Applied Clay Science 108 (2015) 182–190

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Applied Clay Science

journal homepage: www.elsevier.com/locate/clay

Research paper

Effects of bentonite concentration and solution pH on the rheological

properties and long-term stabilities of bentonite suspensions
Ko Yeon Choo ⁎, Kang Bai
Korea Institute of Energy Research, 152 Gajeong-ro, Yuseong-gu, Daejeon 305-343, Republic of Korea

a r t i c l e i n f o a b s t r a c t

Article history: The influences of bentonite concentration and solution pH on the rheological properties and long-term stabilities
Received 3 April 2014 of bentonite suspensions were studied in this research. Rheological properties were measured at bentonite con-
Received in revised form 17 February 2015 centrations of 5, 7, and 9 wt.%. It was found that the viscosity and shear stress increased with increasing bentonite
Accepted 19 February 2015
concentration and storage time. The initial shear stress of the 9 wt.% bentonite suspension grew larger with in-
Available online 6 March 2015
creasing storage time than did the yield stress value obtained from Herschel–Bulkley model fitting. The result
Keywords:
showed that a significant yield value was required to break the particle network due to the large cohesion
Bentonite force between the particles. Rheological properties and zeta potentials were measured with various amounts
Rheology of a 1 M HCl solution added to a 5 wt.% bentonite suspension. The amount of HCl solution added had a significant
Herschel–Bulkley model impact on the zeta potential of the bentonite suspension. The absolute value of the zeta potential decreased as the
Bingham model added amount of HCl solution increased. Therefore, particle aggregation was facilitated due to a decrease in the
pH effect stability of the suspension. Comparing the shear stress obtained from the upward flow curve at a shear rate of 3.4
Particle interaction 1/s with the yield stress obtained from the downward flow curve fitted with the Herschel–Bulkley model or Bing-
ham model, as a function of the added amount of HCl solution, showed that the difference between the two
values was large in acidic media with high HCl content, but insignificant in neutral or basic media. In addition,
the large shear stress phenomenon at a shear rate of 3.4 1/s diminished with increasing storage time, which
was due to the change in the pH of the suspension from acidic through neutral, to basic with increasing storage
time.
© 2015 Elsevier B.V. All rights reserved.

1. Introduction
Aqueous bentonite dispersions are important to many industries
and are especially essential to oil-well drilling and the wastewater treat-
ment industry (Kelessidis et al., 2007). Bentonite dispersions in the oil-
well drilling industry conventionally have a basic pH of 9 to 12 (Gray
and Darley, 1980; Kelessidis et al., 2007). The wastewater treatment in-
dustry, however, involves the adsorption of harmful metals, and the pH
of the suspensions in this industry ranges from acidic to basic (Khan
et al., 1995; Abollino et al., 2003; Kelessidis et al., 2007).
The principal mineral constituent of bentonite is montmorillonite,
which is one of the dioctahedral smectites. Smectites are 2:1
phyllosilicates with a total layer charge between 0.2 and 0.6 per
half unit cell (Bergaya and Lagaly, 2013). They have colloidal proper-
ties, swelling properties and high plasticity when mixed with water,
and they can be employed in a variety of fields (Isci et al., 2004). Benton-
ite can be classified into either a Na-bentonite that has a high swelling
capacity or a Ca-bentonite that quickly generates colloids in water as a
non-swelling clay (Hassan and Abdel-Khalek, 1998; Abu-Jdayil, 2011).
⁎ Corresponding author. Tel.: +82 42 860 3272; fax: +82 42 860 3133.
E-mail address: kychoo@kier.re.kr (K.Y. Choo).
Bentonite contains not only montmorillonite but it also contains various
other minerals such as quartz and calcium- and sodium-feldspar
(Abu-Jdayil, 2011). Na-bentonite contains sodium montmorillonite
at 70–90 wt.% and the sodium montmorillonite is the cause of its
swelling behavior (Karunaratne et al., 2001; Au and Leong, 2013).
Osmosis is the principle force that drives water molecules into the
interlayers of the particles. The water molecules hydrate sodium
ions, causing swelling and ultimately delamination. As a result, ben-
tonite is capable of expanding from its dry volume to more than 10
times its size in water (Murray, 1991; Au and Leong, 2013).
A good quality bentonite should contain mainly montmorillonite,
but in practice bentonites often contain other clay minerals and non-
clay minerals such as quartz and plagioclase in appreciable amounts,
which may have an adverse effect on bentonite quality, for example
swelling capacity (Abdou et al., 2013).
The montmorillonite particle, a major component of bentonite, has a
plate-like structure with layers consisting of a central octahedral sheet
sandwiched between two tetrahedral sheets; it has negatively charged
faces and edges that take up less than 5% of the total surface area, and its
edge is positively charged at a pH below the isoelectric point and is neg-
atively charged at a pH above the isoelectric point (Delgado et al., 1986;
Ramos-Tejada et al., 2001; Zhang and Yin, 2002; Kelessidis et al., 2007).

http://dx.doi.org/10.1016/j.clay.2015.02.023
0169-1317/© 2015 Elsevier B.V. All rights reserved.
 K.Y. Choo, K. Bai / Applied Clay Science 108 (2015) 182–190
The isoelectric point of a dispersion is defined as the pH of a dispersion
that has zero charge (van Olphen, 1977; Kelessidis et al., 2007).
There are three possible association modes between the particles
in an aqueous bentonite dispersion: face-to-face, edge-to-edge and
edge-to-face modes. The face-to-face association mode results in
particles that are larger and thicker than the particles caused by the
other two modes. The other two modes lead to a card-house struc-
ture with a large 3-dimensional volume (van Olphen, 1977; Benna
et al., 1999; Uskarci, 2006). The gel formation of montmorillonite
can have two possible mechanisms. The first mechanism forms gel
through the electrostatic attraction between the negatively charged
face and the positively charged edge (van Olphen, 1951, 1964,
1977; Benna et al., 1999; Heller and Keren, 2001) and the second
mechanism forms gel through face-to-face and edge-to-edge inter-
actions through long-range electrostatic double-layer repulsion
(Norrish, 1954; Callanghan and Ottewill, 1974; Moan, 1992; Benna
et al., 1999; Heller and Keren, 2001). The two mechanisms are not
mutually exclusive, but they may work together (Benna et al.,
1999). The face-to-face structure is called the band-like structure
and the edge-to-edge and edge-to-face structures are called the
card-house structures (Jeong, 2011).
However, to cause gel formation from electrostatic attraction, the pH
must be below the isoelectric point (otherwise the positively charged
edge cannot exist). The isoelectric point for montmorillonite disper-
sions, which has zero charge, has been reported to exist between pH
values of 5.0 and 8.0 by numerous researchers (Kelessidis et al., 2007).
Heath and Tadros (1983) estimated the isoelectric point to be approxi-
mately pH 7, a level which exhibited a minimum yield value and resid-
ual viscosity. They measured the yield value and residual viscosity of the
clay as functions of pH and NaCl concentration.
Rheology is the study of the deformation and flow of substances
under the influences of applied stresses (Barnes et al., 1989;
Czibulya et al., 2010). Although rheology is based on the principles
of classical mechanics, in practice, substances do not exhibit elastic,
viscous, and plastic characteristics separately. Instead, they exhibit
these characteristics in combinations, which cause complex results.
The complex results include viscoelastic and viscoplastic bodies
with shear thinning or shear thickening properties similar to an ac-
tual plastic system, as well as the well-known Bingham body that be-
haves as a rigid body at low stresses but flows as a viscous fluid at
high stresses (Bingham, 1916; Czibulya et al., 2010). Therefore, a
viscoplastic network of dispersed particles in liquid media, such as
a clay mineral suspension, is characterized by different yield stresses
(Czibulya et al., 2010). Furthermore, a bentonite suspension has a
significant thixotropy and it also has high viscosity and yield stress
at a very dilute concentration (even at just a few percent of solid
matter) (Au and Leong, 2013). Thixotropy gives almost solid-like
characteristics at rest, but it gives flowing characteristics under
stress, including the extreme shear thinning property (Barnes,
1997; Czibulya et al., 2010).
The viscosity of a two-phase particle network, such as a suspension,
is controlled by its colloidal and hydrodynamic factors which depend on
the flow rate. Therefore, viscosity is influenced by the arrangement,
composition, size and shape of the particles in a coherent network,
and the colloidal parameters govern the rheological behavior of the sus-
pension under low shear and high viscosity conditions. Colloidal param-
eters include surface properties, such as suspension concentration,
particle size distribution, particle shape, electric charge and adsorption
layer, and solution conditions, such as pH and salt concentration
(Czibulya et al., 2010).
The rheological behavior of a suspension is one of the most sensitive
indicators for determining the interactions between particles and small
changes in the composition of the medium can result in significant rhe-
ological differences (Isci et al., 2004). In addition, rheological properties
can determine under what conditions the clay can be used (Benna et al.,
1999). Consequently, pH may not only determine the association mode
183
between the bentonite particles, but pH may also influence the rheolog-
ical behavior that determines particle interactions.
Therefore, in this paper the influence of the bentonite concentration
and the solution pH on the rheological behavior of a bentonite suspen-
sion was studied. Furthermore, the long-term stability of the association
mode initially formed in the bentonite suspension, was also investigat-
ed, including the relationship between time and the hydration of
bentonite.
2. Theoretical background
The concentration of bentonite affects all of the rheological prop-
erties and a high enough bentonite concentration causes the forma-
tion of a continuous gel structure instead of individual flocs (Abu-
Jdayil, 2011). The gel structure is slowly established over time
because suspended particles orient towards positions of the mini-
mum free energy according to Brownian motion (Luckham and
Rossi, 1999; Abu-Jdayil, 2011). The bentonite concentration is there-
fore an important factor that can influence the length of time re-
quired for the gel to obtain maximum strength (Abu-Jdayil, 2011).
The Herschel–Bulkley model and the Bingham model were
employed to explain the rheological behavior of a bentonite suspension
as functions of the concentration of bentonite and the storage time.
2.1. Herschel–Bulkley model (Brookfield)
n
τ ¼ τ 0 þ kγ ð1Þ
τ shear stress, dyn/cm2
τ0 yield stress, dyn/cm2
k consistency index, cP
γ shear rate, 1/s
n flow index
Yield stress is the magnitude of the shear stress needed to initiate
flow; consistency index is the viscosity of a material at 1 reciprocal sec-
ond; and flow index is the degree with which a material exhibits non-
Newtonian flow behavior. Because Newtonian materials exhibit linear
behaviors in shear stress vs. shear rate, the flow index indicates how
non-linear a material is. A n b 1 means that the apparent viscosity of
the material decreases as the shear rate increases due to shear-
thinning or pseudoplastic behavior. Shear thinning gets larger as n ap-
proaches 0. When n N 1, the apparent viscosity increases as the shear
rate increases due to shear-thickening or dilatant behavior. The model
should be used for non-Newtonian and time-dependent materials
with a yield stress. Materials with yield stresses start to flow after a cer-
tain amount of shear stress has been applied.
2.2. Bingham model (Brookfield)
τ ¼ τ 0 þ ηD ð2Þ
τ shear stress, dyn/cm2
τ0 yield stress, dyn/cm2
η plastic viscosity, cP
D shear rate, 1/s
Similar to the Herschel–Bulkley model, the Bingham model also
shows yield stress, which is the amount of shear stress required to initi-
ate flow. It also provides plastic viscosity, which is the viscosity of a ma-
terial after yielding. This model should be used for non-Newtonian
materials with a yield stress that act in a Newtonian fashion once the
materials start to flow. Consequently, a linear shear stress-shear rate
plot is formed.
184 K.Y. Choo, K. Bai / Applied Clay Science 108 (2015) 182–190
3. Materials and methods
3.1. Materials and suspension preparation
Na-bentonite purchased from Alfa Aesar, A Johnson Matthey
Company, was used to prepare the bentonite-water dispersions. Ac-
cording to the certificate of analysis from Alfa Aesar, the bentonite
had the appearance of a pale brown powder, exhibited a mass loss
on drying of 12.5 wt.% and had a swelling volume of 28.1 ml (2 g in
100 ml water). The main elements of the bentonite were eluted
using acid (HNO3 + HF), followed by chemical analysis by ICP-OES
4300 DV (Perkin Elmer Co., USA). The following parameters were
used: a cross flow nebulizer, a Scott type spray chamber, a RF
power of 1.3 kW, an outer Ar flow rate of 15.0 l/min, an auxiliary Ar
flow rate of 0.2 l/min, a nebulizer Ar flow rate of 0.80 l/min, a peri-
staltic pump flow rate of 1.5 ml/min and a viewing height (mm
above load coil) of 15.0 mm. X-ray diffraction (Philips Expert MPD)
analysis was carried out to obtain definitive information on the min-
eralogical composition of the bentonite. The following parameters
were used for the XRD characterization: 2theta ranges of 3–65°, a
step size of 0.01°, a scan speed of 0.04°/s, a counting time of 1550 s
(25.83 min), a slit width of 1/4°, an acceleration voltage and current
of 40 kV and 30 mA, respectively, and a time/step of 0.25°. The
Siroquent Ver 3.0 software was used for the qualitative analysis. An-
alytical grade HCl and distilled water were used in the research. Dis-
persions were prepared with 5, 7, and 9 wt.% bentonite to measure
zeta potentials and rheological properties. The bentonite was dis-
persed in water by mechanical mixing for 5 min. Each bentonite sus-
pension was covered after mixing and stored at room temperature
for a certain amount of time. Flow curves of the suspension were
measured at different storage times. The suspension was mechani-
cally stirred for 5 min prior to measuring zeta potential and rheolog-
ical properties, in order for the structure of the particle network in
suspensions to be maintained constant. The influence of pH was in-
vestigated using a bentonite-water dispersion of 5 wt.%. The 5 wt.%
bentonite-water dispersion was adjusted to different pH values
using a 1 M HCl solution.
3.2. Measurement of rheological properties
Shear stress and viscosity at various shear rate values as a function of
bentonite concentration and pH were measured with a Brookfield
LVDV-II + Pro viscometer, 1934. The viscometer was connected to a
computer which could automatically control the shear rate and collect
data with Rheocalc 32 software. In addition, the Rheocalc 32 software
was capable of analyzing data and applying mathematical models
such as the Bingham model and the Herschel–Bulkley model. A small
sample adapter was also used. It was equipped with a circulating
water bath for temperature control and composed of a water jacket, lo-
cating channel assembly, spindle, sample chamber, insulating cap, ex-
tension link and embedded RTP temperature probe. An appropriate
amount of the dispersion was placed in the sample chamber and an ap-
propriate spindle immersed in the dispersion was connected to the vis-
cometer with the extension link; the chamber was then covered with
the insulating cap. The viscometric data were obtained by continuously
varying the rotational speed in an up–down geometric speed progres-
sion mode, which varied from 10 rpm to 200 rpm at intervals of
10 rpm at 25 °C. Shear stress data were recorded at time intervals of
30 s at each shear rate. The upward flow curve was determined at a
shear rate ramp of 10 rpm from 10 rpm to 200 rpm, then, the ramp
was reversed to measure the downward flow curve.
Yield stress, which is the amount of shear stress needed to initiate
flow, is an indicator of the magnitude of the strength of attraction be-
tween the particles in the suspension and it is related to the volume
fraction of solids, particle size and the composition of a particle network.
The relative magnitude of the strength of attraction between the
particles can be studied when the volume fraction, particle size and
structure of the network are held constant. In other words, the structure
of the particle network in suspensions with identical powder and vol-
ume fraction can be maintained constant by preshearing the suspension
prior to measurement of yield stress (Franks, 2002). The rheological pa-
rameters were determined by applying a nonlinear regression for the
Herschel–Bulkley model and a linear regression for the Bingham
model to the measured viscometric data. In addition, the thixotropy,
the area between the upward flow curve and downward flow curve,
was also determined (Czibulya et al., 2010). Rheological properties
were measured twice to confirm the reproducibility.
3.3. Measurement of zeta potential
The zeta potential was measured with a ZetaProbe from Colloidal
Dynamics. The pH values in the suspensions were measured with a pH
electrode equipped in the ZetaProbe. Zeta potential is a measurement
of electric charge on the surfaces of particles. When an electric field is
applied to a solution, the particles travel due to the charges of the parti-
cles. The application of an alternating electric field causes the particles
to move back-and-forth, generating sound waves. The velocities of the
particles can be computed from the sound waves and the sound wave
is proportional to the magnitude of the applied electric field. Conse-
quently, zeta potential can be computed from the dynamic mobility
which is the velocities divided by the magnitudes of the alternating re-
gions (www.colloidal-dynamics.com). Zeta potential was averaged over
5 times for each test. The maximum standard deviation was 0.08.
4. Results and discussion
The XRD analysis revealed the bentonite contained impurities such
as gypsum, quartz, plagioclase, dolomite, pyrite, biotite etc. as well as
montmorillonite. It was confirmed that the main phase of the bentonite
was montmorillonite by the SEM images in Fig. 1. The chemical analysis
and the XRD pattern of the bentonite as the starting material are shown
in Table 1 and in Fig. 2, respectively. The ionic formula of the montmo-
rillonite was calculated from EDX data of the supernatant bentonite
separated after 24 h by centrifugation to remove any impurities. The
formula was (Na0.83 K0.06Ca0.17)(Mg0.71Fe2 +0.04Fe3 +0.74Al2.44Ti0.07)
(Al0.56Si7.44)O20(OH)4.
The cation exchange capacity (CEC) value for the ammoniated ben-
tonite was measured, as well. The ammoniation procedure used was
established by Borden and Giese (2001), and it was followed by an am-
monia electrode method. The average and standard deviation of CEC
values were 104.76 meq/100 g and 1.54, respectively.
4.1. Effect of bentonite concentration
The influence of storage time on the viscosity and flow curve of the
5 wt.% bentonite suspension is shown in Fig. 3. The viscosity and shear
stress increased with increasing storage time. Initially, there was almost
no difference between the upward and downward viscosities, but the
difference increased as the storage time increased. While the increment
of the viscosity with time decreased, the viscosity value continued to in-
crease. One possible explanation is that this is related to the hydration of
bentonite in water. The decrease in the increment of the viscosity value
with time might be related to the completion of bentonite hydration
and the hydrated bentonite could influence the measured upward and
downward viscosity values. When the Herschel–Bulkley model was ap-
plied to the upward and downward flow curves, both curves showed
correlation coefficients higher than 99.7%. The area between the up-
ward and downward flow curves increased with increasing storage
time. Although there was no thixotropic behavior during this bentonite
hydration, the behavior emerged after completion of the bentonite hy-
dration, namely after the continuous gel structure was built up. The in-
fluence of storage time on the viscosity and flow curve of the 7 wt.%
 K.Y. Choo, K. Bai / Applied Clay Science 108 (2015) 182–190 185

Fig. 2. The XRD pattern of bentonite.

with the Bingham model than with the Herschel–Bulkley model and
the correlation coefficients were more than 99.0%, excluding the up-
ward flow curve of the suspension after storage time of 72 h which
could not be fitted with either model due to the initial yield value.
The Herschel–Bulkley and Bingham parameters of the bentonite sus-
pensions with respect to the storage times in different solid concentra-
tions are summarized in Table 2. Some yield stress values of the upward
flow curves in the 5 wt.% bentonite suspension, are not shown because
the negative yield stress value was regarded as a behavior such as a sol
and determined to be meaningless. The flow curves in the higher con-
centrations were better fitted with the Bingham model than with the

1000
5 wt.% bentonite
upward downward
fresh
after 4h
after 12h
after 24h
after 52h
viscosity, cP

Fig. 1. The SEM images of bentonite. 100

bentonite suspension is shown in Fig. 4. The influence was similar to

that of storage time shown in the 5 wt.% bentonite suspension. But,
the downward curves were better fitted with the Bingham model
than with the Herschel–Bulkley model. The correlation coefficients
were higher than 99.1% for all of the upward and downward flow
10
curves. 0 10 20 30 40 50 60 70
When the concentration of bentonite in the suspensions was in- shear rate, 1/sec
creased to 9 wt.%, however, the trend of increasing viscosity with in-
creasing storage time was similar to that of the suspensions of lower 40 5 wt.% bentonite
bentonite concentrations. But, significant differences in the flow curves upward downward
fresh
35 after 4h
were observed between the 9 wt.% bentonite suspension and the other after 12h
suspensions. The influence of storage time on the viscosity and flow
shear stress, dyne/cm2

after 24h
30 after 52h
curves of the 9 wt.% bentonite suspension is shown in Fig. 5. From the
flow curves in Fig. 5, a significantly large initial stress value was ob- 25
served at the initial shear rate with the increase in storage time. This
seemed to arise from the large cohesion force between the particles. 20
Therefore, a significant yield value was required to break the particle
15
network. As a result, the area of the hysteresis loop, the area between
the upward flow curve and downward flow curve that represents thixo- 10
tropic behavior increased. In the case of the 9 wt.% bentonite suspen-
sion, all of the upward and downward flow curves were better fitted 5

0
Table 1 0 10 20 30 40 50 60 70
The chemical analysis of bentonite (wt.%).
shear rate, 1/sec
Sample SiO2 Al2O3 Fe2O3 MgO Na2O CaO K2 O
Fig. 3. The rheological properties of 5 wt.% bentonite suspension with increasing storage
Bentonite 65.58 18.72 6.55 1.74 0.78 0.53 0.25
time.
186 K.Y. Choo, K. Bai / Applied Clay Science 108 (2015) 182–190

5000 20000

7 wt.% bentonite
upward downward 10000 9 wt.% bentonite
fresh upward downward
after 4h fresh
after 12h after 6h
after 24h after 12h
1000 after 48h
viscosity, cP

after 24h

viscosity, cP
after 52h
after 72h

1000

100

50 300
0 10 20 30 40 50 60 70 0 10 20 30 40 50
shear rate, 1/sec shear rate, 1/sec

110
400
100
350
90
shear stress, dyne/cm2

80 300

shear stress, dyne/cm 2

70
250
60
50 200

40 150
7 wt.% bentonite
30 upward downward 9 wt.% bentonite
fresh upward downward
after 4h 100
20 fresh
after 12h after 6h
after 24h after 12h
10 after 48h 50 after 24h
after 52h
0 after 72h
0 10 20 30 40 50 60 70 0
0 10 20 30 40 50
shear rate, 1/sec shear rate, 1/sec

Fig. 4. The rheological properties of 7 wt.% bentonite suspension with increasing storage
Fig. 5. The rheological properties of 9 wt.% bentonite suspension with increasing storage
time.
time.

Herschel–Bulkley model. Especially, in the case of the 9 wt.% bentonite
suspension, the upward flow curve measured after 72 h of storage
could not be fitted with either of the two models, because the initial
shear stress value was significantly high. The yield stress value in-
creased with increasing concentration and storage time, excluding
some values of the upward flow curves. The bentonite suspension
showed shear thinning behavior with low yield stress at low concentra-
tions. For the higher concentrations, however, the behavior of a Bing-
ham fluid was investigated and thixotropic behavior was dominant.
As the concentration of bentonite is an important factor which can
affect the length of time required for a continuous gel structure to attain
maximum strength, the fragments of the network broken under shear
needed time to be linked again in a 3-dimensional network (Luckham
and Rossi, 1999). As a bentonite-water suspension without additive is
alkaline, i.e. pH value higher than its isoelectric point, with both edges
and faces negatively charged, and association of the particles in a sus-
pension could be edge-to-edge (EE), edge-to-face (EF) or face-to-face
(FF), with EF and EE giving looser structures, and FF giving the strongest
structures due to the increased area of contact (Kelessidis et al., 2007).
In a higher bentonite concentration, a face-to-face 3-dimensional net-
work was preferred.
4.2. Effect of pH
The downward flow curves of the fresh suspension and the suspen-
sion stored for 72 h, with respect to the amount of 1 M HCl solution
added are shown in Fig. 6. Among the fresh suspensions, the suspension
with 5 ml of added HCl, showed the highest shear stress and a pH value
of 7.3. The pH value of the fresh bentonite suspension without adding
HCl solution was approximately 10.3. The addition of a small amount
of acid increased the shear stress, but the addition of more than 5 ml
of acid decreased the shear stress. The shear stress was predicted to in-
crease with increasing storage time at all pH values, similarly to the ef-
fect of storage time at various bentonite concentrations. However, the
shear stress increased with storage time only for the suspensions with
0, 1, and 2 ml of added 1 M HCl out of the suspensions stored for 72 h.
The shear stress decreased with increasing storage time in the solutions
with more added HCl solution.
When acid is added to a particulate suspension with negative zeta
potential, the charges will be neutralized. This results in a lower zeta po-
tential value, and eventually a lower stability of the colloidal suspension.
But, a lower pH led to decrease in the thickness of the double layer be-
cause the double layer becomes more compressed at a higher ionic
strength. Therefore, addition of acid initially increased the shear stress
due to decrease in the zeta potential. As further addition of acid caused
an increase in ionic strength, the shear stress could not increase any fur-
ther but started to decrease instead.
The shear stress from the upward flow curve at a shear rate of 3.4 1/s,
and the yield stress determined from the application of the Herschel–
Bulkley model or Bingham model to the downward flow curve, were
compared to investigate the influence of pH on the upward flow curves
of fresh suspensions and the suspensions stored for 72 h. The results of
the comparisons are shown in Fig. 7. The changes in zeta potentials with
respect to the amounts of added HCl solution are also shown.
As mentioned above regarding the rheological behavior, shear stress
and yield stress initially increased and ultimately decreased with
 K.Y. Choo, K. Bai / Applied Clay Science 108 (2015) 182–190 187

Table 2
The Herschel–Bulkley or Bingham parameters of bentonite suspensions at different solid concentration.

Solid conc. (wt.%) τ0, dyn/cm2 k or η, cP n R2

Upward Downward Upward Downward Upward Downward Upward Downward

5.0 Fresh 2.21 3.43 174.8 87.4 0.49 0.6 0.999 0.997
4h 1.54 8.23 412.5 95.3 0.38 0.63 1.0 0.999
12 h 0.45 10.6 1002 77.7 0.27 0.77 1.0 0.998
24 h (−) 13.4 1804 68.7 0.21 0.8 0.999 0.998
52 h (−) 16.9 3086 59.6 0.14 0.84 1.0 0.999
7.0 Fresh 14.5 27.1 716.9 52.8 0.38 0.89 1.0 0.998
4h 26.9 43.4 1261 40.8 0.3 Bingham 1.0 0.996
12 h 44.8 55.0 1025 43.8 0.33 Bingham 1.0 0.994
24 h 14.9 63.6 4254 43.5 0.15 Bingham 0.996 0.991
48 h 44.9 75.9 2351 40.6 0.22 Bingham 1.0 0.993
9.0 Fresh 100.5 122.1 92.2 37.8 Bingham Bingham 0.991 0.991
2h 156.7 161.1 72.0 51.4 Bingham Bingham 0.996 0.991
6h 197 186 62.2 77.5 Bingham Bingham 0.993 0.990
12 h 201.4 206.2 82.3 64.9 Bingham Bingham 0.995 0.996
24 h 216.3 223.9 99.2 76.0 Bingham Bingham 0.993 0.997
52 h 272.4 254.3 72.1 107.1 Bingham Bingham 0.994 0.998
72 h – 289.9 – 134.3 – Bingham – 0.996

(−): negative value; –: no fitting.

increasing amounts of added HCl. In the fresh suspensions, the shear
stress at the shear rate of 3.4 1/s and the yield stress obtained from
the downward flow curve were very similar to each other until the
added amount of HCl solution was increased to 3 ml. However, there
was a significant difference between the shear stress at the shear rate
of 3.4 1/s and the yield stress obtained from the downward flow curve
when more than 3 ml of HCl was added. The downward flow curves
of the fresh suspensions with 7 and 10 ml of HCl were easily fitted
with the Herschel–Bulkley and Bingham models, but it was impossible
To further investigate these observations, the shear stresses with re-
spect to the shear rates of the fresh suspensions were normalized and
are shown in Fig. 8. The shear stresses initially decreased and, then in-
creased as the shear rate increased. This trend was similar to the behav-
ior of the high concentration bentonite suspension with a long storage
time. In the case of the suspension stored for 72 h, the difference
90 -14
shear stress or yield stress, dyne/cm2

to fit the upward flow curves. 80 -16

70 -18
90
60 -20

zeta potential, mV
80 fresh suspension
HCl 0 ml
shear stress, dyne/cm 2

70 HCl 1 ml 50 -22
HCl 2 ml
HCl 3 ml
60 HCl 5 ml 40 -24
HCl 7 ml
50 HCl 10 ml
30 -26
40
20 -28
fresh suspension
30 shear stress at 3.4 sec-1
10 yield stress -30
20 zeta potential

10 0 -32
0 1 2 3 4 5 6 7 8 9 10 11 12
0 addition ml of HCl solution
0 10 20 30 40 50 60 70
shear rate, 1/sec 60 -14
shear stress or yield stress, dyne/cm2

-16
90
50
80 suspension after 72h -18
HCl 0 ml
shear stress, dyne/cm 2

HCl 1 ml
70 HCl 2 ml 40 -20
zeta potential, mV

HCl 3 ml
60 HCl 5 ml
-22
HCl 7 ml
50 HCl 10 ml 30
-24
40
20 -26
30
-28
20 suspension after 72 h
10 shear stress at 3.4 sec-1
10 yield stress -30
zeta potential

0 0 -32
0 10 20 30 40 50 60 70 0 1 2 3 4 5 6 7 8 9 10 11 12
shear rate, 1/sec addition ml of HCl solution

Fig. 6. The downward flow curves of the fresh suspension and the suspension stored for Fig. 7. The comparison of initial shear stress with yield stress and the change of zeta poten-
72 h, with respect to the amount of added HCl solution. tial with respect to the amount of added HCl solution.
188 K.Y. Choo, K. Bai / Applied Clay Science 108 (2015) 182–190

1.02
added HCl showed larger pH variations, and the pH varied from acidic
HCl addition 7 ml to neutral, further to basic as the storage time was increased. Conse-
HCl addition 10 ml
1.00 quently, the shear stress decreased, although the storage time increased
normalized shear stress

0.98
0.96
0.94
0.92
0.90
0 10 20 30 40
shear rate, 1/sec
Fig. 8. The normalized shear stresses with respect to shear rates of fresh suspensions.
between the shear stress at a shear rate of 3.4 1/s and the yield stress ob-
tained from the downward flow curve decreased.
The amount of added HCl had a significant influence on the zeta po-
tential (Fig. 7). The absolute value of the zeta potential decreased as the
added amount of HCl solution increased. Zeta potential is an electrostat-
ic potential that exists very close to particles in a suspension, and be-
cause it is the cause of the particle–particle repulsive force it can be
used to predict colloid stability with respect to particle aggregation
(MRK654-01). The pH value naturally decreased as the added amount
of HCl increased. The lower pH lowered the stability of the bentonite
suspension and promoted particle aggregation. This aggregation con-
tributed to the inability to fit the upward flow curves of the fresh sus-
pensions with 7 and 10 ml of added HCl, with the Herschel–Bulkley or
Bingham model.
The zeta potential with respect to the added amount of HCl solution
in the suspensions that acid was added to. The pH variation behavior
was similar to the results of Kelessidis et al. (2007) in which there was
a significant increase in pH value when starting from acidic values and
a small decrease when starting from alkaline values.
The Herschel–Bulkley and Bingham parameters of bentonite sus-
pensions according to storage times with different amounts of added
HCl solution are summarized in Table 3. Although thixotropic behavior
seemed to become dominant when the bentonite concentration was in-
creased, the shear thinning phenomenon stood out when the amount of
added acid was increased. The yield stress values with increasing stor-
age time decreased as the added amount of acid increased. Some of
50 60 70 the yield stress values were not listed because the negative yield stress
value was regarded as a behavior such as a sol and determined to be
meaningless. The viscosity increased with increasing storage time in
the suspensions with a small amount of added acid, but the viscosity
rather decreased with increasing storage time in the suspensions with
a large amount of added acid (Fig. 10).
The fact that the value of pH became high and the viscosity became
low, in the case of the suspensions with large amounts of added acid,
seemed to indicate a change of particle structure in the suspensions.
Based on the fact that an edge-to-face 3-dimensional network structure
was built up in an acidic medium and a face-to-face 3-dimensional
structure was formed in a basic medium (Jeong, 2011), aggregation
was preferred to flocculation by the structure conversion from the for-
mer to the latter with increasing storage time. Aggregation is described
1000
5 wt.% bentonite + HCl solution addition 1ml
upward downward
fresh
after 6h
after 12h
after 24h
viscosity, cP

after 48h
did not change with increasing storage time and was almost constant. after 72h
However, the upward flow curve with prolonged storage time (72 h)
could be fitted with Herschel–Bulkley or Bingham model. This might
mean that the storage time does not affect zeta potential, but it influ-
ences the rheological behavior. Therefore, the changes in the pH of the
suspension with respect to the added amounts of HCl solution were 100
measured as a function of storage time and are shown in Fig. 9. The
pH of the suspension varied considerably with respect to the storage
time. The suspensions with 0, 1, and 2 ml of added 1 M HCl solution
50
showed small pH variations. The suspensions with higher amounts of 0 10 20 30 40 50 60 70
shear rate, 1/sec

11 2000

5 wt.% bentonite + HCl solution addition 7ml

10 upward downward
fresh
after 6h
1000 after 12h
after 24h
9 after 48h
viscosity, cP

after 72h

8
pH

HCl solution addtion

7 0 ml
1 ml
2 ml
3 ml
6 5 ml 100
7 ml
10 ml
12 ml
5 50
0 10 20 30 40 50 60 70 80 0 10 20 30 40 50 60 70
time, h shear rate, 1/sec

Fig. 9. The changes in pH of suspensions with respect to added amounts of HCl solution as Fig. 10. The change of viscosities with increasing storage time in suspensions with HCl so-
a function of storage time. lution added.
 K.Y. Choo, K. Bai / Applied Clay Science 108 (2015) 182–190 189

Table 3
The Herschel–Bulkley or Bingham parameters of 5 wt.% bentonite suspensions at different HCl solution addition.

Addition ml of τ0, dyn/cm2 k or η, cP n R2

HCl solution
Upward Downward Upward Downward Upward Downward Upward Downward

1 Fresh (−) 20.4 6032 29.0 0.08 0.94 0.996 0.999

2h 5.32 23.7 1334 29.7 0.24 0.96 0.998 0.999
6h 15.3 26.6 715.3 27.9 0.35 Bingham 1.0 0.996
12 h 2.50 28.8 2012 27.8 0.19 Bingham 1.0 0.997
24 h (−) 24.9 2030 25.8 0.18 Bingham 0.999 0.997
48 h 4.48 28.7 1810 25.0 0.20 Bingham 0.999 0.996
72 h 13.5 31.3 1263 25.9 0.25 Bingham 0.999 0.995
2 Fresh 36.7 42.5 142.3 14.8 0.59 Bingham 0.999 0.988
2h 36.6 46.6 231.9 11.8 0.49 Bingham 0.991 0.997
6h 28.8 44.4 709 15.3 0.32 Bingham 0.978 0.995
12 h 32.1 46.8 660.2 29.7 0.32 0.85 0.994 0.997
24 h 35.2 39.7 232.7 276.6 0.47 0.36 0.997 0.998
48 h 38.4 43.6 142.0 135.9 0.58 0.50 0.999 0.997
72 h 26.0 44.4 1129 75.5 0.23 0.64 1.00 0.998
3 Fresh – 62.7 – 98.4 – 0.64 – 0.996
2h 45.5 57.0 1057 282.4 0.24 0.43 0.992 0.992
6h 43.6 57.5 1108 188.2 0.23 0.50 0.990 0.995
12 h 37.6 56.8 1421 136.0 0.21 0.57 0.989 0.997
24 h 46.9 53.1 569.1 98.8 0.27 0.59 0.989 0.994
48 h 44.1 54.9 755.7 114.1 0.28 0.59 0.997 0.996
72 h 38.4 54.0 1001 96.2 0.27 0.65 0.988 0.996
5 Fresh – 51.1 – 809.7 – 0.32 – 0.991
2h – 30.3 – 1998 – 0.2 – 0.997
6h 5.33 18.4 5073 3300 0.08 0.13 0.992 0.992
12 h 52.8 44.0 254.6 1007 0.50 0.25 0.995 0.997
24 h 51.3 53.0 487.1 487 0.38 0.36 0.999 0.989
48 h 47.8 56.4 538.1 137.6 0.36 0.59 0.995 0.985
72 h 47.5 51.0 363.7 448.3 0.43 0.35 0.998 0.997
7 Fresh – 30.1 – 1321 – 0.27 – 0.986
2h – (−) – 10,066 – 0.05 – 0.998
6h 40.7 13.3 176.3 2157 0.51 0.16 0.988 0.998
12 h 33.0 20.9 389.0 1428 0.36 0.18 0.992 0.996
24 h 24.5 21.9 698.8 721.5 0.25 0.27 0.998 0.996
48 h 28.1 27.7 149.2 249.5 0.53 0.41 0.994 0.998
72 h 27.0 28.1 99.0 190.0 0.61 0.44 0.994 0.997
10 Fresh – 32.5 – 428.4 – 0.39 – 0.987
2h – 10.7 – 1812 – 0.18 – 0.997
6h 31.0 (−) 42.0 12,161 0.75 0.03 0.985 0.995
12 h 23.7 (−) 338.6 36,789 0.36 0.01 0.997 0.995
24 h – (−) – 2864 – 0.09 – 0.988
48 h 14.1 – 916.6 – 0.19 – 0.994 –
72 h 16.7 15.6 513.4 746.9 0.27 0.19 0.988 0.991

(−): negative value; –: no fitting.

by FF association, and refers to the collapse of the diffuse layer and the
formation of aggregates of parallel platelet space 20 Å or less apart
(Luckham and Rossi, 1999; Uskarci, 2006). Flocculation of clay suspen-
sions has been referred to as a consequence of EF and EE association, re-
sponsible for the continuous gel-like structure in the montmorillonite
clay suspensions (Uskarci, 2006).
related to the change of particle structure in the suspension. In other
words, aggregation was preferred to flocculation by the conversion
from an edge-to-face 3-dimensional network structure to a face-to-
face 3-dimensional structure with increasing storage time.
Acknowledgments

5. Conclusions This work was supported by financial help (Contract Number

An increase in the concentration of bentonite led to an increase in
the viscosity and shear stress of bentonite suspensions. Particularly, a
considerable initial stress was observed at the initial shear rate as the
storage time increased. This indicated that a significant yield value
was required to break the particle network due to the large cohesion
force between the particles, and that a considerable amount of time
was required to form the particle network. In addition, thixotropic be-
havior appeared to be more dominant than shear thinning behavior as
the particle network was built up.
The influence of pH on the bentonite suspension was also significant.
The absolute value of the zeta potential decreased and a significant ini-
tial stress value was observed at the initial shear rate value, as the
amount of HCl added to the fresh suspension increased. However, the
pH value became high and the viscosity low, when the suspensions
were stored for 72 h with large amounts of added acid. This is probably
2011T100200259 & 20133030110870) from the Ministry of Trade, In-
dustry and Energy, Republic of Korea.
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