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FLOCCULATION OF KAOLINITE DUE TO THE

ATTRACTION OF OPPOSITELY CHARGED
CRYSTAL FACES
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BY R. K. SCHOFELDAND H. R. SAMSON*
Physics Dept., Rothamsted Experimental Station, Harpenden, Herb
Received 23rd July, 1954
Pure kaolinite washed first with 1 M NaCl containing 0.001 M HCI and then with
distilled water remains firmly flocculated when salt free. In this state the kaolinite retains
exchangeableNa, which shows that the crystals are negatively charged.
When re-shaken in 0,005 M NaCI, the crystals positively adsorb chloride, which
proves that parts of their surfaces (presumably the edge faces) are positively charged.
The attraction of the positive charges on the edge faces for the negative charges in the body
of the crystals is regarded as the cause of the flocculation which occurs in the absence
of salt.
Deflocculation of the salt-free suspension occurs on the addition of a small but sufficient
amount of NaOH. When kaolinite so treated and then air-dried is re-dispersed in 0 0 0 5 M
NaCI, the crystals negatively adsorb chloride, showing that the edge faces are no longer
positively charged.
Deflocculation can also be brought about by adding small amounts of sodium oxalate,
sodium pyrophosphate, sodium polymetaphosphate,sodium alginate and sodium bentonite.
Regardless of the agent used, when the kaolinite is deflocculated in the absence of salt,
the crystals repel chloride ions when placed in dilute NaCI.
Natural kaolins sometimescontain small amounts of clay minerals like montmorillonite
consisting of very small negatively charged platy crystals. If these are lying against the
positively charged edge faces of the much larger kaolinite crystals they can profoundly
affect the working properties.

Marshall1 in an investigation of the influence of exchangeable cations on

particle-size distribution of various clays, found that kaolinite was ‘‘ peculiar ”
in its behaviour. In contrast tolthe other clay minerals, the stock suspension
of hydrogen-kaolinite remained flocculated, and even the sodium-kaolinite failed
to disperse completely. Marshall concluded that this result was “ probably due
to causes other than the cations concerned ”, and because of the extreme sensitivity
of the kaolinite suspensions towards flocculation, he was unable to draw any con-
clusions regarding the influence of cations on the degree of dispersion. It is
significant that when given the same pretreatment, i.e. electrodialysis followed
by neutralization with a base, e.g. NaOH, LiOW, the other clay minerals-mont-
morillonite, beidellite and Rothamsted clay (probably chiefly il1ite)-readily
gave stable well-dispersed suspensions.
It has long been known from investigations on soils, and from industrial ceramic
practice that clays may be dispersed by the addition of alkalis. A mixture of
sodium carbonate and sodium silicate is commonly used in the preparation of
alkaline casting-slip, an important phase of pottery and porcelain manufacture.
A detailed study of the properties of these fluid ceramic mixes, or ‘‘ slips ”, which
always contain a proportion of kaolinite, was carried out by Webb? Henry
and Taylor,3 and Speil4 are amongst others who have observed the decrease in
viscosity of a kaolinite suspension produced by addition of alkalis. Helz 5 used
a capillary viscometer to measure viscosities of electrodialyzed dickite suspensions
* Division of Industrial Chemistry, C.S.I.R.O., Melbourne, Australia ; died
28th August, 1954.
135
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136 F L O C C U L A T I O N OF K A O L I N I T E

to which various electrolytes were added. He rightly concluded that viscosity

is a reliable measure of the degree of deflocculation, but it is doubtfbl whether
any real significance can be attached to the values he calculated for the hydro-
dynamic volume of the dispersed phase. The observation that oxalic and tannic
acids dispersed the dickite is of special interest.
The first systematic study of the deflocculation of kaolinite suspensions was
carried out by Johnson and Norton,6 who also gave a very comprehensive if un-
critical review of earlier work on the subject. Kaolinite, judged by X-ray examin-
ation to be free from other clay minerals, was further purified by H202 treatment
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to remove organic matter, then electrodialyzed to replace all metallic cations by

hydrogen. The “ hydrogen-clay ” so produced was actually a mixed hydrogen-
aluminium clay. The authors represented the reaction occurring when NaOH
is added to electrodialyzed kaolinite as follows :
clay OH-HfNaOH -+clay OH-NafHOH.
They failed to realize that the first additions of NaOH are used up in the pre-
cipitation of aluminium hydroxide.
The effects produced by addition of various acids, bases and salts to suspensions
of electrodialyzed kaolinite were investigated by means of pH and relative viscosity.
Their interpretation of the mechanism of deflocculation is based on the assumption
that the negative charge in kaolinite originates from a preferential adsorption
of hydroxyl ions on certain “active areas” located at the crystal edges. They
considered that before addition of NaOH, the H-kaolinite is uncharged, whereas
in actual fact it possesses a negative charge throughout the whole pH range.
The important facts emerging from the work of these authors are as follows :
(1) It was recognized that an excess of alkali above that equivalent to the
“ exchange-capacity ” was necessary to maintain deflocculation. As will
be shown later, this holds only in the absence of other anions.
(2) The most efficient deflocculation was obtained when monovalent cations
were present as counter-charges.
(3) Ammonium oxalate was found to deflocculate electrodialyzed kaolinite
very readily. The general interpretation offered by the authors does not
explain this observation.
There have been other indications that Johnson and Norton’s interpretation of
the mechanism of deflocculation does not cover all the known facts. For example,
recent work by van Wazer and Besmertnuck7 has shown that pyro- and poly-
metaphosphates are capable of causing deflocculation of kaolinite suspensions
without raising the pH above 7. The efficiency of sodium polymetaphosphates
(Calgon) as dispersants for clays has often been ascribed solely to complex
formation between the polyanion and flocculating ions such as Ca, Mg. These
studies established that deflocculation occurred even when the only cation present
was Naf. The authors concluded that the ‘‘ liquefying-ability”of the various
phosphates involves two factors : (1) anionic charge and (2) complex formation
between the anion and surface ions of the clay mineral lattice. It is implied that
phosphate ions are adsorbed at the surfaces of the kaolinite particles.
EXPERIMENTAL
A variety of kaolins was used in the course of this work. Each sample was examined
by petrographic and X-ray methods, and in order to detect any small quantity of mont-
morillonite, the technique described by MacEwan 8 was adopted.
Kaolin F Prepared by separating the < 2p fraction of a china clay supplied by English
Clays Lovering Pochin and Company Ltd. Contains kaolinite and a trace
of muscovite.
Kaolin C The > 2p fraction of the same china clay. Contains kaolinite, muscovite and
small amounts of quartz, tourmaline and hydrated iron oxides.
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R . K . S C H O F I E L D AND H . R . S A M S O N 137
Kaolin M (Origin unknown.) Supplied by Merck, and labelled Colloidal Kaolin.
A pure kaolinite.
Kaolin R Supplied by the Institute of Chemistry, Genoa. Contains kaolinite, mont-
morillonite and mica.
Kaolin G The fine fraction of a china clay supplied by Dr. S. J. Gregg, University College,
Exeter. Contains kaolinite, montmorillonite and mica.
KaoZin K From the Meka district, Germany. Contains kaolinite, montmorillonite
and mica.
Kaolin S A soil clay from Rocky Gully, West Australia. Contains kaolinite and some
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hydrated iron oxide.

Kaolin P From South Carolina, U.S.A. Contains kaolinite and muscovite.
When a pure kaolinite is leached with a solution of N NaCl containing 10-3 N HCl
until no cations other than Na+ are detectablein the leachate, and the salt washed out with
distilled water, the kaolinite exhibits rapid flocculation.
This behaviour is in marked contrast to that shoyn by illite or montmorillonite. When
pretreated in an exactly similar manner, these clay minerals exhibit spontaneous defloccula-
tion when the electrolyte concentration is reduced below a certain critical value.
It was also observed that the Na-kaolinite flocculated progressively more rapidly as
the NaCl concentration was reduced. A suspension of Na-kaolinite in distilled water was
actually the " most flocculated " of all, and possessed the highest apparent viscosity.
This unexpected result was in apparent conflict with classical views on the dispersion of
negatively charged colloidal particles. The addition of a small amount of NaOH, or Na
alginate, Na polymetaphosphate was required to produce a stable, deflocculated sus-
pension.
In order to investigate the apparently anomalous dispersion properties of kaolinite, bulk
samples of kaolin F were leached with NaCl + HCl (i.e. a solution containing N NaCl+
10-3 N HCI) CaClz - HCl and 0.2 N HCl respectively, and washed chloride-free with
distilled water. A portion of the Na-kaolinite, obtained by NaCl-HCl leaching, was
treated with sufficient sodium polymetaphosphate just to cause deflocculation. This
treated clay was re-washed with distilled water. A sample of kaolin M was leached with
KC1-HCl and washed chloride-free.
The clays thus prepared for deflocculation studies were as follows:
Kaolin F Na-kaolinite
+
Na-kaolinite adsorbed (NaPO3),
Ca-kaolinite
H-Al-kaolinite
Kaolin M K-kaolinite.
All samples were dried at 105" C.
In these studies the apparent viscosity of a kaolinite suspension (9 % by weight) has
been used as an index of its degree of dispersion. The instrument employed was a
Technic0 torsion viscometer, which is of the concentric cylinder type. A range of 10
to 14,000centipoises was covered by calibration curves, constructed using glycerol solutions
of known viscosity.
The apparent viscosity of a deflocculated suspension is very little in excess of the vis-
cosity of water, and measurements in this range were made using a simple type of capillary
viscometer.
In addition to these measurements, the sedimentation behaviour of each suspension
when diluted, was also noted, i.e. the ratio of floc formation, rate of settling, the sedi-
mentation volume, streaming birefringence, and rheological properties of the sediment
after decantation of the supernatant liquid,
Each suspension was prepared by adding 5 g of kaolinite to 50 ml of solution. After
vigorous shaking to produce a homogeneous suspension, and standing overnight, the
apparent viscosity was measured at 21" C.

RESULTS
DEFLOCCULATION WITH HYDROXIDES
Kaolin F. With progressiveadditions of NaOH, a sudden decreasein apparent viscosity
occurs at the point of deflocculation, and thereafter it maintains a constant value. The
actual decrease in this case is about 1,000-fold, but its magnitude has no particular
 View Article Online

138 FLOCCULATION OF KAOLINITE

significance, being dependent on a number of factors, including concentration of sus-

pension, particle-size distribution, and the type of viscometer.
It is of interest, however, to compare kaolins F and M.
For kaolin M, the decrease is more gradual, its magnitude is smaller, and less alkali is
required to produce complete deflocculation. The contrast in behaviour between kaolins F
and M is borne out by visual observation on dilute suspensions. Kaolin M (Na-kaolinite)
when suspended in distilled water did not exhibit as rapid flocculation as kaolin F. The
flocs were smaller and the supernatant liquid cleared more slowly. These differences are
paralleled by the relative ability of the clays to take up chloride ions, as will be shown later.
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The relative inefficiency of Ca(OH)2 as a deflocculant is indicated by the small decrease

in apparent viscosity, and is supported by observations on sedimentation volume, etc,
With kaolin F, the minimum in apparent viscosity is reached at about the value (1 to
1.5 mequiv. OH-/l00 g kaolinite) as for NaOH, suggesting that the nature of the process
is the same in both cases. Johnson and Norton 6 reported similar differences between
deflocculation with Ba(OH)2, Sr(O€I)2 on the one hand, and NaOH, KOH on the other.
Fig. 2 shows the effects of NaOH on (1) Na-kaolinite, (2) Na-kaolinite pre-treated with
(NaPO3), and (3) HAl-kaolinite.

KAOLIN F

:.:-:.: Na-clay
'loo r &A H,Ak clay [prepared
by acid laaching 1
0-0 &-clay [pwtreated
with (NaPO3)nI

L. I
- , -
:.:
0

me.oF baSo/ioog
t-&-"I.
8 1 2 ..
me.NaOH/roo g
3' 4
I I
5

FIG. I. FIG. 2.
(1) Nu-kuolinite-described above,
(2) Nu-kuolinite, pretreated with (NaPO&. When suspended in water, the clay is
already in a completely deflocculated condition and addition of NaOH is without effect.
A similar behaviour is observed when the Na-kaolinite is pre-treated with Na-alginate.
Evidently the adsorbed polyanion modifies the kaolinite surface in such a way as to prevent
flocculation.
(3) HAl-kaolinite. In this case, extra amounts of NaOH qre required, since first
additions of alkali are used in neutralization of hydrogen and aluminium ions balancing
the negative charge on the clay particles.
A gradual decrease in apparent viscosity is observed, instead of a sudden drop as with
Na-kaolinite, and the minimum value is slightly higher. Both these differences may possibly
be attributed to the precipitation of aluminium hydroxide and subsequent dissolution as
aluminate.
 View Article Online

R . K . SCHOFIELD A N D H . R . S A M S O N 139
EEFECTOF NEUTRAL SALTS
When kaolinite is leached several times with N NaCl -+
10-3 N MCl, the salt washed out,
and the Na-kaolinite so produced is then suspended in (1) distilled water, (2) neutral
N NaCl solution, both suspensions are flocculated. Nevertheless they may be clearly
distinguished by visual observation ; the suspension containing NaCl flocculates more
slowly, and exhibits slight streaming birefringence when swirled. It was also found to
possess a lower apparent viscosity than the salt-free suspension.
Some experiments were, therefore, carried out to investigate the effects produced by
various electrolytes over a wide range of concentrations, and it was observed that with
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increasing salt concentration, a progressive reduction in apparent viscosity occurred

(fig. 3). It is believed that this phenomenon has not previously been reported for kaolinite
suspensions. It is quite clear that kaolinite suspensions may exhibit two distinct types of
flocculation.
I r 1400

KAOLIN
l__l F

10 I I I I II I 1 I
Molar lo-' concn -.lo-' ~xIO-'b3~~l~~ 10~2,0,c,-lo-' 5~10-l
FIG. 3.
CHLORIDE ADSORPTION
The NaCl + HCl treatment was applied to each of the followingkaolins, F, C , M, S and
G . Particular care was taken to wash each sample free of chloride before drying at 105"C.
A separate portion of kaolin F was pre-treated with (NaP03), before the NaCl + HC1
leaching. This material and also kaolin G, which contains a trace of montmorillonite,
deflocculatedspontaneously as the salt concentration was reduced, and it was not possible,
therefore, to wash these clays chloride-free.
Weighed portions of kaolinite were suspended in a series of N/200 NaCl solution
to which graded amounts of HCI or NaOH had been added, and the increase or decrease
in chloride concentration of the clear liquid was determined after centrifuging. Chloride
estimationswere carried out using the differentialelectrometrictitration method of MacPnnes
and D0le.9 Where the kaolinite contained chloride, as for example kaolin G, allowance
was made for this by suspending a separate sample in alkaline N/20 NaN03 and combining
an aliquot of the clear solution with an aliquot of the standard N/200 NaCl.
The results are shown in fig. 4. Kaolins F, C, M and S exhibit a change-over from
positive to negative adsorption of chloride, and on each graph the point of deflocculation
in water is marked by a vertical arrow. This represents the minimum quantity of NaOH
required to deflocculate the Na-kaolinite when suspended in distilled water, and is always
less than that required for the negative adsorption in N/200 NaCl to attain its maximum
vaIue. When this value is reached, the positive charges are either absent, or at least
ineffective as regards chloride adsorption.
Kaolin G, which contains montmorillonite and iIlite, stands out from the rest; it
exhibits negative adsorption over the range where the other kaolinites exhibit positive
adsorption. There is no point of deflocculation since the clay is deflocculated when
suspended in water, even after addition of acid. When 1.4m.e. HC1/100g was added,
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140 FLOCCULATION OF KAOLINITE

however, the beginning of flocculation was observed, though the chloride adsorption
was still slightly negative.
The influence of adsorbed (NaP03), on the defloccdation and chloride adsorption of
kaolin F is shown in fig. 5. Here the apparent viscosity in water, and the chloride ad-
sorption in N/200 NaCI are both plotted against HCI or NaOH added.

o3 r
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02 -

0.1 -
FIG.4.

1
r-
Negariv4

RG. 5.

I 0 I 2 3
m.e.HCl/iooq .- - m.e NaGH/roog

After treatment with (NaPO3),, the kaolinite is completely deflocculated in water,

and repels chlorideions when suspendedin N/200 NaC1. On addition of HCl, the chloride
adsorption again becomes positive, due to development of more positive charges. The
horizontal displacement of the two graphs gives the approximate increase in negative
charge due to the adsorbed polymetaphosphate. Although no viscosity measurements
were made, it was observed that after addition of HCI, the kaolinite flocculated. Evidently
there was not complete coverage of the edge-faces by the polymetaphosphate ion, or else
the anion underwent some hydrolysis.
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R . K . SCHOFIELD A N D H . R . SAMSON 141

DISCUSSION
The chloride adsorption exhibited by kaolinite provides the clue to the nature
of the inter-particle forces. Before addition of NaOH, pure Na-kaolinite exhibits
strong flocculation in salt-free suspension, and also takes up chloride ions from
N/200 NaCl. The flocculation is evidently due to electrostatic attraction between
positive edges and negative cleavage-faces of adjacent kaolinite crystals, and will
be referred to as " edge-to-face " flocculation. When NaOH is added, hydrions
are lost from the edge-faces by proton transfer, the number of positive charges
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decreases, and consequently, the positive adsorption is reduced. Chloride ad-

sorption becomes zero when there is an exact balance between attraction and
repulsion, and eventually changes over to negative.
From fig. 4 it is seen that near the point where the chloride adsorption in
N/200 NaCl is zero, the kaolinite is in the condition where it is capable of de-
flocculation in a salt-free suspension. The addition of this critical amount of
NaOH reduces the number of positive charges to the point where the edge-faces
are no longer capable of attracting the negatively-charged cleavage surfaces of
adjacent crystals. The same effect is obtained if the edge-faces have their positive
charge neutralized by adsorption of a polyanion, e.g. polymetaphosphate. The
inter-particle repulsive forces, due to the net negative charge and the well-developed
diffuse double layer, are then adequate to maintain complete dispersion.
So far, we have seen that deflocculation may be brought about in two ways :
(1) By proton transfer on addition of NaOH, and consequent removal of
positive charges.
(2) By anion adsorption, causing neutralization of positive charges.
Other anions which act in the same way include pyrophosphate, alginate, organic
sulphates, sulphonates, oxalates.
Kaolin G exhibited its maximum negative adsorption when suspended in
neutral N/200 NaC1, i.e. without addition of NaOH, and even when 0.7 mequiv.
HC1/100 g was added, there was still no positive adsorption of chloride. The
conclusion seems inescapable that under these conditions there were no positively-
charged areas capable of taking up chloride ions.
It is known from X-ray examination, that this kaolinite contains a small
amount of montmorillonite and illite. The interpretation offered is that these
small negatively charged platelets are attracted to and held by the edge-faces of
the much larger kaolinite crystals, thereby neutralizing their positive charge.
These surfaces are then incapable of taking up chloride ions, and also exert no
attraction for the negatively-charged surfaces of
other kaolinite particles. Edge-to-face floccula-
tion does not occur, and the suspension remains
deflocculated. The interaction between kaolinite
and montmorillonite (or illite) is shown diagram-
matically in fig. 6. It is not possible to say at
present which mineral would be more readily
adsorbed at the edge-faces of kaolinite, but it montrnorilloni 1s
plotolPts
may be Na-montmorillonite, since it is capable
FIG. 6.
of ultimate dispersion to platelets which are only
lOA in thickness.
It was considered probable that if the traces of clay mineral impurities were
removed, the kaolinite should behave " normally ". Accordingly, a portion of
kaolin G was suspended in water containing enough NaOH to bring the pH to
about 10, and the suspension centrifuged. Under these conditions, the edge-
faces should pass through an isoelectric condition and become negative.
After several centrifugings and decantations to remove the desorbed mont-
morillonite and illite, and unavoidably, some of the finest kaolinite, the residual
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142 F L O C C U L A T I O N OF K A O L l N I T E

+
clay was treated with NaCl HCl and the salt washed out. The kaolinite then
remained flocculated.
The reverse effect may be accomplished by adding a small amount of a dilute
Na-montmorillonite or Na-illite suspension to a flocculated Na-kaolinite. The
streaming birefringence characteristic of deflocculation immediately becomes
apparent. Here, then, is another way in which kaolinite suspensions may be
deflocculated :
(3) By small negatively-charged platelets of another clay mineral overlying
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positive charges on the edge-faces of the larger kaolinite crystals.

Kaolin M, though mineralogically pure, differs from the other kaolinites both
in flocculation behaviour and in its capacity to take up chloride ions. In fig. 4,
the gradient of the line representing change in chloride adsorption with pH is
smaller for kaolin M than for kaolin F or C. The capacity of kaolin M to take
up chloride ions is evidently quite low.
This behaviour could be explained by the presence of thin kaolinite particles
possessing a relatively high permanent (i.e. isomorphous replacement) negative
charge. It is known that the exchange-capacity of kaolin M is high in relation
to surface area (see table 1), and electron micrographs have shown that the finer
particles, of the order of 0.3 ,u in diameter, are very thin plates. Since the clay
possesses a considerable range of sizes, it is even possible that these small plates
are held at the edge-faces of larger particles in much the same way as was proposed
for montmorillonite and illite in kaolin G. This interaction of kaolinite particles
would markedly reduce the number of positive charges available for chloride
adsorption, and also reduce the tendency towards edge-to-face flocculation, a
fact which has already been noted (fig. 1). Both effects could also be explained
on the basis of the high surface density of negative charge, which is 3.6 x 10-7
mequiv.lcm2, i.e. more than twice the value for kaolin F. This means that
surface positive charges are opposed by a considerably larger underlying negative
charge.
DEFLQCCULATION WITH Ca(OH)2
Fig. 1 illustrates the relative ineffectiveness of Ca(OH)2 as a deflocculant for
kaolinite, compared with NaOH. The viscosity minimum occurs in the same region
in both cases, suggesting that the mechanism is the same. Since the pH is suf-
ficiently high to ensure complete disappearance of positive charges, the explanation
of the small decrease caused by Ca(OH)2 must lie in the magnitude of theinter-
particle forces due to the negative charge. Ca.2+, being divaIent, is held more
firmly at the kaolinite surface than Na+; and this reduces the magnitude of the
effective charge. The diffuse portion of the electrical double-layer is only weakly
developed, and there is a consequent decrease in repulsion between adjacent
particles.
TWO TYPES OF FLOCCULATION
The reduction in apparent viscosity and sedimentation volume, retardation
of flocculation, and appearance of streaming birefringence, all of which are ex-
hisited by flocculated-kaolinitesuspensions when high concentrations of electrolyte
are added, may be explained by the co-existence of positive and negative charges
on the clay particles.
lncrease in electrolyte concentration effects a reduction in thickness of the
diffusedouble-layers at both positive and negative surfaces, and this in turn reduces
their mutual attraction. The anions may be regarded as " screening " the positive
charges, and the effectiveness of screening increases with concentration and valency
of the anion. At the same time, there is a decrease in the repulsive force between
two negative surfaces, and as a result, flocculation will tend to occur with flat
surfaces in contact rather than edge-to-face.
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R . K . SCHOFIELD AND H . R . S A M S O N 143

The presence of Caz+ against the negative surface will be particularly effective
in reducing the field of negative charge in its vicinity, more so than with mono-
valent Na+. This is borne out by the results shown in fig. 2.
The fact that a flocculated
kaolinite suspension containing
N NaCl exhibits streaming
birefringence is good evidence
that the particle groups are
capable of some degree of
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orientation. It is suggested
that these particle groups, or
fiocs, possess a surface-to-
surface arrangement of crystals HCl NdCl

(see fig. 7). This may be

termed ‘‘ lamellar ” or “ salt ”-
flocculation. In this condition
there is less tendency towards
the formation of a 3-dimensional
network in the suspension than
when the particles flocculate
“ edge-to-face ”, and the ap-
parent viscosity is consequently FIG. 7.
lower.
The measurement of a yield-value would probably be a better method of dis-
tinguishing between the two types of flocculation; a list of their chief character-
istics is given in table 1.
TABLE1
Edge-to-face flocculation Salt-flocculation
1. Exhibited most readily in salt-free 1. Exhibited best at high salt con-
suspensions, and with monovalent centrations, and with di- or trivalent
counterions. counterions.
2. Particles arranged edge-to-face. 2. Particles arranged lamellar fashion,
face-to-face.
3. High apparent viscosity. 3. Lower apparent viscosity.
4. Suspensions exhibit no streaming bi- 4. Suspensions exhibit streaming bi-
refringence. refringence.
5. Flocculation occurs rapidly, and with 5. Flocculation occurs rather less rapidly
a large sedimentation volume. and sedimentation volume is smaller.

The distinction between the two types of flocculation is less marked with
kaolin M than with kaolin F. This is in accord with the inability of kaolin M
to exhibit strong edge-to-face flocculation, and its low apparent viscosity and
chloride adsorption.
MINERALOGICAL PURITY OF KAOLINS
The ability of small amounts of msntmorillonite to cause spontaneous de-
flocculation of Na-kaolinite has already been discussed. This suggests a method
of estimation of mineralogical purity of kaolinitic clays. Provided the particles
are free of adsorbed polyanions, the test, which consists in NaCl+HCl leaching
followed by washing with distilled water, should indicate whether montmorillonite
or illite are present. If they are, spontaneous deflocculation below a certain
salt concentration takes place; if not, the kaolinite will remain flocculated, and
in fact the rapidity of flocculation should increase as the salt is washed out.
A preliminary treatment with N NaCl containing enough NaOH to give the
suspension a pH of about 9 will ensure removal of anions such as phosphates,
alginates, etc., if present. The results of tests on a series of clays are shown in
table 2.
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144 F L O C C U L A T I O N OF KAOLINITE
In kaolins F, C, P, muscovite was identified by petrographic methods.
In kaolins G, B, K, a line appears at lOA on the X-ray pattern, indicating
the presence of a mica-type clay mineral, probably illite.
TABLE2
kaolin after NaCI+HCI and minerals present
washing out of salt (X-ray diffraction)
M flocculated kaolinite
S $9
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Y9

F 97 kaolinite, muscovite
C Y7 ?, 77
P 97 $9 99
G deflocculated kaolinite, montmorillonite,mica
B 79 9, Y7 9)

K 79 YY Y7 YY

It is clear that muscovite itself does not prevent flocculation of kaolinite,

whereas illite does. This is probably a particle-size effect. The muscovite
particles are comparable in size to the kaolinite and, instead of shielding the
positive charges on the edge-faces, they may even assist edge-to-face flocculation.
DETERMINATION OF SURFACE AREA
By extending Gouy's theory of ionic distribution in the diffuse part of the
electrical double-layer, Schofield 10 obtained an expression for the negative
adsorption of ions repelled at the phase boundary.
In the general case, when all attracted ions have the valency v and repelled
ions the valency v/p,

This equation is a good approximation provided the first term is several times the
second.
Here n = electrolyte concentration ;
T = the total charge in the diffuse layer ;
r = the negative adsorption of repelled ions ;
p = S ~ F ~ / E R=T (dielectric
E constant, F = the faraday) ;
q = a factor depending on the valency ratio p .
Details of the calculation have already been published by Schofield.10, 11
The surface areas of a number of different kaolins were calculated from the
maximum value of negative adsorption in every case (see fig. 4). The results
are shown in table 3, and for comparison, the values determined by N2 adsorption
using the B.E.T. method.
TABLE
3
kaolin area by negative adsorption area by B.E.T. method
m21g mzlg
F 15 -
c 8 6
M 9 10
G 18 16
S 25 39

Kaolin S , a soil clay, contains iron oxide, and was very difficult to disperse
after drying at 105" C .
Considering the difference in the two methods, the agreement is, on the whole,
remarkably good.
 View Article Online

R. K . SCHOFIELD AND H . R . S A M S O N 145

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Published on 01 January 1954. Downloaded by Fudan University on 25/01/2018 22:48:27.

11 Schofield, Trans. Brit. Ceramic SOC.,1948, 47, 207.