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319–327
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.
1. Introduction
)
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
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
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.
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%..
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
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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