Clay Science12,91-96 (2003)

EFFECTS OF SODIUM CHLORIDE CONCENTRATIONS ON

ZETA POTENTIALS OF CLAY MINERALS ESTIMATED BY
AN ELECTROKINETIC SONIC AMPLITUDE METHOD

YASUO KITAGAWA, SHINYA YAMAGUCHI and YASUAKI YoROZu

Fukui Prefectural University, Kenjojima, Matsuoka, Fukui 910-1195, Japan

(Received March 27, 2003. AcceptedMay 27, 2003)

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

INTRODUCTION divalent ions compared with monovalent ones.

The effects of electrolyte concentrations on the

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

estimated the changes in the potentials of montmor-

potentials of clay minerals are generally determined by
the electrophoresis methods (Horikawa, 1970; Mori et illonite, kaolinite and allophane determined by the ESA

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

kinetic sonic amplitude (ESA) method was introduced modes.

for the Ā potential estimation of clay minerals in pre-

vious papers (Kitagawa et al., 2001; Yorozu and Kita- MATERIALS AND METHODS

gawa, 2002). This method was developed by Oja et al.

(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.

yses, hardly any organic coexistents were detected in all

the samples.

The potential of each clay specimen was determined

with an ESA 8000 type apparatus developed by Matec

Applied Science, USA (Oja et al., 1985). The electro-

magnetic wave frequency was automatically adjusted to

gain the maximum potential value in the range of 0.8

to 1.2 MHz inside this apparatus. At first, each clay

specimen of 0.25 g was suspended thoroughly in 250 mL

of distilled water and NaC1 solution. The NaC1 con-

centration and the pH value of clay suspension were

determined by its electroconductivity and with a glass

electrode in the measurement respectively. In the allo-

phane specimen, two pH values, 7.5 and 3.5, of sus-

pensions were prepared because of its amphoteric nature.

The pH value of the latter allophane suspension was

adjusted to 3.5 by adding a suitable amount of 0.1

mol L-1 HC1. The mean size of clay particles considered

to be a factor for calculating the C potential was de-

termined by a laser scattering method (Kurihara et al.,

1999) using a Horiba LA910-type apparatus. The den-

sity of kaolinite, montmorillonite and allophane, another

factor for calculating the potential, was used indicating

values of 2.65, 2.55 and 2.75 respectively (Kitagawa,

1976; Egashira, 1987).

The flocculation degree of clay suspension was esti-

mated from the relative turbidity at the point of 10 mm

in depth, after this suspension was dispersed thoroughly

with an ultrasonic vibration and left standing for one

hour. The montmorillonite, however, was left for one

day. The relative turbidity was shown by the ratio To/T

of 660 nm visible-radiation. Here, To is the transmit-

tance of the dispersed suspension which is not added

NaCl, and T is that of the NaCl-added suspension.

RESULTS AND DISCUSSION

FIG.1. Relation betweenNaCl concentrationand 4 potential by ESA
Montmorillonite method and relative turbidity in montmorillonite suspension of
fi gure 1 shows the change in potential of mont- pH 8: Relative turbidity, T0/T, is transmittance of dispersed
morillonite by the ESA method with the NaCl concen-
suspensionversus that of NaCl-added suspensionat 660 nm after
one day standing.
tration in its suspension at pH 8 and the relative tur-

bidity at 20 mm in depth of its suspension after one day

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

with the neutralization by Na+ due to a small quantity

of its layer charge. Nakaishi and Kuroda (1995) re-

ported the value of 2.2•~10-3 mol L-1 NaCl as the

critical concentration of flocculation in kaolinite sus-

pension at pH 10. That value was different from

1•~10-4 mol L-1 at pH 6 obtained in this study, which

may have resulted from the difference in pH value

between both suspensions. Namely, kaolinite has the

variable pH-dependent negative-charge caused by the

dissociation of broken bonds in the edges of its layer

structure.
suspensions by Van Olphen (1991), these flocs con-

formed to "Aggregated but deflocculated (Face-to-face Allophane

association),""Edge-to-face flocculated but dispersed" The changes in C potential of allophane estimated by
and/or "Edge-to-edge flocculated but dispersed." This the ESA method with the NaCl concentration in its
suggested that the critical concentration of the flocs suspension of pH 7.5 and the relative turbidity at 10mm
formation of montmorillonite was about 10-3 mol L-1, in depth of its suspension after one hour standing are
but its suspension was still dispersed in this NaCl con- shown in Fig. 3. The 4 potential of allophane in the
centration. suspension of pH 7.5 was-10, -6, -6, -10, -25 and
The flocs formed below 1.5•~10-2 mol L-1 NaC1
-57 mV at 3•~10-4, 9•~10-4, 2.4•~10-3, 5.8•~10-3
should be fluffy abundantly charged because the mont- and 1.1•~10-2 mol L-1 NaCl respectively. The absolute
morillonite particle is flaky and highly negatively value of C potential decreased slightly with the increase
charged. It is well-known that montmorillonite has a of NaCl concentration below about 1.5•~10-3 mol L-1,
large quantity of negative permanent charge originating but increased above this concentration. The relative
in the isomorphic substitution on the inside position of turbidity of the allophane suspension at pH 7.5
its layer structure. The relative turbidity of the still- decreased rapidly above 1.5•~10-3 mol L-1 NaCl which
dispersed suspension was increased slightly by the for- was regarded as the apparent critical concentration for
mation of these flocs. On the other hand, the mont- occulation. fl
morillonite particles in the flocs formed above 1.5x10-2 The slight decrease in potential in the allophane
mol L-1 NaC1 were tightly clustered and precipitated suspension at pH 7.5 below 1.5•~10-3 mol L-1 NaCl
although the mean diameter of particles or flocs was suggested that the formation of flocs already began in
5 ,um and relatively small. Such contraction of flocs the region of this concentration but it still dispersed
with the increase of the salt concentration was presented because of the relatively large quantity of negative
in kaolinite by Kuroda et al.(1998). The flocs in high charges as in the case of montmorillonite. The floccu-
concentration were compared with "Edge-to-face," lation value of allophane at pH 7.5, however, was
"Edge -to-edge
," and "Edge-to-face and edge-to-edge apparently low in comparison with montmorillonite.
occulated and aggregated" by Van Olphen fl (1991). Moreover, the range of NaCl concentration from the

beginning of flocs formation by the contraction of

Kaolinite electric double layer to the beginning of flocs precipi-
The changes in C potential of kaolinite estimated by tation was limited in allophane. The modes of flocs
the ESA method with the NaC1 concentration in its formation in the allophane suspension should be dif-
suspension of pH 6 and the relative turbidity at 10mm ferent from montmorillonite which was mentioned be-
in depth of its suspension after one hour standing are fore. It is well-known that the negative charge of
shown in Fig. 2. The C potential of kaolinite was-20 allophane at this pH value is a variable one caused by
,
7, -8 and -26 mV at 3•~10-5, 2.3•~10-3, 5.6•~10-3 - the dissociation of a large amount of the hydroxyl
and 1.1•~10-2 mol L-1 NaCl respectively. The absolute groups combined with aluminum and silicon in its
value of C potential estimated by the ESA method de- structure. All these hydroxyl groups are exposed on the
creased gradually with the increase of NaCl concen- surface of allophane, which is composed of spherical
tration below about 6•~10-3 mol L-1, but increased aggregates in micro-morphology and has a large specific
inversely above this concentration. The relative turbidity, surface area (Kitagawa, 1971).
however, already decreased at about 1•~10-4 mol L-1 The changes in C potential estimated by the ESA
NaC1, and the flocs in the kaolinite suspension began to method and the relative turbidity of allophane suspen-

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.

allophane suspension at pH 3.5 decreased rapidly above

5•~10-3 mol L-1 NaCl, which was a higher concen- CONCLUSION

tration than the one at pH 7.5. The flocs formation in

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-

ually with the increase of NaCl concentration below the

particles were diflerent from the negatively charged ones.
The positive charge of allophane occurs in acid sus- occulation value of 1.5•~10-2 and 1.5•~10-3 mol L-1
fl
in the suspension of montmorillonite at pH 8 and al-
pension at a lower pH value than its isoelectric point at
about pH 5.5, and is variable. It is caused by proton lophane at pH 7.5 respectively. The potentials in-
 Effects of Sodium Chloride Concentrations 95

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.

the flocculation value in the montmorillonite suspension

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