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ABSTRACT
The absolute values of zeta (Ā) potentials estimated by an electrokinetics sonic amplitude (ESA)
method decreased gradually with the increase of NaC1 concentration below the flocculation value of
1.5•~10-2 and 1.5•~10-3 mol L-1 in the suspension of montmorillonite at pH 8 and allophane at pH
7.5 respectively. TheĀ potentials increased inversely above the flocculation values. The absolute value of
potential in kaolinite suspension at pH 6 was found to decrease even above its flocculation value, and
increased inversely above 5.6•~10-3 mol L-1 NaCl. The flocs already began to form below the
occulation value in the montmorillonite suspension at pH 8, but the formation and precipitation of fl
the
ocs began almost simultaneously in the kaolinite suspension at pH 6. TheĀ potential of allophane fl at
pH 3.5 began to increase at about 1.5•~10-3 mol L-1 NaC1, which coincided with the absolute value at
pH 7.5. The flocs in the allophane suspension at pH 3.5 began to form at near 2•~10-3 mol L-1 NaC1,
but to precipitate above 5•~10-3 mol L-1 NaCl. The aspects of flocs formation in allophane were a little
different from montmorillonite and kaolinite.
Key words: Allophane, ESA method, Flocculation, Kaolinite, Montmorillonite, Zeta potential
It is well-known that zeta (Ā) potential strongly affects potentials of clay minerals have been investigated using
the dispersion and the flocculation of clay and soil par- the electrophoresis methods (de Keizer, 1990; Mehrian et
ticles during aqueous suspension (Kida, 1962). The Ā al., 1991; Nakaish and Kuroda, 1995). In this paper, we
al., 1980). The electrophoresis methods, however, tend to method with concentrations of sodium chloride in the
delay the measurement (Furusawa, 1996). An electro- suspension media, in connection with their flocculation
vious papers (Kitagawa et al., 2001; Yorozu and Kita- MATERIALS AND METHODS
(1985) according to the following principles of ESA Kunipia-F Bentonite, Indonesia Kaolin and Kanuma-
effect: Ultrasonic waves are generated when electro- tsuchi weathered pumice was used as montmorillonite,
magnetic waves are radiated in the suspension of col- kaolinite and allophane samples respectively. From
loidal particles; the ultrasonic waves are measured with a these, the Na+-saturated clay samples for the estimation
detector by applying the piezoelectric effect; and the Ā of the Ā potentials and the flocculation were prepared by
potential of the colloidal particles is determined. Kita- the following methods. The clay fractions less than 2ƒÊm
gawa et al.(2001) pointed out that the ESA method was in diameter were initially separated by a sedimentation
sufficient for the Ā potential estimation of clay minerals method according to Stokes' law, and the fractions were
as a new method. Yorozu and Kitagawa (2002) ex- washed with NaCl solution and distilled water. The
amined the effects of adsorbed ion species on the Ā purity of each sample was tested by an X-ray diffraction
potentials of clay minerals by the ESA method, and method, and a very small amount of mica minerals was
showed a decrease in their absolute values in the case of confirmed in the kaolinite sample. After thermal anal-
92 Y. Kitagawa et al.
standing. The C potential of montmorillonite was-27, electrophoresis increases in line with the development of
22,-16 and-67 mV at 3•~10-4, 1.4•~10-3, - 1.1•~ ocs formation with an increase of NaCl concentration, fl
10-2 and 2.7•~10-2 mol L-1 NaCl respectively. The and does not conform to the theory of diffuse double
absolute value of potential decreased gradually with layer in this concentration.
the increase of NaC1 concentration below about 1.5x With regard to montmorillonite, it was considered
10-2 mol L-1, but increased inversely above this con- that the gradual decrease of potential and the increase
centration. On the other hand, the relative turbidity, in relative turbidity with the increase of NaC1 concen-
T0/T of the montmorillonite suspension, also increased tration below 1.5•~10-2 mol L-1 was due to the con-
slightly below about 1.5•~10-2 mol L-1 NaCl, but traction of electric double layer accompanied by the
decreased rapidly above this concentration. These data neutralization of its negative charge by Na+ on the clay
showed that the flocculation value of Na-saturated particles. Apparently, flocculation did not occur in the
montmorillonite at pH 8 was apparently near 1.5x10-2 concentration below 1.5•~10-2 mol L-1, but small flocs
mol L-1, which is similar to the values reported by were certainly formed as shown in Table 1. The mean
Keren et al.(1988) and Kuroda and Nakaishi (1996). diameter of particles or flocs in the montmorillonite
Furthermore, a rapid increase in C potential above suspension increased from 1.7 pm at 1.7•~10-4 mol L-1
1.5•~10-2 mol L-1 of NaCl concentration was also to 11ƒÊm at 1.2•~10-2 mol L-1, which indicated the
observed-in kaolinite. Nakaishi and Kuroda (1995) formation of flocs in the dilute NaCl solution. Com-
reported that the mobility of kaolinite particles in pared with the modes of particle association in clay
Effects of Sodium Chloride Concentrations 93
TABLE 1. Changes in particles or flocs . size of montmorillonite with with montmorillonite. It was considered that the kao-
NaC1 concentration of suspension measured by laser scat- linite flocs precipitated rapidly as they lost their negative
tering method
charge by the contraction of the electric double layer
structure.
suspensions by Van Olphen (1991), these flocs con-
precipitate. The absolute value of C potential increased sion with NaCl concentration at pH 3.5 are presented in
above 5.6•~10-3 mol L-1 NaCl. Figure 4. The C potential of allophane at pH 3.5 was
The flocs in kaolinite suspension were found to easily +16,+21,+29,+44 and+67 mV at 9•~10-4, 2.4•~
precipitate in the low NaCl concentration in contrast 10-3, 3.5•~10-3, 6.4•~10-3 and 1.1x10-2 mol L-1
94 Y. Kitagawa et al.
FIG. 2. Relation between NaCl concentration and C potential by ESA method and
relative turbidity in kaolinite suspension of pH 6: Relative turbidity, To/T, is
transmittance of dispersed suspension versus that of NaCl-added suspension at
660 nm in depth of 10 mm after one hour standing.
NaCl respectively. The Ā potential began to increase at addition to the hydroxyl groups combined with alu-
about 1.5•~10-3 mol L-1 NaCl. The NaC1 concen- minum which are exposed on the allophane surface. The
tration for beginning the change of potential at pH 3.5 relations among allophane particle charge, changes in
almost coincided with that at pH 7.5, but the absolute electric double layer and modes of flocculation, however,
value at pH 3.5 was higher than at pH 7.5 below could not be explained in positively charged allophane,
1•~10-2 mol L-1 NaCl. The relative turbidity of the and remain an issue for future research.
the allophane suspension at pH 3.5, however, seemed The changes in potentials of montmorillonite, kao-
to begin at near 2•~10-3 mol L-1 NaCl, because the linite and allophane with NaCl concentration in the
relative turbidity decreased slightly at 2•~10-3 through suspension media were estimated by the ESA method in
5•~10-3 mol L-1 NaCl. These results suggested that the connection with the modes of their flocculation.
occulation modes of the positively charged allophane fl The absolute values of potentials decreased grad-
FIG.3. Relation betweenNaCl concentration and Cpotential by ESA FIG.4. Relation between NaCl concentration and Cpotential by ESA
method and relativeturbidity in allophane suspension of pH 7.5: method and relative turbidity, MIT,
T, in allophane suspension of
Relative turbidity, T0/T, is transmittance of dispersed suspension pH 3.5: Relative turbidity, To/ T, is transmittance of dispersed
versus that of NaCl-added suspension at 660nm in depth of suspension versus that of NaCl-added suspension at 660nm in
10 mm after one hour standing. depth of 10mm after one hour standing.
creased inversely above the flocculation values. On the the allophane suspension at pH 3.5 began to form at
other hand, the absolute value of potential in kaolinite near 2•~10-3mol L-1 NaCl, but to precipitate above
at pH6 was found to decrease even above its floccu- 5 •~10-3mol L-1 NaCl. The modes of flocculation in
lation value, and increased inversely above 5.6•~10-3 the positively charged allophane could not be accounted
mol L-1 NaCl. The flocs already began to form below for, and should be a topic for future research.
electrophoresisof clay particles.Progr. ColloidPolym Sci. 83, 118- Clay Sci. Soc. Japan) 36, 1-8.
126. MEHRIAN, T., DE KEIZER,A. and LYKLEMA, J.(1991). Effect of tem-
KEREN,R., SHAINBERG, I. and EVAKLEIN(1988) Settling and floc- perature on the adsorption of organic cations on charged surfaces.
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