concentration and average slurry velocity. In other
dissipation cluster relate to the power law traditionally
words at concentration above the percolation threshold
determined using the pressure drop across the length of
the fluid acted in a Newtonian manner at very low shear
the tube. The Rc/R values were used to calculate the
rates and transitioned to a power law fluid as the velocity
power law as predicted in Equation 9. This power law
increased. The size of the core increased to an asymptotic

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percolation based theory was then plotted in a parity plot
against the power law calculated from the classical
pressure drop data for flow in a tube, Figure 6.
rheometers. Thus it is proposed that the reduction in
dissipating volume in the structure in the filled system is
independent of the imposed shear field and is a
characteristic of the percolation induced clusters that do
not internally rearrange at these shear rates and thus do
not contribute to the slurry dissipation. In most flow
fields these percolated clusters would be distributed
thorough the sheared mass but if n is the same it would
follow that they have the same reduction in sheared-
dissipating volume as observed in the Poiseuille flow
described in the previous paragraphs at equivalent filler
concentrations.

Figure 5. Slurry velocity profile demonstrating structure

formation in low shear stress zone of tube.
A linear relationship is found with a slope of about
45o indicating an excellent correlation. This strongly
suggests that the proposed theory based on percolation
and structure development explains the development of
power law characteristics for Poiseuille Flow of
spherical particles in a Newtonian fluid. It should be Figure 6. Parity plot of power law "n" from capillary
noted that the percolation derived power law function, pressure drop vs. calculated from plug size in
Equation 9, has no adjustable parameters. Therefore, the the flowing slurry.
excellent correlation found in the parity plot strongly
suggests that the development of a non-dissipation cluster
is the root cause of the shear thinning in these slurries.
Both Zak [2] and Radhakrishnan [3] used the same
equation to correlate the power law in the percolation
concentration range:
-2/3

1

n = m - 2/3 (11)
c
1
m
However, they used different criteria to determine the
constants, c, and, m. The results using these separate Figure 7. Power law constants from two data sets [3].
criteria are presented in Figure 7. It is seen that both
approaches produced excellent correlation for the data Application of Theory to a Filled Polymer
taken by both Zak and Radhakrishnan. These results led to an investigation of how this
Here we suggest that nature would be consistent dissipation mechanism proposal would be used to
regarding the development of macro clusters in a flowing interpret the development of the power law in a filled
system regardless of the shear field. Experimentally it is polymer system. The system used was a LDPE filled with
generally observed that the power law for a filled system TiO2 incrementally up to 0.495 volume fraction. The neat
is the same regardless of the shear field. That is in the polyethylene viscosity shear rate relationship is plotted in
laboratory the observed power law, n, is usually found to Figure 8. Using the last 8 points, shear rates from 223 s-1
be the same in parallel plate, cone and plate, and capillary to 4999 s-1 the power law index, n, was found to be 0.361.
The base resin was then filled with TiO2 with solid

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fraction from 0.0265 to 0.495. It is well know that at the
critical molecular weight PE has essentially no shear
thinning, and therefore might be considered to be a theta
solvent at all temperatures for the higher molecular
weight polymer molecules. As the molecular weight
increases the fraction of this solvent decrease such that
the large molecules, ~ 10 nm, become insoluble and
because they have collapsed into a Gaussian sphere.
They are proposed here to act in the molten polymer as
deformable fillers. When the melt is sheared, they thus
decrease the volumetric dissipation in a similar manner
that was observed for the Newtonian fluid slurries.
Figure 8. Viscosity vs. shear rate for LDPE at 398K.
Equation 9 defines the relationship between power law n
and the fraction of the flowing system that dissipates
energy and was found to work very well for Newtonian
filled systems. This relationship has non-linear structure
as shown in Figure 9. When the core radius is equal to
the tube radius the power law is 0.0 and essentially all of
the slurry is in the non-deformable infinite cluster.
Equation 3 has been shown to correlate with many filled
systems over a wide range of filler concentrations at
limiting shear.
Figure 9. Power law core size relationship for tube flow.
It is apparent that none of the data in this study reaches
low enough shear rates to truly be limiting shear. The
lowest shear rate for the data sets from 0.0 to 0.495
volume fraction filler content was 10 s-1. Equation 3 was
used to evaluate the low shear viscosity shown in Figure
10. In this case, the percolation concentration was found
to be 0.24 and the maximum concentration was found to
be 0.98 to provide a good fit over the entire filler
concentration range at 10 s-1. It would have been
expected that the percolation concentration would be 0.3
or higher since Brownian motion would increase this
value from the nominal value of 0.16 for
hydrodynamically dominated slurries. However, the
shear rate is well above the limiting shear rate. This is
thought to explain this somewhat low percolation
concentration.
Figure 10. Data correlated with the Campbell-Forgacs
percolation model [24].
The plot of the power law for all of the samples with
concentration from 0 to 0.495 volume fraction filler is
shown in Figure 11. It is observed that at the low
concentration, the power law values at the highest x-axis
values do not fall on the power law line of 1. The
previous results of the Newtonian slurries in this paper
indicate that all of the sheared volume is dissipating
energy when n = 1 per Figure 7 from Equation 11 when
is equal to or less than c. The base polymer in Figure 11
had an n = 0.36.
Figure 11. Power law of TiO2 filled LDPE at 8 loadings.
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 In the polyethylene polymer case, the dissipation of
the base polymer and of the slurry at low filler
concentrations is thought to be dominated by the proposed
cluster formed by the large polymer molecules, in the
base resin over this filler concentration range. The
relatively constant power law from the lowest
concentration of 0.0265 volume fraction suggests that the
increase in the resistance to cluster deformation resulting
from the increase in particle concentration essentially
offsets the expected increase of shear stress at the
boundary of core cluster from the higher Newtonian
viscosity in the annulus so that there is very little increase
in the size of the core cluster up to the maximum volume
fraction of 0.495. The TiO2 also has a broad particle size
distribution, PSD, as shown in Figure 12.
Figure 13. Parity plot of data vs. theory for n for volume
fractions from 0 to 0.495.
The fraction of the tube of the filled system that is
dissipating energy decreases slowly from 49 to 45%
(=0.51, =0.06; =0.55, =0.495) as the filler is
increased per Figure 11. This leads to an increase in the
shear stress at the wall and an increase in the Bingham,
plug interface, stress using this currently proposed theory
as shown in Figure 14. This assumption is based on the
filled Newtonian system discussed in the earlier sections
of this paper. The more or less constent Rc/R at higher
concentrations may be due, in part, to the observation that
the power law, n, at the maximum shear rate of this data
Figure 12. PSD of 30 wt. % TiO2 in LDPE letdown in the set may not have reached a stable critical cluster size. The
batch mixer from an 80 wt. % masterbatch. large fraction of the flowing system that is dominated by
the infinite cluster of the base polymer at all
Radhakrishnan [3] found that increasing the particle size concentrations of filler suggests that a lot of shear stress
distribution increased both the critical filler concentration would be needed to break up the filler clusters during any
and the maximum filer concentration. He also found that type of compounding, particularly at the highest filler
the power law increased more slowly with filler concentration from 30 to 49 vol. % per Figure 14.
concentration for a bimodal distribution. This suggests
that for this broad distribution, the rate of increase of the
power law with concentration would be much slower than
with narrow distribution fillers. The power law n was
calculated using Equation 9 for all of the filled data sets
by finding an optimum to fit the experimental data. The
Parity plot of this relationship for this polymer filled
system is shown in Figure 13. From our Newtonian based
theory, only 35 and 37 % of the fluid volume dissipated
energy.

Figure 14. Slurry stress in capillary flow.

Summary
A new theory based on percolation theory and the
deformation of the percolated clusters predicts that the
power law for flowing slurries is related to structure

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development in the flowing slurry. This new theory has
been tested by comparing its predicting with traditional
power law calculations from pressure drop in Poiseuille
Flow. The development of macroscopic clusters would
be expected in other shear regimes. The power law in
those regimes would also be expected to be the result of
non-dissipating macroscopic cluster development. This
may explain why it is very difficult to compound high
filler concentration into polymers that are to be used as
color concentrates and other systems like sheet molding
compound slurries. The filler concentrations in the
Newtonian fluid for these studies were limited to less than
35 vol. %. In many industrial cases, polymer filler
content is often in the 45 to 50 vol. % when making color
or other concentrates. The filled PE experiments suggest
that the dissipation is dominated by interaction of the
large molecules in the polymer matrix even when filled
with a moderate volume fraction of nanometer-size
particles. When this matrix was filled up to a
concentration of 0.495 volume faction, the power law did
not change appreciably. The relatively small change was
observed when the filler concentration was greater than
25 %. This may be due to the broad particle size
distribution of the TiO2 that was used. It also may be due
to the fact that much of the filler is of the same order of
size as the largest PE molecules and thus intermixes with
these molecules. The clusters at this percentage would
take a substantial shear stress gradient to deform, for this
system about 0.6 MPa per Figure 14.
References
1. G. A. Campbell , M. E. Zak, High Shear Rheology
Of Calcium Carbonate Slurries, SPE ANTEC , p.
382, 2001.
2. M. E. Zak, An Investigation of the Shear-Thinning
Behavior an Power-Law Modeling of Concentrated,
Non-Colloidal Suspensions, Ph.D Dissertation,
Clarkson University, 1994.
3. J. S. Radhakrishnan, Investigation of Poiseuille
Flow of Concentrated Monodisperse and Bidisperse
Suspensions Ph.D Clarkson University, 2002.
4. G. Segr and A. Silberberg, J. Fluid Mech., 14, 115
(1962).
5. A. Karnis, H. L. Goldsmith and S. G. Mason, J. Coll.
and Int. Sci., 22, 531 (1966).
6. A. Karnis, H.L. Goldsmith and S. G. Mason, Can. J.
Chem. Eng., 531 (Aug. 1966).
7. R. G. Cox and S. G. Mason, Ann. Rev. of Fluid
Mech., Vol. 3, 291 (1971).
8. F. Gauthier, H.L. Goldsmith and S.G. Mason, Trans.
Soc. Rheol., 15(2), 297 (1971).
9. J. T. Park, R.J. Mannheimer, T.A. Grimley and T.B.
Morrow, D.O.E. Quarterly Technical Progress
Report No. 5, Feb, 1988.
10. R. L. Hoffman, Trans. Soc. Rheol., 16(1), 155
(1972).
11. A. L. Graham and R.B. Bird, Ind. Eng. Chem.
Fundam., 23, 400 (1984).
12. A. L. Graham and R.D. Steele, Ind. Eng. Chem.
Fundam., 23, 411 (1984).
13. F. Gadala-Maria and A. Acrivos, J. Rheol., 24(6),
799 (1980).
14. D. M. Husband and F. Gadala-Maria, J. Rheol., 31,
95 (1987).
15. F. Parsi and F. Gadala-Maria, J. Rheol., 31(8), 725
(1987).
16. B. J. Ackerson, J. Rheol., 34(4), 553 (1990).
17. L. Petit and B. Noetinger, Rheol. Acta, 27, 437
(1988).
18. G. Bossis and J. F. Brady, J. Chem. Phys., 80(10),
5141 (1984).
19. J. F. Brady and G. Bossis, J. Fluid Mech., 155, 105
(1985).
20. G. Bossis and J. F. Brady, J. Chem. Phys., 87, 5437
(1987).
21. R. J. Phillips, J.F. Brady and G. Bossis, Phys. Fluids,
31(12), 3462 (1988).
22. L. J. Durlofsky and J. F. Brady, J. Fluid Mech., 200,
39 (1989).
23. H. Brenner, Phys. Fluids, 1(4), 338 (1958).
24. G. A. Campbell and G. Forgacs, Phys. Rev. A, 41(8),
4570 (1990).
25. D. M. Heyes and J. R. Melrose, Molec. Simul., 2, 281
(1989).
26. A. Einstein, Ann. Phys., 19, 289 (1906).
27. V. Vand, J. Phys. Coll. Chem., 52, 277 (1948).
28. R. Simha, J. App. Phys., 23(9), 1020 (1952).
29. N. A. Frankel and A. Acrivos, Chem. Eng. Sci., 22,
847 (1967).
30. E. J. Hinch, J. Fluid. Mech., 83(4), 695 (1977).
31. H. Tanaka, J.L. White, J. Non-Newton. Fluid Mech.,
7, 333 (1980).
32. G. K. Batchelor, J. Fluid Mech., 83(1), 97 (1977)
33. T. G. M. van de Venn and R. J. Hunter, Rheol. Acta,
16, 534 (1977).
34. G. J. Jarzebski, Rheol. Acta, 20, 280 (1981)
35. C. R. Wildemuth and M. C. Williams, Rheol. Acta,
23, 627 (1984).
36. V. Vand, J. Phys. Coll. Chem., 52, 277 (1948).
37. A. L. Graham, R. D. Steele and R. B. Bird, Ind. Eng.
Chem. Fundam., 23, 420 (1984).
38. R. L. Hoffman, J. Coll. and Int. Sci., 46(3), 491
(1974).
SPE ANTEC Indianapolis 2016 / 700
39. S. A. Altobelli, R. C. Givler and E. Fukushima, J. 41. Ostwald called it the de Waele-Ostwald equation:
Rheology, 35(5), 721 (1991). Kolloid Zeitschrift (1929) 47 (2) 176-187
40. P. G. de Gennes, Physico Chemical Hydrodynam.,
2(1), 31 (1981).

The advice contained herein is based upon tests and information believed to be reliable, but users should not rely upon it absolutely for specific
applications since performance properties will vary with processing conditions. It is given and accepted at users risk and confirmation of its validity
and suitability in particular cases should be obtained independently. The authors and their affiliate entities make no guarantees of results and assume no
obligation or liability in connection with its advice. This publication is not to be taken as a license to operate under, or recommendation to infringe, any
patents.

SPE ANTEC Indianapolis 2016 / 701