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Colloids and Surfaces A: Physicochem. Eng. Aspects 318 (2008) 217–226

Yield stress of water–bentonite dispersions

V.C. Kelessidis a,∗ , R. Maglione b
a Department of Mineral Resources Engineering, Technical University of Crete,
Polytechnic City, 73100 Chania, Crete, Greece
b Vercelli, Italy

Received 9 August 2007; received in revised form 1 November 2007; accepted 20 December 2007
Available online 6 January 2008

Abstract
Yield stress of aqueous bentonite dispersions was determined at two concentrations, with two bentonites, over a range of pH values, with the vane
technique and by extrapolation of the full rheograms, derived with concentric cylinder viscometer, fitted to Herschel–Bulkley and to Casson models.
All samples exhibited a yield stress and gave very similar yield stress values determined by the three techniques and hence, any of the techniques
can be used for measurement of the yield stress. Data extrapolation using either the Herschel–Bulkley or the Casson model would be favoured,
though, because it gives, in addition to the yield stress, the rheological model parameters. The close matching observed for all three techniques is
attributed to preparation and intensive preshearing procedures, similar to ones experienced by fluids in flow situations. pH of dispersions affected
their yield stress but the effect was different for the two bentonites and the two concentrations tested. Measurement time at each rotational speed
should be kept at a minimum of 60 s. Bentonite dispersions build continuously structure over time and the yield stress evolution with time could be
well described by power law. A model to predict yield stress, previously suggested for suspensions at the isoelectric point, could be a good starting
point for yield stress prediction of bentonite dispersions.
© 2008 Elsevier B.V. All rights reserved.

Keywords: Yield stress; Bentonite; Vane; Herschel–Bulkely; Casson

1. Introduction oratory and field measurements using rheological models with

Water–bentonite dispersions at concentrations more than 1%
exhibit a yield stress, which is defined as ‘the stress above which
the material flows like a viscous fluid’ [1]. The true existence
of the yield stress of various dispersions and whether it is a
material property has been debated over many years [2–7] but
many researchers consider it a true material property [8–13].
This controversy is in essence, a controversy about the shear
rate range that shearing is observed for relatively short times.
If the very long-term stability of suspensions at extremely low
shear rates is of interest, the existence or not of the yield stress
could be questioned [7], but if, on the other hand, flow situa-
tions of such suspensions are of interest, as is the case for the
current article, then the yield stress is indeed a reality. In the
latter cases, the successful match of pressure loss predictions
in flow of such dispersions through various conduits with lab-
∗ Corresponding author . Tel.: +30 2821037621.
E-mail address: kelesidi@mred.tuc.gr (V.C. Kelessidis).
a yield stress [13–17] may be considered a direct proof that
the yield stress is indeed an engineering reality. Furthermore,
drilling industry relies heavily on the existence of a yield stress
of the drilling fluids for suspending weighting solids (such as
barite) and for transferring drill cuttings to surface [12,18,19].
Extensive reviews on yield stress materials have been presented
previously [20–22].
Various techniques to determine the yield stress have been
reported in the past and are used in research and industry and
these have been reviewed by Nguyen and Boger [23]. No single
method, however, has been universally accepted as the stan-
dard method for measuring the yield stress. Determination of
the yield stress as a true material property is very difficult
because not only it depends on the measurement technique, but
also on the model used to evaluate rheological data [7,23,24].
Furthermore, the yield stress has been characterized as a time-
dependent property [9,24] although the intensive preshearing
occurring prior to measurement according to drilling fluid indus-
try practice [25,26] should minimize thixotropic effects [27].
Never-the-less, yield stress can be determined either by using

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 Author's personal copy

218 V.C. Kelessidis, R. Maglione / Colloids and Surfaces A: Physicochem. Eng. Aspects 318 (2008) 217–226

success and this could be the result of not knowing which is the
Nomenclature real property that is measured. Hence, one must assess which
of the yield stress values is the real engineering property, not
A term in Eq. (9)
dependent on the measuring methodology and furthermore a
AH Hamaker constant (J)
procedure should be standardized on how to measure it.
B term in Eq. (9)
It is the scope of this work to provide further evidence that the
d particle diameter (m)
yield stress of aqueous bentonite dispersions is an engineering
D vane diameter (m)
reality. The yield stress of bentonite dispersions will be deter-
h0 inter-particle distance (m)
mined at different conditions such as, different raw material,
H vane height (m)
different preparation procedures, different concentrations and
K fluid consistency index (Pa sn )
different pH values, by the vane technique and also estimated
n fluid behavior index
by extrapolation of concentric cylinder viscometric data using
r radius (m)
Herschel–Bulkley and Casson rheological models. The values
SQ2 sum of square errors (Pa2 )
will be compared so that a best approach for obtaining the engi-
t time (s)
neering property of bentonite dispersions known as yield stress
Tm torque (N/m)
will be proposed. An attempt will also be made to predict yield
Greek letters stress of such dispersions from proposed relationships between
γ̇ shear rate (s−1 ) microstructure and macroscopic properties, which, if successful,
ζ zeta potential (V) could provide evidence that yield stress is a material property.
μC Casson viscosity (Pa s)
μp plastic viscosity (Pa s) 2. Background theory
τ yield stress (Pa)
τB Bingham yield stress (Pa) The yield stress from the vane measurements can be com-
τ CA Casson yield stress (Pa) puted, following the approaches of Nguyen and Boger [8], James
τe yield stress on bottom and top surface of vane (Pa) et al. [10] and Alderman et al. [28]. If the stress is non-uniform
τ HB Herschel–Bulkley yield stress (Pa) over the circumscribed cylinder by the vane, then
  
τ HSRB high shear rate Bingham yield stress (Pa) τy D D/2
τvn vane yield stress (Pa) Tm = πDH +2 π τe (r)r dr (1)
2 0
τLSRB linear shear rate Bingham yield stress
τ y,max maximum yield stress (Pa) where Tm is the maximum measured torque with the vane instru-
φ solid volumetric concentration ment, τ y is the yield stress, H is the height of the vane and D is
the diameter of the vane. τ e is the shear stress developed on the
bottom and top surfaces of the vane, which is assumed to vary
from the center to the outer circumference by
direct measuring devices or by implementing indirect measuring
 m
techniques. τe 2r
Direct measurement techniques rely on an independent = (2)
τy D
assessment of the yield stress, normally carried out with the
rotating vane method [8,11,24,28,29], a technique used widely in Substitution into Eq. (1) and integration yields,
soil mechanics and adapted for use in fluids. Numerical simula-  
πD3 H 1
tion [30,31] has provided further support for the reliability of the Tm = τy + (3)
2 D m+3
technique. The vane has usually four thin blades and is rotated at
very slow speed while immersed in the material. The resulting If m is zero or very small, it may be concluded that the fluid
torque is measured continuously as a function of time and anal- ‘yields’ and the shear stress along the radius of the bottom or top
ysis of the curve provides the yield stress, which is often called of the vane is constant and equals the yield stress, τvn [23,34].
the static yield stress [32]. The technique is not prone to errors James et al. [10] using vanes of different height and diameter
attributed when use is made of the indirect techniques, because, in illite suspensions of various concentrations found that (m)
firstly, no wall slippage occurs, with the material yielding in ranged between 0.01 and 0.05, hence, it may be concluded that
itself and secondly, it causes less structural disruption, which is the stress is uniform over the cylindrical surface and equal to the
particularly important for fluids having fragile gel structure like yield stress. Setting thus m = 0 in Eq. (3) results in
water–bentonite suspensions. The vane technique, although an  
πD3 H 1
established method used with many suspensions, it has not been Tm = τvn + (4)
2 D 3
used widely in the drilling fluids industry [19,33].
Various efforts have been reported in the past aiming at devel- A typical stress (torque) versus time diagram is shown in
oping models which relate microstructure (the interaction among Fig. 1, with data of sample 6, to be analyzed later. The value of
molecules and suspending particles) to macrostructure (rheol- the vane yield stress, τvn , is estimated then by Eq. (4), taking the
ogy and in particular the yield stress) but none had significant maximum shear stress (torque) value from the diagram.
 Author's personal copy
V.C. Kelessidis, R. Maglione / Colloids and Surfaces A: Physicochem. Eng. Aspects 318 (2008) 217–226
Fig. 1. Yield stress measurement with vane. Actual data of sample 6.
In the indirect techniques, the yield stress is estimated from
the rheograms obtained with a viscometer after extrapolating the
τ–γ̇ (shear stress–shear rate) curve to zero shear rate, with the
rheogram obtained with a variety of instruments like rotating
cylinders, cone and plate or parallel plates [35]. The parameter
thus estimated is often called the dynamic yield stress [33,36].
This technique has been criticized and the estimated yield stress
has not been considered by some researchers a true fluid yield
stress because its accuracy depends on several factors such as,
the assumed model, the consistency of the data or the instrument
used [23]. Furthermore, at very low shear rates, slippage of the
fluid near the wall may occur giving false readings. It is for
these reasons that researchers should be aware, not only of these
problems [23,28,37], but also of the methods used to identify
them [38].
A number of models have been proposed in the past to
estimate the yield stress of bentonite dispersions. The linear
Bingham plastic model is very often used,
τ = τB + μp γ̇
where τ is the measured shear stress, γ̇ is the imposed shear rate
and μp is the plastic viscosity. The shear rate range over which
Eq. (5) is fitted to derive the so-called Bingham yield stress dif-
fers among different investigators. Some researchers may utilize
only the two high shear rate readings, as is done by drilling fluid
industry [18,25,26], which are taken as the 600 rpm and 300 rpm
(giving Newtonian shear rates on the fixed inner cylinder of
1021 s−1 and 511 s−1 , respectively for the rotating viscometer
used in oil-field, with inner cylinder diameter of 1.7245 cm and
an outer cylinder diameter of 1.8415 cm), thus obtaining the high
shear rate Bingham yield stress, τ HSRB . Conversely, only the lin-
ear portion of the curve may be used, normally at high, and often
more than two, shear rates [39,40] thus giving the linear shear
rate Bingham yield stress τ LSRB . Many times, though, the full
rheological data set obtained at all shear rates may be used thus
giving the Bingham yield stress τ B . The use of various Bing-
ham yield stresses, without many times having a reference on
how exactly it was determined, could be one of the reasons that
there are great discrepancies among yield stress values reported
by different investigators, even for solid suspensions in under
otherwise similar conditions.
219
In most cases, however, water–bentonite dispersions exhibit
shear thinning behavior with a yield stress [14,27,41–44].
To take into account the non-linearity of rheological data
of these bentonite suspensions, non-linear models such as
Herschel–Bulkley model [45], Casson [46] or Robertson–Stiff
[47] models have been used. The latter model uses three rheo-
logical parameters with none related to a true yield stress [48].
Hence, in this work, only the first two mentioned models have
been utilized. The Herschel–Bulkley model, given by
τ = τHB + K(γ̇)n (6)
uses three rheological parameters, the Herschel–Bulkley yield
stress (τ HB ), the flow consistency index (K) and the flow behavior
index (n).
The Casson model is given by
√ √ 
τ = τC + μC γ̇ (7)
where τ C is the Casson yield stress and μC is the Casson vis-
cosity.
Considering the yield stress an engineering reality, the ques-
tion would arise as to which might be the yield stress of a
particular suspension [7]. The answer would certainly depend
on the application [4]. Barnes [7] claimed that for yield stresses
determined for shear rates greater than 0.001 s−1 , the Sisko
model [49] would be the best, but he finally suggested to use
the Bingham model, because it has more worked out solu-
tions to fluid problems, especially when compared to Casson
or Herschel–Bulkley models. But, while this is true, there are
several reports showing the disparity between theoretical and
experimental results using the Bingham plastic model for the
flow of many non-Newtonian fluids [16,17,41] and a reason for
the discrepancies could be the different Bingham yield stresses
used. On the other hand, the use of Herschel–Bulkley model has
proven to be a good choice for many cases [27,42–44], while in
(5)
many other cases, the Casson model has proven to work the best
[41,50,51]. Of course, modeling can be attempted to describe
the flow behavior of such suspensions with different flow equa-
tions, applicable only over a certain (and even narrow) range of
shear rates. Another method, also, to determine the true yield
stress could be through measurements of pressure loss − flow
rate (p − Q) under various flow conditions, matching predic-
tions with measurements in order to single out the true yield
stress. For this approach to work, however, good theoretical
models, covering laminar, transition and turbulent flows of such
fluids in various conduit shapes is essential.
3. Materials, preparation and equipment
3.1. Materials
Various bentonite-water dispersions of 5.0% (w/w) and
6.42% (w/w) were prepared using two commercial bentonite
products, Zenith© (S&B Industrial Minerals SA, Greece), a Na-
activated bentonite containing more than 90% montmorillonite
and Wyoming bentonite (Haliburton-Cebo, Holland), a natural
sodium montmorillonite, both used in oil-well drilling with par-
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220 V.C. Kelessidis, R. Maglione / Colloids and Surfaces A: Physicochem. Eng. Aspects 318 (2008) 217–226

Table 1
Sample information and measured and estimated values of yield stresses
Sample # Sample information (wt%) pH τvn (Pa) τ HB (Pa) R2c SQ2 (Pa2 ) τ CA (Pa) R2c SQ2 (Pa2 )

1 Zenith 5% 7.31 5.66 5.51 0.9993 0.02 5.92 0.9928 0.21

2 Zenith 5% 8.02 7.54 7.06 0.9993 0.02 6.55 0.9988 0.03
3 Zenith 5% 9.47 8.34 8.23 0.9908 0.30 8.38 0.9882 0.38
4 Zenith 5% 11.06 23.83 19.15 0.9991 1.23 28.84 0.9655 46.80
5 Zenith 6.42% 7.92 11.45 7.91 0.9985 0.11 10.39 0.9675 2.52
6 Zenith 6.42% 10.77 82.98 77.53 0.9670 21.51 86.62 0.9283 46.70
7 Wyoming 5% 7.6 24.06 20.80 0.9984 0.53 19.80 0.9962 1.23
8 Wyoming 5% 7.69 23.95 20.92 0.9977 0.77 20.61 0.9972 0.94
9 Wyoming 5% 8.87 14.71 10.36 0.9987 0.14 10.20 0.9992 0.09
10 Wyoming 5% 10.56 17.31 21.76 0.9984 2.12 32.11 0.9622 50.90
11 Wyoming 6.42% 6.52 43.12 40.85 0.9984 1.73 39.87 0.9980 2.28
12 Wyoming 6.42% 5.29 22.59 17.09 0.9993 0.56 15.58 0.9978 1.77
13 Wyoming 6.42% 8.98 37.25 32.95 0.9991 1.32 33.38 0.9976 3.13
14 Wyoming 6.42% 10.41 30.95 21.34 0.9981 6.86 25.06 0.9900 35.25

ticle sizes for both bentonites smaller than 70 ␮m, with most
of them around 10–20 ␮m [27,44]. The samples were prepared
according to American Petroleum Institute (API) procedures
[25,26] with deionized water, using a Hamilton Beach high
speed mixer to stir the samples at 11,000 rpm for 20 min when
preparing the dispersion. In order to have dispersions covering
an extended yield stress range, the pH of the dispersions was var-
ied. The sample pH was adjusted to the desired value with 1 M
NaOH or 5 M HCl, while the ‘natural’ pH of the dispersions,
without any additive, was around 8.8. The samples were then
poured in a covered container and left undisturbed for 16 h for
full hydration at room temperature. Prior to testing, the samples
were stirred for 5 min at 11,000 rpm and the final pH value was
recorded and it is this value that is reported in Table 1, as there
is a shift in pH of bentonite dispersions [27]. After pH measure-
ment, the sample was poured into the viscometer container to
get the rheograms and it was then poured into the container to
measure the vane yield stress.
3.2. Equipment
Rotational viscometric data was obtained with a variable
speed rotational viscometer (Grace Instruments, USA) which
offers electronically controlled and continuously varied speeds
from 0.01 rpm to 600 rpm, connected to a PC for data storing
and analysis. The inner fixed cylinder diameter is 1.7245 cm and
the outer rotating cylinder diameter is 1.8415 cm thus giving a
gap with a diameter ratio of δ = 1.06785. Viscometric data were
obtained at fixed speeds of 600 rpm, 300 rpm, 200 rpm, 100 rpm,
60 rpm, 6 rpm and 3 rpm, which give Newtonian shear rates on
the inner fixed cylinder of 1021.38 s−1 , 510.67 s−1 , 340.46 s−1 ,
170.23 s−1 , 102.14 s−1 , 10.21 s−1 and 5.11 s−1 , respectively.
The readings were taken from high to lower speeds, while
rotation lasted for 60 s at each rotational speed, with readings
recorded every 10 s, thus giving six measurements for each rota-
tional speed. These six values were then averaged and recorded
for rheological parameter estimation according to the two chosen
models.
Direct yield stress measurements were performed with a
Brookfield yield stress vane measuring device using two dif-
ferent four bladed vane spindles, in order to cover the extended
yield stress range, one with length of 4.333 cm, and diameter of
2.167 cm while the second had length of 2.535 cm and diameter
of 1.267 cm. Vane was rotated at 0.1 rpm.
3.3. Methodology
All measurements were done at 25 ◦ C. pH was measured with
Inolab pH-meter and ranged from acidic (pH of 5.3) to alkaline
(pH of 11.1). The conditions of testing the 14 samples are shown
in Table 1.
The effects of length of measuring time while at a particular
rotational speed on the measured rheological properties was also
determined. This was done by using measuring times of 60 s,
120 s and 180 s. An extensive literature search did not return
any particular standard but the usual practice [25,26] recom-
mends rotation until ‘reading stabilizes’. Such testing should
be performed under otherwise similar conditions of samples.
For this reason, three separate batches of Zenith dispersions at
6.42 wt.% were prepared exactly the same way, following API
preparation procedures, with the samples left overnight for 16 h
for full hydration and agitated for 5 min at 11,000 rpm prior to
testing, thus experiencing the same preshearing history.
The build up of the structure of these dispersions over time
was measured by measuring the vane yield stress, using a 6.42%
Zenith bentonite dispersion prepared as per API specifications
and left to hydrate overnight for 16 h. Prior to first measurement
(t = 0), the dispersion was agitated at 11,000 rpm for 5 min and
then the vane yield stress was determined after 60 min, 120 min,
180 min and 240 min. At 300 min, the dispersion was presheared
according to the normal practice (i.e. 11,000 rpm for 5 min)
before final measurement.
4. Results and discussion
4.1. Comparison of yield stress measurement techniques
For each of the samples, the rheograms were fitted to the
Herschel–Bulkley and Casson models, computing the relevant
rheological parameters together with the estimation of the good-
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V.C. Kelessidis, R. Maglione / Colloids and Surfaces A: Physicochem. Eng. Aspects 318 (2008) 217–226
Fig. 2. Rheograms of measured data, of Herschel–Bulkley and of Casson mod-
els, estimated yield stresses from Herschel–Bulkley and Casson models and
measurement with vane for sample 6 (Zenith, 6.42%, pH 10.8).
ness of fit, using a standard non-linear regression package.
A typical comparison for one sample (sample 6) is shown in
Fig. 2, where the full rheograms, measured, predicted with the
Herschel–Bulkley model and with the Casson model, are shown
together with the Casson yield stress, the Herschel–Bulkley yield
stress and the vane yield stress. For the particular case it is seen
that τ HB is estimated at a lower value than τ CA , which is very
close to the 6-rpm and the 3-rpm readings, while τvn , is between
the two estimated yield stresses.
The values of the yield stresses from the two rheological
models are plotted versus the vane yield stresses in Fig. 3, with
the error bars corresponding to the standard error, as estimated
from the non-linear regression routine. Yield stresses cover an
extended range between 5 Pa and 80 Pa, with all but one being
less than 45 Pa. The results show that both τ HB and τ CA plot
around the 1:1 (perfect matching) line with τvn and both val-
ues are close to each other. Thus, for these dispersions, any of
the proposed techniques is good for measuring the yield stress.
Concentric cylinder data would then be preferable because they
also give the full rheograms from which the rheological model,
either Herschel–Bulkley or Casson model, could be derived.
The sum of square errors, SQ2 , an indication of the good-
ness of fit, defined as the sum of the square of errors between
measured shear stress values and predicted shear stress values
Fig. 3. Comparison of yield stress measured by vane to yield stress estimated
from Herschel–Bulkley and Casson models for all 14 samples.
221
Fig. 4. Sum of square errors in the estimating models by Herschel–Bulkley and
Casson vs. the measured vane yield stress.
according to either of the rheological model, have been com-
puted for all samples and are reported in Table 1 and plotted in
Fig. 4 for both models. They vary between a very low 0.02 Pa2
and a maximum of 50.9 Pa2 , with the majority of them being less
than 10 Pa2 , thus indicating a very good fit of either model with
experimental data, which was also evident from the regression
coefficient which for all samples was higher than 0. 99 but in one
case, where it was 0.9283 (Table 1). For some samples (samples
1, 2, 3, 5, 9, and 13), SQ2 values are small for both models, for
some samples (samples 7, 8, 11, and 12), SQ2 values are low
for the Casson and high for the Herschel–Bulkley models and
for samples 4, 6, 10 and 14, SQ2 values are high for Casson and
low for Herschel–Bulkley models. However, these results do not
seem to correlate with the small differences obtained between
the Casson and the Herschel–Bulkley yield stress values.
The Herschel–Bulkley model has also been found to per-
form good representation of rheograms of similar dispersions
[27,36,43,44,52] while it has been reported [53,54] that solid
particle suspension rheological data that were explained by Cas-
son model, could be well described also by the Herschel–Bulkley
model.
The close match of the vane yield stress with either τ HB or τ CA
can be further quantified if an index of the degree of deviation,
DD , defined by Tsamantaki et al. [33] as
N 
 2
τy,k
DD = −1 (8)
τvane
i=1
is computed, where τ y,k can be either τ HB or τ CA . A value of DD
close to zero would indicate that τ y,k is very close to vane yield
stress. Computation of the degree of deviation gave DD = 0.5 for
the Herschel–Bulkley model and DD = 1.1 for the Casson model,
indicating that not only the values are close to each other but also
close to the vane yield stress.
The close matching of vane yield stress with yield stresses
estimated by extrapolation using either Herschel–Bulkley or
Casson models observed for all samples in this work has been
reported previously by only few investigators [19,55], while the
majority of prior work shows much higher vane yield stress
values than values obtained by extrapolation.
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222 V.C. Kelessidis, R. Maglione / Colloids and Surfaces A: Physicochem. Eng. Aspects 318 (2008) 217–226
Large differences between static and dynamic yield stresses
of various yield-pseudoplastic fluids, including bentonite dis-
persions, have been reported by previous investigators. Saak et
al. [56] referenced prior work on yield stress of oil well cement
slurries, with Haimoni and Hannant [57] reporting static yield
stresses twice as high as the dynamic ones determined with
concentric cylinder viscometer and with Banfill and Kiching
[58] reporting large differences between static yield stresses and
dynamic yield stresses obtained with parallel plate viscometer,
with all attributing these differences to wall slip in the concentric
cylinder or parallel plate instruments.
Ulherr et al. [59] reported static and dynamic yield stresses
of Carbopol solutions and of TiO2 suspensions. Static yield
stresses were determined by vane and slotted plate technique,
while dynamic yield stresses were determined by rotating
viscometer and extrapolation using fourth order polynomial,
Herschel–Bulkley or Casson models. Static and dynamic yield
stresses of Carbopol solutions were similar, but static yield
stresses of the TiO2 suspensions were three times as much
as the yield stresses determined by extrapolation. They have
attributed the huge differences to wall slip and to prior shear
history, expected to play significant role for TiO2 suspensions
but not for Carbopol gels.
Nguyen et al. [60] have compared yield stresses of 50% and
60% TiO2 dispersions employing static methods (vane and slot-
ted plate) and from extrapolation of Herschel–Bulkley curves
and found that vane yield stresses were 1.5 and 2.5 times
more than the yield stresses obtained by extrapolation. The val-
ues reported were averages among different laboratories but it
should be noted that preparation and preshearing procedures
were not similar among the different laboratories.
If the estimated yield stresses by extrapolation are consid-
erably smaller than the vane yield stresses, then the fluid may
‘slip’. Most of the dynamic yield stress values obtained in this
work using either the Herschel–Bulkley model or the Casson
model were close to the static yield stresses measured by the
vane and no huge differences were observed of the magnitude
reported by previous investigators. Thus no slipping should be
taking place within the concentric cylinder viscometer, and this
should be attributed to the extensive and strong preshearing prior
to measurement [27].
Zhu et al. [55] reported close matching of vane yield stresses
with extrapolated yield stresses using Herschel–Bulkley model
on parallel plate rheometric data, for 40–70% TiO2 water sus-
pensions, with τ HB , though, being constantly slightly higher than
τvn , however, they used sand paper to cover the plates avoiding
thus wall slip while they applied prior shearing by stirring the
samples with spatula before testing.
Power and Zamora [19] found that τ HB was much closer to
the vane yield stress for a series of drilling fluids, with yield
stress values between 0 Pa and 15 Pa, particularly when com-
pared to the high shear rate Bingham yield stress, τ HSRB or to
the Bingham yield stress, τ B . But there was greater variation of
τ HB with τvn compared to the variation reported in this work,
giving a much higher degree of deviation of DD = 18. The sim-
ilarities of the results of the work of Power and Zamora [19]
with the results of this work are attributed to prior intensive
Fig. 5. Variation of vane yield stress with pH for two different bentonites
(Z = Zenith, W = Wyoming) at the two stated concentrations.
shearing of the samples because they have also followed API
specifications.
4.2. Effect of pH on the yield stress
The variation of the vane yield stress with pH, grouped for the
different bentonite types and concentrations is shown in Fig. 5.
There are various trends for the different conditions. For the
5% concentration of bentonites and pH range of 7.0–10.5, very
little variation with pH is observed of the vane yield stress. Zenith
bentonite, however, at pH of 11.1, gives a vane yield stress which
is twice as great compared to yield stresses at the other pH values.
This behavior is different from the results of 6.42% Wyoming
bentonite concentration, which showed a maximum in the vane
yield stress at pH range of 6.5–8.0, similar to results from prior
work [27], where a maximum of τ HB was obtained at pH of 8.8.
Zenith bentonite results, although with only two points, show
that vane yield stress drastically increased when pH was strongly
alkaline.
4.3. Effect of measuring time and rest period
In Fig. 6 the results of the tests to estimate the effect of
measuring time at each rotational speed are shown, where data
points (τ–t) are plotted for three rotational speeds (600 rpm,
200 rpm and 100 rpm) for the three measuring times of 60 s,
120 s and 180 s. It can be seen, Fig. 6a, that for the highest
shear rate employed (600 rpm), shear stress values taken with
120 s rotational time almost coincide with the values taken with
180 s rotational time, while the values taken with 60 s rotational
time fluctuate between the values of the 120 s time and values
slightly lower, with differences less than 10%. For the lower
rotational speeds (300 rpm and 200 rpm, Fig. 6b and c, respec-
tively) the measured values essentially coincide for all three
measuring times. Similar results were observed for the lowest
rotational speeds, not shown here for brevity. Hence, this time
series analysis shows that there exist no significant differences
for rotation times of 60 s, 120 s and 180 s. Computation of τ HB
and τ CA for each of the three samples gave the values depicted
in Fig. 7. Interestingly enough, the yield stress estimated by
 Author's personal copy

V.C. Kelessidis, R. Maglione / Colloids and Surfaces A: Physicochem. Eng. Aspects 318 (2008) 217–226 223

Fig. 7. Variation of estimated yield stress by Herschel–Bulkley model and by

Casson model with length of measurement time at each rotating speed. Zenith
bentonite dispersion at 6.42% (w/w).

with a fairly high regression coefficient of 0.902. Interest-

ing to note that the last measurement, taken after preshearing
the sample, shows that preshearing after 300 min for 5 min
did not affect the fluid structure since the point falls well
within the curve that describes prior rest history of the
dispersion.

4.4. Prediction of yield stress

Models have been proposed to relate microstructure of

charged particle dispersions to macroscopic parameters such as
rheology and yield stress through phenomenological modeling
using DLVO theory [61,62]. Proposed models [63–66] can be
cast in a form of
τy ∝ φ2 (A − Bζ 2 ) (10)
where the term (A) represents van der Waals attractive forces, the
term Bζ 2 represents electrostatic forces, ζ is the zeta potential
and φ is solid volumetric concentration. Eq. (10) predicts a max-
imum yield stress at the isoelectric point (iep), i.e. the value of
pH at which zeta potential is zero (ζ = 0), which is proportional
to the square of volumetric concentration. The proposed equa-
tion described well experimental results as reported by Leong et
al. [67] with ZrO2 particles at fairly high concentrations, with
Fig. 6. Comparison of variation of shear stress with time allotted for measure-
ment, for 180 s, 120 s, and 60 s for the three rotational speeds: (a) 600 rpm, (b)
300 rpm and (c) 200 rpm. Zenith bentonite, 6.42% (w/w).

the Casson model is almost the same with that estimated from
the Herschel–Bulkley model, if data from 180 s measurement
time are used, while it is larger at 120 s measurement time (ratio
of τ CA /τ HB = 1.16) and much larger at 60 s (τ CA /τ HB = 1.25).
Unfortunately, no vane yield stress measurements were made
for these samples.
The results of the time evolution tests of the vane yield stress
while the dispersion is at rest are shown in Fig. 8. It is seen that
the fluid builds continuously structure over time and the yield
stress data follow a power type of growth, given by

τvn = 22.7 + 0.076(t)0.893 (9) Fig. 8. Evolution of vane yield stress with time. Zenith bentonite at 6.42% (w/w).
 Author's personal copy
224 V.C. Kelessidis, R. Maglione / Colloids and Surfaces A: Physicochem. Eng. Aspects 318 (2008) 217–226
yield stress measured by the vane technique, by Scales et al. [64]
with alumina slurries and yield stress measured by vane, while
Prestige [68] found Eq. (10) could describe Bingham yield stress
data of galena suspensions at concentrations less than 10% but
only for pH values greater than 6.0, while an additional param-
eter had to be included for the yield stresses taken at pH less
than 6.0. Sakairi et al. [69] proposed also a model for bentonite
dispersions in electrolyte solutions but the predictions have been
recently questioned [70] because it grossly under predicted mea-
sured values and furthermore, it was found to work only in a very
narrow range.
Zeta potential of bentonite dispersions is negative over the
entire pH range [39,71–73] with the iep, considered the pH of
the medium at which the edges of bentonite platelets have no
charge, covering a range of values of pH between 5.0 and 8.0
[27]. Eq. (9) could thus be applicable if there was a minimum of
zeta potential over this pH range, but Missana and Adellm [71]
have reported no variation of ζ with pH for sodium–bentonite
dispersions, while Niriella and Carnahan [74] have reported a
local maximum.
In the absence of any predictive models, it would be inter-
esting to compare maximum measured vane yield stress values,
within the reported (iep) range of bentonite dispersions, with
values predicted by the equation proposed by Zhou et al. [75]
for concentrated alumina slurries, given by
36AH φ2
τy,max = (11)
24π2 h20 d
where AH is the Hamaker constant, φ is the solid volumetric
function, h0 is the inter-particle distance and d is the diameter
of the particle. To use Eq. (11), the Hamaker constant must
be known but it has been reported as an extremely difficult to
measure quantity and may be completely different from values
predicted from theory [71,76]. For bentonite dispersions, a value
of 2.25 × 10−20 J has been predicted [77], Missana and Adellm
[71] had to use a higher value of 6.0 × 10−20 J and reported
even higher values used by other investigators of 1 × 10−19 J,
in order to match theoretical coagulation predictions with their
experimental data. Missana and Adellm [71] attributed the need
to use higher AH values in order to explain experimental results,
to additional attractive forces, other than the van der Waals forces
not considered in classical DLVO theory, such as hydration and
swelling energies.
Maximum yield stress values could be predicted using
Eq. (11), taking values for particle diameter, d = 20 nm, for
inter-particle distance, h0 = 1.0 nm and different values for the
Hamaker constant, for the two concentrations tested. The com-
puted values have been compared with the maximum measured
values from both bentonite dispersions within the pH range of
the (iep), with the results shown in Fig. 9. Measured maximum
yield stresses for Zenith bentonite closely matched predicted
maximum values, for the value of the Hamaker constant of
AH = 0.04 × 10−20 J, while a good match was also evident for
Wyoming bentonite dispersions but for higher Hamaker con-
stant value, AH = 0.15 × 10−20 J. A range, of course, of degrees
of matching could have been obtained taking different combina-
Fig. 9. Measured and predicted maximum yield stress values of Wyoming and
Zenith bentonite dispersions for two different concentrations at various assumed
values of Hamaker constant.
tions of inter-particle distances, particle diameters and Hamaker
constants.
Interestingly enough, the values of AH that gave very sim-
ilar maximum yield stresses to the measured ones, are one to
two orders of magnitude lower than the values utilized by pre-
vious investigators reported above. Zhou et al. [75] suggested
that their proposed model should be accurate enough to a first
order of magnitude. Of course, a difference of one or two orders
of magnitude can result in complete different conclusions in
stability predictions, with several authors using different values
without stating the reasons for doing so [71]. These results then
indicate that Eq. (11) could be a very good starting point for
estimation of yield stress of bentonite dispersions provided that
more accurate values of Hamaker constants, of particle diameter
and of particle thickness become available.
5. Conclusions
Aqueous dispersions of two different bentonites, used in oil
well drilling, at 5 wt.% and 6.42 wt.% concentrations and over
a range of pH values, exhibit non-linear rheograms that can be
equally well described by Herschel–Bulkley and Casson mod-
els. The yield stress predicted by both models and the yield stress
measured by the vane are very close to each other. This close
match is attributed to the good preparation and preshearing pro-
cedures which are similar to the ones that the dispersions may
experience under various flow conditions.
pH affects yield stress of these dispersions and the variations
observed is the same for the yield stresses measured by the three
techniques. Different effects have been observed for the two
different bentonites and for the two concentrations.
Measuring time of shear stress at each rotational speed should
be at a minimum of 60 s as no variation has been observed for the
longer measurement times of 120 s and 180 s for all rotational
speeds. The vane yield stress increases with rest time after inten-
sive preshearing indicating that the fluid continuously builds
structure. The evolution could be well described with a power
 Author's personal copy
V.C. Kelessidis, R. Maglione / Colloids and Surfaces A: Physicochem. Eng. Aspects 318 (2008) 217–226
law over a period of 5 h. Intensive preshearing after 5 h was not
sufficient to destroy the structure of the dispersion.
A theoretical model proposed for the maximum yield stress
of charged particle suspensions at the isoelectric point could be a
good starting point to predict yield stress of bentonite dispersions
because it gives a close match with the maximum measured yield
stress of the dispersions within the range of the iep, after using
values of Hamaker constants which were one or two orders of
magnitude lower than the ones reported previously.
Acknowledgement
The authors would like to acknowledge Mrs. C. Tsamantaki
for the data collection and analysis.
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