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Invited Keynote Paper on Fundamentals of


rheological classification and measurement of
high solids concentration slurries and pastes.
CONFERENCE PAPER APRIL 2004

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Nigel Heywood

Neil Alderman

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Fundamentals of rheological classification and measurement


of high solids concentration slurries and pastes
N I Heywood and N J Alderman
Aspen Technology, Harwell, UK

Proc Hydrotransport 16 Conference, Santiago, Chile, pp 675 to 699, 26 to 28 April 2004.

SYNOPSIS
Recently interest in the design of handling and transfer systems involving highly concentrated,
fine particle non-Newtonian slurries and pastes has increased substantially. This is to some
extent the result of increased interest in the disposal of high concentration tailings in the
mining industry, either on land or through mine backfilling, and partly facilitated through
recent improvements in thickener technology. Coupled with the application of suitable types
and concentrations of flocculants, these thickener improvements allow much higher
concentrations of thickened tailings to be created. This results in many benefits such a
reduction in the required land area for tailings disposal because smaller volumes of tailings are
involved as the solids concentrations increase, and because storage slopes can be increased as
paste viscosity and yield stress levels are increased.
However, high concentration pastes can also lead to problems in the rheological
characterisation and control of their rheological properties. Relatively small changes in solids
content, particle size distribution, pH and other slurry parameters can have very large effects
on rheological properties, so it is even more important than previously to control all these
slurry parameters over a narrower degree of variability than for lower concentration slurries, if
relatively constant rheological properties of the high solids content material are to be
maintained. Sampling and preconditioning for rheological measurements also become more
critical, and time-dependent and as well as time-independent rheological behaviour may be
exhibited. This time-dependency could be fully reversible, partially reversible or irreversible
thixotropy, or, more unusually antithixotropy.
This paper describes the main categories of rheological behaviour that high concentration
slurries can exhibit. Some of the behaviour conforms to conventional rheological property
while other behaviour can cause significant problems when trying to characterise the slurries
and apply the information in process engineering design. The paper also describes approaches
to make both relevant and accurate rheological measurements by making measurements only
over relevant shear rate and/or shear stress ranges, and identifying and correcting for four of
the most important errors in viscometry.

NOTATION
Cv
d
dr
D
Da
e
ks
K
L
m
n
n
N
Np
p
Rb
Rc
S
Ta
To
Tac
V
VS
Vt

av
max
p

solids volume concentration


sphere diameter
m
diameter of rotor in progressive cavity pump
m
diameter of tube
m
agitator diameter
m
rotor eccentricity in progressive cavity pump
m
proportionality constant between torque-averaged shear rate and agitator speed consistency coefficient in power law or Herschel-Bulkley models
N sn m-2
tube or bob length
m
exponent in Eqn (3)
power law exponent in power law or Herschel-Bulkley models
local power law exponent
rotational speed
rps
rotor speed in progressive cavity pump
rps
pitch of rotor in progressive cavity pump
m
bob radius
m
cup radius
m
constant defined by either Eqn (2) or (3)
mixing tank diameter
m
error-free torque
Nm
critical value of Taylor number
mean velocity in pipe
m s-1
wall-slip velocity
m s-1
terminal settling velocity of a sphere under gravity
m s-1
ratio of bob diameter to cup diameter
shear rate
s-1
average shear rate
s-1
maximum shear rate
s-1
average shear rate in a progressive cavity pump
s-1

B
C
N
r

e
w
y
yB
yC
yHB

wall shear rate


s-1
difference between cup and bob diameters
m
plastic viscosity
Pa s
Casson viscosity
Pa s
Newtonian viscosity
Pa s
relative viscosity
Pa s
density
kg/m3
shear stress
Pa
equilibrium shear stress
Pa
wall shear stress
Pa
yield stress
Pa
Bingham yield stress
Pa
Casson yield stress
Pa
Herschel-Bulkley yield stress
Pa
cylinder or agitator angular velocity
rad.s-1
critical cylinder angular velocity at which primary laminar flow breaks down rad.s-1

INTRODUCTION

The purpose of this paper is to summarise the types of rheological properties that high solids
content slurries or pastes can exhibit. The paper also outlines the types of rheological
measurements that can be undertaken with both the identification, and, where possible,
correction of associated viscometric errors, using either tube or rotational viscometers. The
aim is to characterise the slurry rheological properties for the purposes of system design.
High concentration slurries occur in the process industries in a wide range of physical forms
depending largely on the moisture level in the solids and on the particle size and particle
distribution. In most solids handling plants, it is usual to find intermediate and final products
in at least one of these physical states. Various terms are applied to wet solids depending on
their appearance, their handling properties and consequently the type of handling equipment
used either to store or convey the material. Starting with dry bulk solids, a progressively
increasing mixture level would cause the material to move through various classifications
such as a damp powder, cake, paste, high concentration slurry, low concentration slurry, and
finally, dirty liquid. This paper focuses on high concentration slurries and pastes only.
The possibility of some viscometric errors, such as the wall-slip effect which can occur in
both tube and rotational viscometry, increases in high solids content pastes. It is important to
be aware of the existence of these errors, and either to minimise their significance or to carry
out additional rheological measurements to characterize and correct for these errors. Only in
this way can serious errors in system design be avoided. Sometimes conventional viscometry
is not applicable because anomalous rheological behaviour is exhibited (1). This can
sometimes be explained through microscopic scale considerations, but cannot readily be
quantified using conventional rheological data reduction techniques. In these situations, fullscale flow processes need to be simulated or mimicked on the small-scale, and scale-up
rules developed to predict behaviour at full-scale.
2

CLASSES OF RHEOLOGICAL BEHAVIOUR

Fluids, in general, may be classified by their phase condition as homogeneous,


pseudohomogeneous (that is, able to be treated as homogeneous) or heterogeneous. A number
of factors affect the phase condition, one of which is sedimentation under gravity. Slurries
may be either settling or non-settling. For instance, coarse-particle, granular slurries tend to
settle whereas stabilised or concentrated, flocculated fine-particle slurries have a low settling
tendency. However, the distinction between non-settling and settling slurries is not clear as
judgement has to be made with regard to the time frame over which settling is deemed to be
important. This can be done by considering the specific engineering application. For example,
for pipeline design the slurry settling rate needs to be related to the residence time of the slurry
in horizontal, inclined or vertical pipework. Three different procedures allow the distinction
between non-settling and settling slurries to be made with respect to the application (2).
If solid particles in a suspending liquid medium settle sufficiently slowly under gravity, the
slurry can be characterised rheologically. These non-settling slurries are considered to be
pseudohomogeneous (that is, the particles are uniformly distributed throughout the liquid).
The usual viscometric methods for measuring the flow curve of homogeneous fluids can be
used for these slurries, with appropriate modifications to account for specific slurry attributes
(e.g., fibrous particles, large maximum particle size, very high viscosity, etc).

If, however, the solid particles in a suspending medium undergo rapid settling, the slurry can
no longer be treated as pseudohomogeneous (that is, the slurry is heterogeneous). Here, flow
curve measurements using rotational or tube viscometry are difficult and often meaningless.
Sometimes, it is possible to use the Metzner-Otto method (3) to measure the flow curve. This
method maintains the particles in suspension whilst carrying out the flow curve measurement.
Pseudohomogeneous slurries may be further classified into various rheological types on the
basis of their rheological behaviour when subjected to shear. Slurries and pastes can exhibit
either time-independent or time-dependent flow properties. In either case, the slurry is
characterised by a viscosity (i.e. the ratio of shear stress to shear rate) which varies with
changes in shear rate or shear stress. For a time-independent slurry, the viscosity is constant
with time at a given shear rate or shear stress level. The slurry can be Newtonian (constant
viscosity with varying shear rate), shear-thinning (reduction in viscosity with increasing shear
rate), viscoplastic (reduction in viscosity with increasing shear rate, once a yield stress has
been exceeded), or shear-thickening / dilatant (increase in viscosity with increasing shear
rate).
Time-dependent property occurs when slurry viscosity varies with time under constant shear
stress or shear rate conditions. This behaviour is sometimes also referred to in the literature as
shear-sensitive, but the use of this term is to be discouraged owing to its imprecision. Slurry
viscosity has also been observed to either increase or decrease with time as a result of changes
in one or more of the slurry physical properties which combine to determine the slurry
rheological properties. For instance, slurry viscosity has been observed to increase with shear
owing to particle attrition effects, and the corresponding progressive increase in the
percentage of fines in the slurry which exhibit Brownian motion.
The most frequently met time-dependent property is thixotropy which is characterised by
shear rate-dependent and time-dependent viscosity. For a well-rested slurry sample (that is,
one that has been allowed to rest for a time to recover from the effects of previous shear and
so rebuild its internal structure), the application of shear results in a decrease in viscosity with
the time of shear. However, for a slurry sample that has undergone significant shear, reducing
the shear stress level from a previous higher level, or removing the shear entirely, will lead to
a progressive viscosity increase with time arising from the rebuilding of structure in the slurry.
Quite frequently some people make the error of referring to a time-independent, shearthinning slurry as thixotropic. This is a confusion in terminology. In fact, most industriallyrelevant thixotropic slurries and pastes are also shear-thinning, but by no means all shearthinning slurries are also thixotropic.
2.1 Time-independent behaviour
It is important to know whether the flow properties are time-dependent. The simplest case is
where the flow curve does not depend on the time period over which the slurry is sheared. A
constant shear rate (or conversely shear stress) results in a constant shear stress (or conversely
shear rate) being observed instantaneously. This flow curve is said to be time-independent.
For many slurries, the variation of viscosity with shear rate as a function of solids content is
complex when measured over a wide shear rate range (Figure 1). At low solids concentrations,
the viscosity curve indicates shear-thinning behaviour (viscosity decreases with shear rate)
with well-defined zero-shear and infinite shear viscosities. At higher solids concentrations,
shear-thickening behaviour

Figure 1 Typical slurry viscosity curves (Cheng, 1980)


(viscosity increases with shear rate) is observed at high shear rates. This becomes more
pronounced with increasing solids concentration. The characteristic shear rates for either the
onset of shear-thinning or shear-thickening behaviour decrease with increasing concentration.
The slope of the viscosity curve at low shear rates within the shear-thinning region also
increases, until at very high solids concentrations it attains a value of -1. If replotted as a flow
curve, this slope of -1 shows a yield stress and the flow behaviour would be viscoplastic (4).
A consequence of this behaviour is that, strictly speaking, there are no such materials as
Newtonian slurries and non-Newtonian slurries. Instead there may be slurries which
exhibit Newtonian behaviour over a wide (and perhaps the only relevant) shear rate range, and
there are slurries which may exhibit non-Newtonian behaviour over the relevant shear rate
range, but which may also exhibit Newtonian behaviour outside this shear rate window.
Furthermore, there are slurries which may exhibit both Newtonian and non-Newtonian
property within the relevant shear rate window.
It follows from Figure 1 that a single point viscosity measurement is often inadequate to
describe the flow behaviour of slurries. Here, for any end-use of the viscosity data, the
relevant shear rate (or shear stress) range must be assessed and used in determining the
measurement conditions for the viscometer. A common error is to allow the shear rate (or
shear stress) range of the one and only available viscometer to dictate the test conditions for
measurement rather than to define the relevant range upfront. Another common error is to use
the full shear rate or shear stress range of an instrument when a much narrower window is
often all that is required. Making more rheological measurements than is necessary is a waste
of time, but more than one viscometer may be needed to cover the required shear rate or shear
stress range. Once the shear rate or shear stress window is estimated, a check on the
viscometer suitability to measure viscosity levels over the specified shear rate or shear stress
range must be made. Sometimes the shear stress or shear rate and the viscosity may be too low
or too high for the viscometer, so one or more alternative viscometers must be used.

2.2 Time-dependent behaviour


If a time-dependent slurry is held under constant shear for a sufficiently long time (typically
minutes but sometimes hours for thixotropic materials), the viscosity will attain a steady-state
value. Plotting this viscosity as a function of shear rate in the form of a shear stress versus
shear rate plot will provide the equilibrium flow curve for thixotropic materials. This means
that under steady-state operation in a process such as pumping slurry through a pipeline, it
may be possible to relate the frictional pressure loss for the flow of thixotropic slurries to the
equilibrium flow curve as if they were time-independent.
It is important to know whether the flow properties of the slurry are time-independent or timedependent in a number of applications. In steady pipe flow, a time-independent slurry will
have a constant pressure gradient along the pipeline whereas a time-dependent slurry will
develop a variable pressure gradient along the pipeline until the slurry structural state has
reached an equilibrium level. If pipe flow is interrupted, the structure of a time-dependent
slurry will develop causing the viscosity to increase with time. On start-up, the pump must be
capable of moving a pipeline of slurry at the higher viscosity associated with the static slurry.
The opposite of thixotropic property, i.e., the situation where the viscosity of a previously
unsheared slurry increases progressively with time under constant shear conditions, is very
rare in industrial environments provided there is no change to the fundamental slurry physical
properties, such as total solids content, particle size distribution, pH, temperature, etc. This
rare behaviour has been referred to as rheopexy. However, Cheng (5) pointed out that the
term rheopexy should really be used as a subset of the thixotropy definition, and the
alternative terms negative thixotropy, or antithixotropy, should be employed when describing
the opposite behaviour to thixotropy. The full complexity of time-dependent behaviour is
described using several terms: rheopexy, negative thixotropy (antithixotropy), and irreversible
thixotropy (rheomalaxis or rheodestruction), and partial thixotropy (see Table 1).
Table 1 Comparison of different classes of time-dependent slurry flow behaviour

Thixotropy

At rest when
freshly
prepared
Gel

Rheopexy

Gel

Negative
Thixotropy
(Antithixotropy)
Irreversible
Thixotropy
(Rheomalaxis,
Rheodestruction)
Partial Thixotropy

Under shear

At rest after
shear

Rate of structural build


up at rest after shear

Breaks down

Fully recovers

+ve, the rate of build up at


rest is faster than at higher
shear rates
+ve, the rate of build up at
rest is slower than at
moderately low shear rates

Fully recovers

Fluid

Breaks down
under moderate
and high shear
rates
Builds up

Breaks down

-ve

Gel

Breaks down

Does not recover


at all

zero

Gel

Breaks down

Partially recovers

+ve

NB Rheopexy as stated in this table is the original definition. However, since the 1950s rheopexy has become
synonymous with the negative thixotropy definition (see BS 5168:1975 - Glossary of rheological terms)

FLOW CURVE MEASUREMENT

3.1 Good sampling practice


When high concentration slurries and pastes are sampled for laboratory analysis, good
sampling practice is crucial to ensure that the samples are indeed representative of the bulk
properties of the slurry or paste. Ideally, fine particle slurry samples should not be taken in
flowing situations, and certainly not close to shearing wall surfaces, where various
hydrodynamic effects can lead to variations in both solids content and particle size
distribution. Normally several samples should be taken from a well-mixed vessel. Moreover,
the use of syringes or pipettes for taking slurry samples is strongly discouraged since this will
affect the shear history of the sample prior to the flow curve measurement. In addition, their
use will increase the variability of solids concentration and particle size distribution between
samples. Placement of the slurry sample in the viscometer should always be done carefully
with a spatula or pouring from an agitated bottle.
As the slurry solids content increases above about 40% by volume, both solids concentration
and particle size distribution (psd) can have a progressively bigger effect on slurry viscosity
and flow curve shape, and therefore classification. Figure 2 shows how rapidly slurry viscosity
increases with solids content. Relatively small variations in the solids content of high
concentration slurries can lead to disproportionately large variations in slurry viscosity. The
plot shows the typical relationship between the slurry relative viscosity (ratio of slurry
viscosity to viscosity of suspending liquid) and the solids volume concentration. By way of
example, at a solids concentration of 60% by volume, the relative viscosity, according to the
Eilers equation (6), will be about 24, but varies from 17 to 34 if the solids content were to
vary from 57% to 63%. Such sensitivity to solids content variations increases at progressively
higher solids contents, as indicated by the increasing slope of the curve in Figure 2.
1000

Eilers Equation
2

Relative viscosity,

1.25 C v

r 1

1 1.35 C v
100
39
24
17

10

63%

57%

1
0

10

20

30

40

50

60

70

Solids concentration, CV

Figure 2 Typical plot of slurry relative viscosity versus


solids concentration by volume

A second parameter which can affect slurry viscosity is the slurry psd. Farris (7) has shown
theoretically how psd variations can have very large effects on slurry viscosity for fullydispersed slurries at solids concentrations above about 40% by volume. Figure 3 gives a
simple example of a bimodal slurry (7), and how variations in the proportions of the fine and
coarse solids can lead to very large variations in slurry viscosity. Multimodal slurries exhibit
similar behaviour at high concentrations, but again, not at lower concentrations. As in the case
of the effect of overall solids concentration on slurry viscosity, the greater the solids content
of the slurry the greater the sensitivity of slurry viscosity to variations in psd. It follows that
the greater the solids content, the more care should be taken in slurry sampling, and probably
the larger the number of slurry samples required for rheological testing.

Figure 3 Predictions of relative viscosity of a slurry as function of coarse


fraction in a bimodal psd slurry (After Farris, 1968)
Other parameters which affect slurry viscosity include pH, particle shape and temperature. All
these parameters also need controlling during sampling and testwork.
3.2 Shear rate and shear stress ranges
With the range of viscometers commercially available, it is possible to measure viscosity over
12 orders of magnitude of shear rates from 10-6 to 106s-1. However, most process applications
require data only over two to three orders of magnitude of shear rate. Table 2 lists the shear
rates typical of various slurry flow processes of interest to engineers (8-13).
When a material passes through the process plant, it invariably encounters situations where
different shear rate ranges apply. For instance, slurry can be agitated in a storage vessel and
can be subjected to a range of shear rates, depending on the design and speed of the agitator. It
will then experience different shear rate ranges in a discharge pump and pipe system.

Table 2 Shear rates typical of some slurry flow processes


Shear rate, (or shear stress, )
expression

Flow Process

Sedimentation of solids
in a suspending liquid

Pipeline flow

Mixing and stirring Proximity agitator

Ref

Typical shear
rate range, s-1

14,15

10-6 to 10-3

1 3n' 8V
4n' D

16

1 to 103

Da
Ta D a

11

3 Vt
d
Vt
9 7n for power law slurry

max

av

max

10 to 103
Mixing and stirring Non-Proximity agitator
(Metzner-Otto method)

Pumping - Progressive
cavity pump

av k s N

where ks ranges between 9 and 15

N p ((1.5 d r ) 2 p 2 ) 0.5

4,17

or

e
2
0.8N p ( (4e d r ) 2 p 2 ) 0.5

100 to 103

3.2.1 Shear rate and shear stress estimation


Methods exist for defining the shear rate range for many processing applications (18). The
minimum shear rate often approaches zero whereas the maximum shear rate can be estimated
according to the application. Equations which can be used to estimate shear rate for several
flow situations are summarised in Table 2.
If a method for shear rate estimation in a particular processing application is not available,
define the flow region of interest, determine the differences between fluid velocities at two
points across the region (one point will often be the surface of some moving element such as a
pump impeller or mixer agitator, and the other will be a stationary equipment surface) and
divide this velocity difference by the separation distance between the two points. The full
shear rate range for measurement is estimated by considering the minimum shear rate as the
combination of the lowest difference in fluid velocities across the largest dimensional
separation, and the maximum shear rate using the highest fluid velocity difference across the
smallest dimensional separation.
Rather than ensuring the viscosity/flow curve measurement is carried out over an appropriate
shear rate window, it is sometimes more appropriate to carry out the measurement of the shear
stress appropriate to the application. Here, a controlled stress rheometer should be used in
preference to a controlled shear rate rheometer. However, the newer models of controlled
shear rate rheometers have a controlled stress option, and this capability should be used.

3.3 Recommended viscometer geometries for slurries and pastes


Flow curve measurements for engineering design should be made using either a tube or
coaxial cylinder. The use of cone-and-plate or parallel plate geometries is also feasible in
some circumstances, provided problems arising from particle-jamming (a gap separation of at
least 30 to 50 times the mean particle diameter is required to avoid any particle-jamming
effects), sample expulsion at high shear rates, and setting the gap are all appropriately dealt
with (2). Use of a rotating disc viscometer should also be avoided because of the problem of
defining the shear rate (which varies across the disc) and its somewhat restrictive shear rate
range (typically 1 to 100 s-1), although the geometry is appropriate for quality control.
3.3.1 Tube viscometry
Tube viscometers are generally once-through batch devices consisting of either a horizontal or
vertical length of precision-bored, straight tube through which the test slurry is passed at
varying rates from a reservoir. However, recirculating pilot-scale pipeline viscometers are also
commonly used. Tube diameters typically range from 0.3 mm to 5 mm. In the controlled rate
tube viscometer, a piston or ram forces the fluid through a horizontal or vertical tube at a
constant flowrate and the resultant pressure drop is measured. In the controlled pressure tube
viscometer, compressed air (or nitrogen) is applied to drive the slurry through a horizontal or
vertical tube and the resultant volumetric flowrate is measured. Measurement of the pressure
drop and volumetric flow rate allows the shear stress and shear rate to be calculated (18, 19).
3.3.2 Coaxial cylinder viscometry
The coaxial cylinder viscometer consists of a bob (the inner cylinder) located in a cup (the
outer cylinder) with the test sample contained in the annular gap between the bob and cup.
This viscometer can be operated either in the controlled-rate or controlled-stress mode.
There are two types of controlled-rate instruments, the Couette and the Searle types. In a
Couette-type, the cup is rotated and the torque exerted on the bob by the test sample is
measured. In the Searle-type, the cup is stationary and the bob is both the rotating element and
the torque driver. In controlled-rate instruments, the bob or cup is rotated at a constant speed
that can be sequentially stepped by the operator, or by using a steadily-changing speed ramp.
The resultant torque on the bob is measured by a torsion spring. In controlled-stress
instruments, constant torques that can be sequentially changed or a torque ramp is applied to
the bob, and the resultant speeds are measured. Expressions for shear stress and shear rate on
the cylindrical surface of the inner cylinder are available (18, 20).
3.4 Flow curve measurement for slurries and pastes
Flow curve measurements should be repeated at least twice. This will allow assessment of the
variability of viscosity with solids concentration and particle size distribution. With controlled
rate instruments, the flow curve is usually generated using at least three cycles of ramping the
speed, either by a sequence of intermittent steps or a continuous ramp. This is done up to a
maximum set speed in a given time period and down again over a similar period. The
resulting torque is measured. In controlled stress instruments, the torque is ramped in a similar
manner, and the resultant speed is measured. The time over which the shear ramp up or down
is to be carried out is left to the operator to decide. However, a good starting point would be
the time that gives 30 s per step, but this will depend on the slurry.
Repeated shear cycles carried out on the test sample will show if the sample exhibits timedependent flow behaviour such as thixotropy. If the up and down curves for the first and

successive cycles coincide the sample is said to exhibit time-independent flow behaviour.
However, if hysteresis loops between the up and down curves are observed for each
successive cycle, then the sample is said to exhibit time-dependent flow behaviour, in which
case repeat the experiment where the speed (or torque) is held constant until the torque (or
speed) attains a steady value before the ramping the speed (or torque) to the next value. This
will yield an equilibrium flow curve where the up and down curves coincide.
The solids concentration above which anomalous rheological behaviour starts to occur (1) is
somewhat relative. For 1 m particles, the solids volume concentration is about 60%, whereas
for 100 m particles, it occurs at about 40%. When carrying out flow curve measurements on
these materials, a check for reproducibility should be made. This can be done using four test
methods:
1. testing again on the same sample;
2. testing a new sample for the same bulk sample using the same viscometric geometry;
3. testing a new sample from the same bulk sample with the same viscometric geometry but
with different dimensions;
4. testing a new sample from the same bulk sample with a different viscometric geometry.
Even after eliminating or correcting for major viscometric errors (see Section 3.5), two or
more of these tests will tend to give a flow curve band rather than a unique flow curve. The
existence of a flow curve band arises from either the lack of reproducibility in the test sample
of the inhomogeneity of the bulk sample (as in the case for test 2) or the solids moving
separately from the liquid phase and taking up different packing structures depending on the
shearing conditions (as is the case for tests 1, 3 and 4). If the flow curve band can be attributed
to the irreproducibility in composition of the small volume of the test sample, then the mean
of the flow curve data should be taken. However, if the flow curve band arises from the
rearrangement of packing structures during shear, then it is advisable to construct an upper
bound to the flow curve data for a conservative assessment.
3.5 Errors in flow curve measurement
There are four common error sources for both tube and co-axial cylinder viscometers which
should normally be properly accounted for.
3.5.1 Secondary flow (co-axial) and transitional / turbulent flow (tube)
Flow curve measurements are made for (primary) laminar flow conditions only. The data
collected must be checked to ensure they are not subject to secondary laminar flow conditions
in a co-axial cylinder viscometer, or transitional / turbulent flow conditions in a tube
viscometer. This is achieved by calculating the laminar flow limit for the slurry under test and
rejecting data subject to secondary or transitional / turbulent flow. Alternatively, an
experimental method using different sizes of the same viscometric geometry can be used in
which the flow curve data affected by secondary or transitional / turbulent flow (assuming the
end effect and wall slip effects have been corrected for) show up as deviations from the main
curve (21).

3.5.2 End-effect
This error arises because the assumption that the tubes or cylinders are infinitely long in the
derivation of shear stress and shear rate equations cannot, of course, be met in practice. Endeffect can be dealt with by minimisation, experimental determination or prediction (19).
3.5.3 Wall-slip
Wall-slip may occur when a slurry or paste is sheared. This effect gives a resultant wall shear
stress at a given wall shear rate lower than expected owing to the formation of a thin layer of
fluid (caused by the depletion of the dispersed phase at or near the shearing surface) having a
viscosity lower than the bulk of the fluid. Conversely, for a given wall shear stress, the
measured shear rate is greater than the true shear rate. In tube viscometry, for example, wallslip is present when curves of wall shear stress versus nominal wall shear rate obtained with
different tube diameters do not superimpose after all other corrections to the data have been
made. This effect can be quantified through a wall slip velocity, Vs. Different methods are
used to estimate Vs values to correct flow curve data for wall-slip error.
3.5.4 Viscous Heating
Viscometric tests should be designed to avoid significant temperature increases due to viscous
heat dissipation, which occurs when any fluid is sheared. However, serious experimental
errors are generally found only in high viscous fluids at high shear rates. The data collected
must be checked to ensure that they are not affected by viscous heating. This is done by
calculating the viscous heating limit given for the appropriate geometry. Alternatively, an
experimental method using different sizes of the same viscometric geometry can be used in
which the flow curve data affected by viscous heating, assuming the end effect and wall slip
effects have been corrected for, show up as deviations from the main curve (21).

Figure 4 Errors in flow curve measurement

Figure 4 summarises the way in which these four errors affect the flow curve. Higher-thanexpected viscosity values will be obtained if the torque-speed data are affected by end-effect
in coaxial cylinder and tube viscometers. Data affected by secondary or turbulent flow will
also give rise to apparently erroneously large viscosity values. Lower-than-expected viscosity
values will be obtained if the torque-speed data are affected by the wall-slip effect and viscous
heating.
3.6

Correcting for errors

3.6.1 Correcting for errors in tube viscometry


Transitional/turbulent flow - The expression for wall shear rate is valid only for laminar flow
conditions and does not apply for transitional or turbulent flow. Hence any transitional or
turbulent flow data collected during the course of an experiment must be rejected. This
requires that the laminar flow limit for the slurry under test should be calculated. The criterion
for the laminar flow limit for power law non-Newtonian fluids is given by Eqn (1)
2

1+ 3 n

2
D2 n
4n 8V

w >
( n 2 ) /( n 1)
D
8 404 (n + 2 )

(1)

This equation can be plotted as a double logarithmic plot of w against 8V/D to give the
laminar limit line (Figure 5); data to the left of the line (which has a slope of 2) correspond to
laminar flow, while data lying on it or to the right of the line must be rejected. The laminar
flow limit with n = 1 is the worst case, leading to a conservative approach to data elimination.

Wall s

Laminar flow limit


with n = 1

Figure 5 Plots of W versus 8V/D for digested sewage sludge passing


through a 18.85mm tube with the laminar limit

End effect - This arises in the form of additional pressure losses at the entrance to and from
the tube. These losses result from:
(a) energy losses arising from viscous or elastic behaviour as the fluid converges at the
entrance to the tube or diverges at the end of the tube,
(b) losses in the kinetic energy of the fluid brought about by rearrangement of the fluid
streamlines on entry and exit,
(c) time-dependent properties of the fluid which result in an additional variation of wall shear
stress along the tube entrance or exit length for steady flow, and
(d) energy losses, arising from either elastic deformation of viscoelastic fluids or structural
change of thixotropic fluids, not recovered during flow in the tube.
It is usual to treat the losses at the exit as being negligible compared with those at the
entrance. Equations are available for estimating the entrance length to obtain 98% of fullydeveloped flow of Newtonian, power law and Bingham plastic fluids (10). However, it is
preferable to correct for end effect experimentally using a number of tubes of the same
diameter but of different lengths (16, 20).
Wall slip - To correct for wall slip, the wall slip velocity, Vs, is assumed to be given by (19)

Vs S w

(2)

and this assumption is validated when the plots of 8V/D versus 1/D for various constant
values of w are straight lines. Otherwise, Vs can be expressed as (22)

Vs

S w
D

(3)

where m takes a value such that plots of 8V/D versus 1/Dm + 1 for various constant values of
w give straight lines; this condition is usually found by trial-and-error, assigning different
values of m (such as 1.25, 1.5, 2.0, 2.5 and 3.0).
As an example, plots of wall shear stress versus nominal wall shear rate (8V/D) were obtained
for a fine particle slurry using a controlled-pressure tube viscometer fitted with three tube
diameters of 0.408, 0.602 and 0.981 mm, Figure 6. The three curves did not superpose, and so
wall-slip was shown to be present. To correct for wall-slip, wall-slip velocities were estimated
using the procedure outlined above. Wall-slip velocities ranged from 44 mm/s at a wall shear
stress of 350 Pa to 68 mm/s at 600 Pa. Values of 8(V-VS)/D were then used in place of 8V/D
for the three curves to give a single wall-slip corrected curve as shown by the uppermost solid
line in Figure 6. This shows that if the 0.408 mm tube alone had been used, the slurry
viscosity would be underestimated by about 10%.
It should be noted that, in general, the relationship between slip velocity and wall shear stress
using the tube geometry will not usually apply to other viscometric geometries. Thus, if wallslip is present and the application for the viscometric data is pipeline design, the tube
viscometric geometry should be selected, if possible.

800

0.981 mm
0.602 mm
0.408 mm

Shear stress (Pa)

600

400

200

0
0

2500

5000

7500

10000 12500 15000 17500

8V/D (s-1)
Figure 6 Shear stress versus nominal wall shear rate for a fine particle slurry
using three capillary tube sizes
3.6.2 Correcting for errors in coaxial cylinder viscometry
Secondary Flow- For experimental data not to be affected by secondary flow when the bob is
rotating (Searle type), the following criterion developed for Newtonian fluids (used as an
indicator for non-Newtonian fluids) must be satisfied:

>

4
2 3/2

(1 - )

2
Ta1/2
c

(4)

where = Rb/Rc , = Rc - Rb, is rotational speed in rad/s and Tac is the Taylor number at
the critical speed at which primary laminar flow breaks down, c, given by Alderman (2) as

Ta c 2350

1050

(5)

1.8

This equation can be plotted as a double logarithmic plot of against to give the laminar
limit line (straight line with slope of 2); data to the left of the line correspond to laminar flow,
while data lying on it or to the right of the line must be rejected for further analysis.

If the cup is rotating (Couette type), the higher velocity at the cup radius has a stabilising
effect on fluid flow and secondary laminar flow occurs at a speed about 10 times higher than
that for the case where the bob is rotating (23).
End effect This error arises because of the viscous drag on the ends of finite length cylinders
and can account for up to 30% of the measured torque. End effect can be minimised with
limited success by

using a bob with a large L/Rb ratio,


trapping an air bubble in the fluid using a bob with a recessed bottom, or
using a Mooney-Ewart bob whose bottom is conically shaped to give the same
Newtonian shear rate as that in the annulus.

Alternatively, end effect can be determined experimentally so that the data can be corrected.
This involves the use of either a series of bobs of same radius but of different lengths or a
single bob partially immersed to different depths (16, 20).
Wall slip - This can be identified when flow curve data obtained with a series of bobs of
different radii do not coincide after the data have been corrected for end effect. This effect is
normally dealt with either by using bobs and cups with walls roughened to eliminate the wall
slip or by experimental methods which allow the wall slip velocity to be determined and
corrected for. The assumption that roughened wall surfaces eliminate wall slip should be
verified using bobs and cups of varying degrees of roughness (20, 24).
3.7 Rheological assessment of the yield stress property
The yield stress (y) of a slurry is defined as either the minimum stress required to maintain
steady shear flow in a material when using a controlled rate (CR) viscometer or the maximum
stress that the material will sustain without developing steady shear flow when using a
controlled stress (CS) viscometer. For stresses below y, the slurry behaves as an elastic solid
whereas for stresses above y, the slurry flows with a shear rate dependent on the excess stress (
- y). The relationship between the shear rate and the excess stress is linear for slurries exhibiting
Bingham plastic behaviour and non-linear for slurries exhibiting viscoplastic behaviour. As the
yield stress is often linked to the material structure, it will depend on the slurrys previous shear
history. Thus, a low y will occur when the material structure is broken down by shear whereas a
higher y will result when the material is allowed to rest causing the structure to develop.
Many methods are used for yield stress measurement of high concentration slurries (11, 25),
including vane rheometry (26). A vane rheometer has several advantages over conventional
measuring geometries including the insertion of a vane causes much less structural damage to
the sample and the absence of wall-slippage since the yield surface is within the material itself.
The vane immersed in the cup containing the slurry sample is either made to rotate at a fixed rate
and the resulting torque is measured as a function of time, or small step increases in torque are
applied until the resulting strain is no longer constant with time. From the maximum torque, the
yield stress can be evaluated. Provided care is taken to ensure no wall slip, it has been found for
many materials that the yield stress results agree well with those obtained from extrapolation of
the flow curve obtained from CS rotational viscometry beyond the lowest measurable shear rate
to the zero shear rate.

The slump test is also available for yield stress measurement of high concentration pastes (27).
This test is carried out by first filling the slump cone in three layers, each layer being tamped 25
times. After smoothing the surface, it is placed upside-down on a surface. The cone is raised
vertically causing the material to slump. From the slump height, the yield stress is evaluated.
There is much controversy in the literature over the existence of a yield stress (25). However, the
requirement for the concept of a yield stress depends on the application. If a slurry is
characterised by its property at zero shear rate, a yield stress cannot be measured because the
slurry property attained is always unknown and cannot be obtained by extrapolation. One would
perpetually be developing more sophisticated viscometers for measurement of ever-decreasing
shear rates. So, no-one will ever measure a true yield stress! However, from an engineering
perspective, such measurements are expensive and unnecessary because a part description of the
flow curve over the relevant shear rate range using a yield stress is sufficient. The magnitude of
the yield stress was shown (28) to be dependent either on the length of the observation time used
to determine whether flow is established or has ceased in a CS experiment, or on the lowest
shear rate used in a CR experiment. As the yield stress is essentially then a time-dependent
property, it becomes important to ensure the choice of the observation time or shear rate to use is
matched to the characteristic time or shear rate to which the results are to be applied.
3.8

Rheological assessment of time-dependent property

3.8.1 Hysteresis loop tests


The presence of time-dependent flow behaviour in slurries/pastes can be assessed by carrying
out repeated shear cycles on a test sample in a rotational viscometer (5). If hysteresis loops
between the up and down curves are observed for each successive cycle, the sample is said to
exhibit time-dependent flow behaviour. Figure 7 shows positive hysteresis loops
(clockwise) for slurries whose internal structure is breaking down under cyclic shearing, but
negative loops (anticlockwise) are also obtained for slurries whose internal structure is
increasing under cyclic shearing. With positive loops, the first loop may show the catastrophic
breakdown of a yield stress but the following few loops will not generally coincide.
However, as the shearing cycles are repeated, two successive loops will eventually
superimpose, giving the equilibrium loop. This is invariant with respect to the number of
shearing cycles involved. The area between the up and down curves of any one loop test is
indicative of the thixotropic nature of the slurry. This area is zero for slurries exhibiting timeindependent flow behaviour. In other words, the up and down curves should superimpose,
provided that there are no errors arising from measurement, as discussed in Section 3.5. As
there is always some error in the measurement involved, this superposition will always be
approximate.
The hysteresis flow loop measurement is useful as a quality control tool to compare two or
more samples of slurry or paste from the same or different batches, provided that the
equilibrium flow curve is used as the basis for comparison in order to eliminate any differing
previous shear history effects. However, the loop test suffers unfortunately from two
disadvantages, namely:
(i) it is often carried out too quickly and inertia effects from the measuring head are
introduced but not always recognised.

(ii) the response cannot be resolved separately into shear rate and time (29).

Figure 7 Typical behaviour of a thixotropic slurry when subjected to


repeated cyclic shearing

3.8.2 Step shear rate experiments


If the slurry appears to exhibit time-dependent flow behaviour, the experiment where the
speed (or torque) is held constant should be repeated until the torque (or speed) attains a
steady value before the ramping the speed (or torque) to the next value. This will yield an
equilibrium flow curve in which the up and down curves coincide. Typical results are depicted
in Figure 8.
Alternatively, a different type of step-shear rate experiment is carried out to determine lines
of constant structure (5). Instead of waiting for the shear stress to attain an equilibrium value
after a change in shear rate has been imposed upon the sample, the new shear rate is held for
only as long as necessary to obtain the initial shear stress and the initial slope of the shear
stress versus time plot, before the shear rate is returned to a reference shear rate.
Figure 9 summarises how this type of step-shear rate experiment is carried out (5). The sample
is first sheared at a reference shear rate R = E until equilibrium is attained and = eE. The
shear rate is then suddenly changed to a test shear rate T = A and the shear stress is recorded
as a function of time. The shear rate is returned to E and the sample brought again to
equilibrium. A new test shear rate T = B is now applied and the shear stress recorded. This
sequence of sample conditioning at E and tested at T is repeated for other values
of T = C , etc.

Figure 8 Thixotropic behaviour observed from step changes in shear rate

Figure 9 Step-shear rate experiments to obtain constant-structure curves


From the shear stress versus time traces, the initial shear stresses 0 immediately after the step
change to T are read and plotted versus T ; and also the reference point ( T , eE). It is assumed
that the structure has not had time to change just before and just after the step change and so
all the data points refer to the same structure, that in equilibrium at E . The flow curve plotted
(Figure 10) is therefore a line of constant structure.

By repeating the test using a range of reference shear rates R = F , G , H , a family of constant
structure curves can be mapped out (Figure 10). Constant structure curves combined with the
measurement of curves illustrating the rate of change of structure with time (4) provide a full
characterization of a time-dependent slurry. However, the practical application of this method
has still to be developed adequately for many slurry engineering applications.

Figure 10 Plotting constant-structure curves


4

FLOW CURVE MODELLING AND INTERPRETATION

The main classes of flow curve exhibited by slurries under steady-state shear are given in
Table 3. These are idealised representations as most slurries, as we have seen, show more than
one flow curve classification over the measurable shear rate range of 10-6 to 106 s-1. As a
result, sometimes more complex models are required, such as the Cross (30) or Sisko (31)
models. These models can be particularly useful in product formulation, but for most process
engineering applications the simpler models involving just two or three model parameters will
generally suffice.
Having completed the calculation procedure for the corrected flow curve, the data may be
amenable to a single curve fit. Sometimes, because of considerable scatter in the data, it may
be more appropriate to construct at least two curves: a mean curve obtained from regression
analysis using all the data and an upper bound curve obtained from regression analysis using
(, ) data selected from the curve that was initially drawn by eye. The upper bound curve
would normally represent the worst case for many engineering applications. This curve would
normally account for any possible variations in solids concentration, particle size distribution,
particle shape and pH.

Table 3 Flow curve models


Flow Curve Description
Newtonian

Flow Curve Model


Newtonian model:

= N

Shear-thinning or
pseudoplastic

Power law model:

= K n

n<1

Shear-thickening
(dilatant)

Power law model:

= K n

n>1

Bingham plastic

Bingham plastic model:

= yB + B

Viscoplastic

Casson model:

0.5
0.5 0.5
yC C

Generalised Bingham plastic or Herschel-Bulkley model:

= yHB + K n

Further factors can cause difficulties in attempting to draw a single flow curve through the
data. These factors include the use of two or more different viscometric geometries which may
give differing degrees of phase separation during shear, sample variability taken from the
same batch, and uncorrected errors associated with the use of any viscometric geometry.
5

FLOW CURVE
ESTIMATION

MODEL

SELECTION

AND

MODEL

PARAMETER

It is often not immediately obvious from the data which of the flow models summarised in
Table 3 should be selected for further design usage. The following approach is suggested:
(i)

Plot all the (, ) data on linear axes and separately, on double logarithmic axes. This
is to assess the suitability of the Newtonian, Bingham plastic and power law models.

(ii)

If there is considerable scatter in the data, decide by eye or from the correlation
coefficient obtained by linear regression analysis whether a straight line through the
linear or the log-log plot gives the better representation. Similarly decide for the upper
bound curve. If one of these alternatives is acceptable, the use of the Herschel-Bulkley
model is probably not warranted.

(iii)

If neither of these alternatives appears satisfactory because there is significant


curvature of the data on both linear and log-log plots, the following can arise:
(a)

If there is data curvature on the log-log plot with the slope of the curve
increasing with shear rate axis and if the linear plot does not produce a straight
line then the Herschel-Bulkley model should adequately describe the data.

(b)

If there is data curvature on the log-log plot and the slope of the curve
decreases with shear rate axis, the use of the Herschel-Bulkley model is

inappropriate as this implies a negative yield stress parameter. However, a


curve fit is possible and would result in a negative value for the yield stress
parameter. Force-fit either a Bingham plastic or power law model to the data.
Estimates need to be made for the parameters defined in the flow models given in Table 3. As
the Herschel-Bulkley model can be reduced to the Newtonian, power law and Bingham plastic
models, a least squares regression analysis can first be performed on the (, ) data to obtain
yHB, K and n. It may then be possible to simplify the model by setting the yHB to zero if the
estimate is close to zero and/or setting n to 1 if the estimate is close to unity. Two methods are
commonly used when carrying a regression analysis on the (, ) data:

a non-linear least squares regression on unweighted data,


a non-linear least squares regression on weighted data.

Standard non-linear regression software packages can be used. Alternatively non-linear


regression can be performed using Microsoft Excel via the Solver tool (32). Both methods
above provide sets of yHB, K and n estimates which give viscometric data predictions to 2%
of the original data within the original shear rate range. Outside this shear rate range,
agreement can be poor and extrapolations to shear rates above the highest experimental value
should be avoided. Extrapolation to shear rates below the lowest experimental value is
unavoidable when predicting frictional pressure loss for laminar pipeflow (16).
6

CONCLUDING REMARKS

Slurry rheological properties need to be adequately measured for many process engineering
applications, including equipment selection and sizing, and specification of operating
conditions. These measurements may need to take into account both time-dependent flow
properties, as well as time-independent properties. Unfortunately, the application of timedependent flow property data to process engineering is not nearly so well-developed as it is
for time-independent property, and further work is required in this area. However, additional
testwork which assesses any time-dependent property can be very useful in design.
The flow properties of relatively low concentration fine particle slurries and pastes can usually
be readily measured. However, at higher solids concentrations, unusual responses from slurry
samples to conventional measurement methods should be expected (1). These responses
include time-dependency due to particle packing rearrangements under shear, the stick-slip
phenomenon, particle holdup in tube viscometers, and the influence of pressure when the
solids concentration starts to approach the maximum packing fraction. These effects are
documented in the rheological literature and may need to be considered during rheological
data interpretation for high concentration slurries.
By making both relevant and accurate rheological measurements on slurry samples that have
been correctly taken, and, if necessary, pre-conditioned, measurement effort can be minimised
and focused on the engineering requirement more precisely. The need for accuracy may
introduce additional laboratory experiments, particularly if end-effect and/or wall-slip errors
are identified. However, ensuring that only viscometric data relevant to the process
engineering applications of interest are collected will minimise the effort. Figure 11 gives the
steps to take to ensure the relevance and accuracy of slurry rheological measurements.

APPLICATION

Determine shear rate / shear


stress over which flow curve
should be measured

SLURRY
CONSIDERATIONS

Consider the impact of slurry


properties on viscometric
geometry selection, including
1. Maximum particle size
2. Concentration
3. Temperature
4. Pressure
5. Corrosive?
6. Volatile?
7. Abrasive?

VISCOMETER
SELECTION

Select viscometric geometry

Obtain flow curve using loop tests

Yes

Undertake additional tests to


determine time-dependent
behaviour

FLOW CURVE
MEASURMENT

Are there significant timedependent effects?


No

Are the data subject to


secondary/turbulent flow or
viscous heating effect?

Yes

Eliminate data affected by


secondary/turbulent and/or
viscous heating effects

Yes

Minimise effects of error, or


correct flow curve data

Yes

Minimise effects of error, or


correct flow curve data

No

FLOW CURVE
CORRECTIONS

Are the data subject to


end-effect error?
No

Are the data subject to


wall-slip error?
No

Obtain corrected flow curve

Obtain model parameters


for design calculations

FLOW CURVE
MODELLING

Select flow model

Figure 11 Summary flowchart for making slurry flow curve measurements

REFERENCES

1.

Cheng, D C-H (1984) Further observations on the rheological behaviour of dense


suspensions, Powder Technology, 37, 255-273.

2.

Alderman, N J (1996) Non-Newtonian Fluids: Obtaining viscometric data for frictional


pressure loss estimation for pipeflow, ESDU 95012, ESDU International plc, London,
UK.

3.

Metzner, A B & Otto, R E (1957) Agitation of non-Newtonian fluids. AIChEJ, 3, 3-10.

4.

Cheng, D C-H (1980) Viscosity-concentration equations and flow curves for


suspensions, Chem and Ind, 17 May, 403-406.

5.

Cheng, D C-H (1987) Thixotropy. Int J of Cosmetic Sci., 9, 151-191.

6.

Eilers, V H (1941) Kolloid-Z, 97, 313.

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Farris, R J (1968) Prediction of the viscosity of multimodal suspensions from unimodal


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Alderman, N J (2004) Shear rate estimation for viscosity/flow curve measurement,


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9.

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Amsterdam.

10. Macosko, C W (1994) Rheology Principles, Measurements and Applications, WileyVCH, New York.
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Press, Michigan.
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Fluid Mechanics, University of Wales, Aberystwyth.
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New York.
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