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Applied Clay Science 14 Ž1999.

319–327

The effect of the electrolyte concentration and pH


on the rheological properties of the original and the
¨
Na 2 CO 3-activated Kutahya bentonite
N. Yildiz a , Y. Sarikaya b, A. Çalimli a,)

a
˘
Department of Chemical Engineering, Faculty of Science, Ankara UniÕersity, 06100 Tandogan,
Ankara, Turkey
b
˘ Ankara,
Department of Chemistry, Ankara UniÕersity, Faculty of Science, 06100 Tandogan,
Turkey
Received 20 January 1998; received in revised form 4 February 1999; accepted 16 February 1999

Abstract

¨
The effect of the Na 2 CO 3 activation on the rheological properties of a bentonite from Kutahya
ŽTurkey. was investigated. The bentonite was activated with Na 2 CO 3 at different dosages Ž1–15 g
Na 2 CO 3r100 g bentonite.. The activated samples were examined by chemical and X-ray
diffraction analysis. The calcium bentonite was completely converted to sodium bentonite when
the Na 2 CO 3rbentonite ratio was 2.5%. The rheological values showed a maximum after addition
of 2.5% Na 2 CO 3 Žbentonite concentrations 2–6% wrw.. At 2.5 g Na 2 CO 3r100 g bentonite, the
shear stress was also measured at several NaCl and Na-hexametaphosphate concentrations. NaCl
addition decreased the rheological properties up to NaCl concentrations of 0.005 mol ly1. Further
addition of NaCl increased the rheological properties again. The addition of Na-hexa-
metaphosphate caused a decrease in the rheological properties to a constant value higher
phosphate concentrations. The lowest yield stress was obtained around pH 7. q 1999 Elsevier
Science B.V. All rights reserved.

Keywords: bentonite; montmorillonite; soda activation; rheology; thixotropy; viscosity

1. Introduction

Bentonite dispersions are widely used in industrial processes because of their


exceptional rheological behaviour. In order to increase the viscosity and to

)
Corresponding author. E-mail: calimli@science.ankara.edu.tr

0169-1317r99r$ - see front matter q 1999 Elsevier Science B.V. All rights reserved.
PII: S 0 1 6 9 - 1 3 1 7 Ž 9 9 . 0 0 0 0 6 - X
320 N. Yildiz et al.r Applied Clay Science 14 (1999) 319–327

improve the thixotropic behaviour of bentonite suspensions, Na 2 CO 3 , NaOH,


MgŽOH. 2 are added to bentonite suspensions Ž Szanto et al., 1967; Bleifuss,
1973; Lagaly et al., 1981; Alther, 1982. .
Lagaly Ž1989. investigated the effect of soda addition on the rheological
properties of bentonites. Addition of soda increased the viscosity and the
thixotropy. Further addition of soda reduced these values again. Volzone and
Garrido Ž1991. studied the effect of Na 2 CO 3 on several Argentine bentonites.
They observed an increase of the gel strength and of the apparent viscosity at
160 sy1. This increase was related to the content of the particles 0.5 F mm and
the NaqrCaq2 ratio.
The type of flow, the viscosity and the yield value of clay suspensions are
affected by the following factors: Ži. the clay concentration, Žii. the size and
shape of clay particles, Žiii. the electrostatic properties of clay particles, Ž iv. the
exchangeable ions, Ž v. the concentration of the electrolytes in suspensions and
Žvi. the type of bentonite Ž Brandenburg and Lagaly, 1988; Keren, 1989; Chen et
al., 1990.. Generally, the flow of bentonite dispersions is very sensitive to the
NaqrCaq2 ratio. In practical applications the properties of bentonites can be
improved by changing the NaqrCaq2 ratio ŽAlther, 1986.. The rheological
properties of dispersed bentonites depend on the cation that is originally present
in the bentonite. A Ca-bentonite dispersed in a sodium salt solution behaves
differently from a dispersion of a bentonite in its sodium form in a calcium salt
solution, even though the NaqrCaq2 ratio is the same ŽBrandenburg and
Lagaly, 1988; Tombacz et al., 1989. .
The objective of the present study is to determine the influence of NaCl,
Na-hexametaphosphate and pH on the rheological behaviour of the original and
¨
the activated Kutahya bentonite suspensions.

2. Experimental methods

¨
Fractions of white colour Kutahya Ca-bentonite smaller than 36 m were used
in this study. A locality map for the bentonite sample is provided in Fig. 1. The
total reserve of this bentonite area is estimated to be about 1 million ton Ž The
Mineral Research and Exploration Report, 1972, 1996 Seyhan, 1972; Akbulut,
1996.. The chemical analysis of the bentonite is given in Table 1. The activated
samples were analyzed for Caq2 and Naq by a Unicom 939 AAS and JENWAY
PFP7 model flame photometer, respectively. The X-ray powder diagrams of the
original and the activated samples, prepared as random powder material, were
obtained with a Philips Powder Diffractometer model PW 1730 CuK a radiation
Ž40 kV, 20 mA.. Montmorillonite was the main mineral. Minor amounts of
quartz, a-cristobalite and albite were also identified in the raw material.
Ca-bentonite was activated with Na 2 CO 3 at various mass ratios Ž0.1, 2, 2.5,
5, 10 and 15 g Na 2 CO 3r100 g bentonite.. Ca-bentonite and Na 2 CO 3 were
N. Yildiz et al.r Applied Clay Science 14 (1999) 319–327 321

Fig. 1. The locality map of the bentonite sample.

added to 800 ml boiling water and the dispersion was left boiling for 1 h. After
dilution with water, the dispersion was allowed to settle in a large bottle for 48 h
and the supernatant suspension was separated by decantation. The sediment was
again dispersed in water, the supernatant was again decantated and this proce-
dure was repeated until bentonite was no longer dispersed in the supernatant.
The supernatants were collected, concentrated by evaporation and dried in an
oven at 1058C.
For the rheological measurements, the activated samples were suspended at 2,
4 and 6% concentrations in solutions containing different concentrations of NaCl
and Na-hexametaphosphate. The rheological measurement were carried out with
a Haake RV 20 viscometer Ž rotating cylinders NV. at 258C. Before the

Table 1
Chemical analysis of the original bentonite
Al 2 O 3 SiO 2 K 2 O Fe 2 O 3 CaO MnO TiO 2 P2 O5 Na 2 O MgO KPK a Others
% 14 68.2 1.7 0.9 2.82 0.2 0.1 0.1 0.70 1.40 9.1 0.78
a
Weight loss at 10008C.
322 N. Yildiz et al.r Applied Clay Science 14 (1999) 319–327

measurements the suspensions were allowed to age for 1 week at 258C. The
dispersions were mixed with known volumes of HCl Ž the acid concentration was
between 10y4 and 2 mol ly1 in the dispersions. and the pH was adjusted
between 10 and 3. The pH values of the dispersions were measured with
colorimetric test papers just before the rheological measurements.

3. Results and discussion


The basal spacing decreased from 1.504 nm to 1.209 nm by Na 2 CO 3 addition
ŽTable 2. . The strong increase of the Na 2 O compared with the decreasing
amounts resulted from the excess Na 2 CO 3. Since the activated samples were
washed only twice, the excess Na 2 CO 3 was not completely removed. When
2.5% Na 2 CO 3 was added, 74% of the Caq2 ions were exchanged by Naq ions.
Further addition of Na 2 CO 3 increased the degree of exchange of Caq2 ions to
90%.
The shear stress–shear curves of the activated bentonites indicated a pseudo-
plastic flow with yield stresses ŽRand et al., 1980; Tombacz et al., 1989. . The
flow curves were evaluated according to the classical Bingham model Žt s t B q
hpl D ., where t is the shear stress, t B is the Bingham yield value Žor stress., hpl
is the plastic viscosity and D is the shear rate. The Bingham yield value is
determined by extrapolating the linear part of the flow curve, and the plastic
viscosity is calculated from its slope. The yield stress and the plastic viscosity
values are presented in Figs. 2 and 3. At 2.5 g Na 2 CO 3r100 g bentonite, the
yield stress and plastic viscosity reached maximum values. The yield stress
values for the Na-bentonite suspensions is higher because of larger number of
particles as a consequence of delamination. Further addition of Na 2 CO 3 Ž i.e.,
increasing salt concentration. reduced the number of particles and the yield
stress and viscosity again. Similar results were also found by Lagaly Ž1989. .
When the Na 2 CO 3 ratio was 2.5%, thixotropy was maximum ŽFig. 4. . A
hysteresis loop was distinctly smaller at 1 and 10% Na 2 CO 3. Similar changes
were observed when the amount of sodium carbonate was 2% and 6% ŽLagaly,
1989; Singh and Sharma, 1991; Volzone and Garrido, 1991; Sarikaya et al.,
1994..
For the Na 2 CO 3-activated bentonite with 2.5 g Na 2 CO 3r100 g bentonite the
flow curves of the suspensions with 2, 4 and 6% solid content were measured at

Table 2
The basal spacing Žair-dried samples. and Na 2 O, CaO content after Na 2 CO 3 addition
Na 2 CO 3% 0 0.5 2 2.5 5 10 15 20
CaO% 2.82 2.05 1.68 0.92 0.87 0.76 0.62 0.55
Na 2 O% 0.63 1.25 2.85 3.20 6.25 22.50 41.75 45
dŽ001. wnmx 1.504 1.447 1.260 1.209 1.209 1.250 1.273 1.290
N. Yildiz et al.r Applied Clay Science 14 (1999) 319–327 323

Fig. 2. Yield value vs. sodium carbonate addition at different bentonite contents Ž' 2%, = 4%,
I 6%..

different NaCl and Na-hexametaphosphate concentrations and pH ( 10. The


apparent viscosities were determined from the ratio of the shear stress to the
shear rate of 348 sy1. Similar changes were observed at shear rates of 124 sy1
and 969 sy1. The thixotropy coefficient Ž u . was determined from the slope of

Fig. 3. Plastic viscosity vs. sodium carbonate addition at different bentonite contents Ž' 2%, =
4%, I 6%..
324 N. Yildiz et al.r Applied Clay Science 14 (1999) 319–327

Fig. 4. Shear rate vs. the shear stress of 4% wrw bentonite dispersions after activation with 1
Ž`., 2.5 Ž'. and 10 Žl. %Na 2 CO 3.

the line obtained by plotting the reciprocal shear rate against the apparent
viscosity. The units of thixotropy are N my2 Ž Norton, 1970; Yildiz et al., 1998. .
The dependence of the yield stress, the thixotropy Ž u ., the plastic and the
apparent viscosities for the activated bentonite suspensions on the NaCl concen-
tration is presented in Table 3. The yield stress and the thixotropy of the
bentonite with 2.5% Na 2 CO 3 decrease with increasing electrolyte concentration
up to C NaCl s 0.005 mol ly1. At higher concentration the values increase again.
The considerable decrease of the yield stress at low NaCl concentrations is
explained as a general consequence of the compression of the electrical double-
layer ŽPermien and Lagaly, 1994a. . The plastic and the apparent viscosity also
showed a minimum at C NaCl s 0.005 mol ly1. At higher salt concentrations

Table 3
Rheological properties of the Na 2 CO 3-activated bentonite suspensions at different NaCl concen-
trations Ž4% wrw bentonite content.
Na 2 CO 3 content 2.5% 2% 1%
3 3 3
C NaCl tB u ŽPa. hp =10 ha =10 tB hp =10 tB hp =10 3
Žmol ly1 . ŽPa. ŽPa s. ŽPa s. ŽPa. ŽPa s. ŽPa. ŽPa s.
0 5.90 4.00 10.90 23.11 5.10 10.97 4.01 6.33
0.0025 3.30 2.90 10.05 17.90 3.50 10.00 5.20 9.61
0.005 3.10 2.10 9.15 16.86 4.10 10.61 5.20 10.97
0.017 4.70 3.00 10.02 20.45 3.20 10.94 6.51 9.58
0.085 5.60 5.20 9.02 25.57 8.50 12.82 9.93 12.82
N. Yildiz et al.r Applied Clay Science 14 (1999) 319–327 325

Table 4
Rheological properties for the Na 2 CO 3-activated bentonite suspensions at different sodiumhexa-
metaphosphate concentrations C Žmg ly1 . Ž4% wrw bentonite content.
Na 2 CO 3 content 2.5% 2% 1%
3 3 3
C Žmg l y1 .
tB u hp =10 ha =10 tB hp =10 tB hp =10 3
ŽPa. ŽPa. ŽPa s. ŽPa s. ŽPa. ŽPa s. ŽPa. ŽPa s.
0 5.90 4.00 10.90 23 5.10 10.97 4.01 6.33
500 3.86 2.87 9.62 17.33 5.11 10.51 4.12 10.02
1000 2.10 1.81 8.66 14.82 4.13 10.46 2.94 7.76
5000 2.10 1.81 9.52 14.82 2.74 8.66 2.94 6.38
10,000 2.10 1.81 9.63 13.88 2.68 8.23 2.94 6.84

coagulation and formation of three-dimensional networks, probably band-type


structures, increases the viscosity and yield values.
Addition of sodiumhexametaphosphate Ž Table 4. decreased the yield stress,
the thixotropy, the plastic and the apparent viscosity to a constant value at
concentrations above 500 mg ly1 Ž 2.5%. or above 1000 mg ly1 Ž 2%, 1%. . The
liquefying effect of the hexametaphosphate is caused by the adsorption of this
compound on the edges which increases the density of the negative edge
charges.

Fig. 5. The relation between pH and shear stress for the suspensions with different amounts of
NaCl. Ž1. no salt addition, Ž2. 0.0025 mol NaCl yl , Ž3. 0.005 mol NaCl yl and Ž4. 0.085 mol
NaCl yl Ž4% bentonite, 2.5% Na 2 CO 3 ..
326 N. Yildiz et al.r Applied Clay Science 14 (1999) 319–327

The relation between the pH, the NaCl concentration and the yield stress is
shown in Fig. 5. The yield stress showed a minimum around at pH 7. Permien
and Lagaly Ž1994b. found similar changes. They showed that the shear stress
and the yield value decreased to a minimum at about 10y2 mol ly1 acid
concentration ŽpH s 4. for a solid content of 2% Ž wrw. . At a pH value below
the iep of the edge, it seems likely that edge-to-face attraction predominates and,
therefore, the rheological parameters increase with decreasing pH Ž Fig. 5. . The
decrease in the rheological parameters with increasing electrolyte concentration
below 0.085 mol ly1 NaCl again demonstrates the electroviscous effect men-
tioned above. At a NaCl concentration above 0.010 mol ly1 the particles are
coagulated ŽPermien and Lagaly, 1994c. , i.e., that forces between the particles
are attractive which increases the yield stress.

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