Unique Settling Behaviour of Processed China Clay from South Kerala 75

Unique Settling Behaviour of Processed China Clay

from South Kerala
S. Chandrasekhar*, P. Raghavan and S. Ramaswamy
Regional Research Laboratory, Thiruvananthapuram–695 019, India
*E-mail: chandrasekharsathy@rediffmail.com

ABSTRACT: During the size classification of a china clay from Kerala, the product slurry of 2” standard
hydrocyclone separation was found to undergo a sudden settling thus separating 40% by wt in the settled
fraction. The particle size distributions in the two fractions were found to be different and nearly 99.5%
particles were below 1 µm size in the dispersed fraction. Chemical and mineralogical compositions of the two
fractions were found to be almost similar. An attempt was made to find plausible explanation for this unique
settling behavior. Detailed studies by X-ray diffraction and Transmission Electron Microscopy with micro
analytical probe showed that the dispersed fraction contained kaolinite particles with finer size, more
disordered structure and higher surface layer charge. The particles in the settled fraction were relatively
coarser, ordered and neutrally charged. Traces of Na, K, Cl, colloidal silica, crandallite and illite minerals
were also found in the sample. It was concluded that the flocculation and separation of particles may possibly
be occurring due to these factors especially in presence of the soluble salts.

Key Words: Kaolin, Settling, Surface Charge, XRD Analysis, TEM.

1. INTRODUCTION charged part (smectite, mixed layer illite/

Size separation of clay particles at 1 µm level is a
challenging task in mineral processing. During
the investigation on a kaolin from southern part of
Kerala, the sample was subjected to blunging,
screening and size classification using hydro-
cyclones. The product slurry of 2” standard
hydrocyclone separation was found to undergo a
sudden settling (40% by wt in the settled and 60%
in the dispersed fractions). The particle size
analysis of the settled and dispersed solids
showed that the former contained all particles
below 20 µm and 62% below 2 µm size whereas
the latter contained all particles below 2 µm
with 99.5% below 1 µm size. Chemical and
mineralogical contents of both fractions were
found to be almost similar and this size separation
at 1µm level was found to be interesting. In
nature, this phenomenon can be seen very often.
For example, in estuaries from the dispersed
fraction (soil fraction) the neutral charged coarse
fraction (mostly kaolinite, mica and illite)
normally flocculate very fast and so builds
unwanted sludge in the harbors while the strongly
montmorillonite etc) remain dispersed and go into
the sea. But in the present study, the feed sample
contains only one mineral (kaolinite) and particles
of very fine size which separates to give a fraction
with almost all particles below 1 µm. Hence, the
phenomenon was found interesting.
2. EXPERIMENTAL
2.1 Materials & Methods
Nearly one ton of the china clay collected from
Thonnakkal (Thiruvananthapuram district, Kerala)
was thoroughly blended. A representative sample
(~10 kg) was subjected to blunging, size
separation at 300 µm using a vibrating screen and
further classifications by small diameter hydro-
cyclones (2”stub and 2” standard cyclones giving
cut sizes of 45 and 20 µm respectively). The
overflow slurry of the 2” standard hydrocycloning
was allowed to settle for about one hour and the
settled and dispersed fractions were separated and
dried.
76  Mineral Processing Technology (MPT 2007)
2.2 Characterization analysis of the dispersed fraction was also carried
out by Zeta Sizer which showed that all particles
Particle size distribution, chemical assay, optical are having size in the range 1162–100 nm with
properties and mineralogy of the feed sample and average size 367 nm (0.367 µm). The optical
the settled and dispersed fractions were deter- properties of the feed sample are also found to be
mined by standard methods. in between those of the two fractions.
The samples of two fractions were subjected XRD powder patterns of the two fractions
to HR TEM and selected particles were also were almost identical. The peak intensities were
studied by EPMA. Si/Al ratios of a number of more for the settled fraction indicating that it is
particles were calculated from the EPMA data and more crystalline. Chemical assay and mineralogy
charge deficiencies were calculated and plotted. of both fractions were more or less identical and
X-ray analysis (both powder and texture) was very near to that of kaolinite mineral.
done for mineral identification. For checking the
presence of swelling minerals, texture samples Table 1: Properties of the fractions
were dried in air or treated with ethylene glycol
Sl. Properties Feed Settled Disperse
and investigated by reflex analysis by a computer No (2”std.H/ fraction d fraction
program. Intensities of 3 strongest X-ray peaks of . C O/F)
1 Particle
the identified minerals were compared with a size
calibration mixture for the semi quantitative distribution
mineral content calculations. (% wt.) 0.00 0.00 0.00
+ 45 µm 0.00 0.00 0.00
For detailed characterization of kaolinite in – 45, + 20 0.71 2.00 0.00
–20, + 10 2.86 7.00 0.00
the two fractions, a line profile analysis of the 1 st –10, + 5 12.50 29.00 0.00
base reflection of the texture analysis was done by –5, + 2 12.50 29.00 0.5
–2, + 1 71.43 52.00 99.5
a commercial program (Winfit). Reliability of –1
about 97% could be achieved when two peaks are 2 XRD
taken. One of them (main peak) is near to the Major Kaolinite Kaolinite Kaolinite
phase
theoretical basic distance for good ordered 3 Optical
kaolinite with d = 7.15A and the second one 0.2A properties
Brightness 84.70 82.32 86.85
higher (d = 7.35A) for disordered kaolinite. By L 93.72 92.60 94.84
fitting, the d values could be optimized and the a -0.36 -0.40 -0.332
b 2.46 2.73 2.37
intensities of the two peaks could be calculated. HW 74.67 71.31 77.08
Furthermore, Coherent Structure Domains (CSD) HY 3.75 4.21 3.58
values have been calculated by Fourier analysis.
The flocculation in the ratio 40:60
(flocculated to dispersed part) with the relative
3. RESULTS & DISCUSSION
sharp cut point is mainly caused by the material
The physical properties of the feed sample and the itself, that means, the flocculation or peptization is
two fractions are given in Table 1. The feed effected by the particles involved in the two
sample has ~85% particles below 2 µm size. The different processes. If this is true, there should be
a difference in the material itself which can
dispersed fraction has all particles below 2 µm
explain the processes of the state or condition.
and 99.5% particles below 1 µm and the settled The investigation indicated X-ray based
fraction has all particles below 20 µm, 62% differences in the state of order and micro-
below 2 µm and 33% below 1 µm. The fast analytical detected differences in the composition
settling and separation at 1 µm level is a very of kaolinite and poorly crystallized/ low ordered
unique phenomenon and is found to be typical for nanoparticles were found to be present.
this clay. Generally, separation in kaolin at this
level is very difficult and hence this property is of 3.1 X-ray Analysis of Kaolinite
great industrial significance. The particle size
Unique Settling Behaviour of Processed China Clay from South Kerala 77
The X-ray powder diffraction diagram shows that Reliability 96.64 98.16 97.36 97.85
(%)
the settled fraction contains 97.3% kaolinite and
Ordered part
the dispersed fraction 99.4%. In the region of 020 dA 7.164 7.160 7.159 7.148
band, different resolutions of the reflections were I 2056 1609 2027 1632
observed pointing out differences in the state of CSDA 204-216 244-260 228-242 220-231
order, which is indicated by the calculated Disordered part
Hinkley index (HI) of the samples. The HI of the dA – 7.217 – 7.176
kaolinite of dispersed and settled fractions are I – 190 – 376
found to be 0.93 and 1.12 respectively. The CSDA – 128-133 – 128-133

difference in the state of order is significant and

can be seen by the X-ray reflection profile analysis 3.2 Electron Microscopic Analyses
of the 1st basal reflection (Tables 2 and 3).
The kaolinites in both fractions have sharp edged
Table 2: X-ray reflection profile analysis of the pseudo hexagonal sheets and they are smaller in
dispersed fraction the dispersed fraction compared to the bigger inter
grown particles in the settled fraction. The micro
Air dried Ethylene glycol
treated analytical data shows traces of Fe, Ca and other
Reliability (%) 95.47 98.26 95.33 97.51 impurities and a significant difference in the Si/Al
Ordered part ratio. This should be theoretically 1:1, by the
dA 7.195 7.180 7.175 7.163
I 2117 1456 1140 838
formula [Al4(OH)8Si4O10]. Using the structural
CSDA 167-173 233-242 155-161 222- 229 formula calculated from the analyses, the content
of Si as well as Al is found to vary. Starting from
Disordered 173 242
part
a completely filled anionic lattice (28 negative
dA  – 7.225 charges) which is assumed by most of the clay
 – 7.209
I  – 850
 – 395
minerals, Si and Al variability means a difference
CSDA  – 121-126
 – 109-114 of the lattice charge resulting in particle charge. In
Fig. 1 charge deficiencies of single particles are
The air dried as well as the ethylene glycol treated arranged by their order of magnitude so that the
samples of settled fraction showed predominantly total spectrum could be seen.
good ordered kaolinite with d = 7.16A and only a For the settled fraction, the Al content is
relatively small peak (10 to 20% of the main peak higher so that the charge of the layer is near to
intensity) with higher d-value (d = 7.2Å) . CSD zero which means that the particles are almost
values of good ordered kaolinite are in the range neutral as it is known for kaolinite in general. In
of 220 to 260 Å and of more disordered kaolinite the dispersed fraction, more particles are with a
are in the range of 110 to 130 Å. The disordered
lower Al content (a higher positive charge
kaolinite is significantly higher in the dispersed
deficiency, or higher negative layer charge) which
fraction as shown by the intensity relationship.
Additionally, the d values of both varieties are controls the behavior of all clay minerals in
higher so the state of order is generally higher aqueous systems. Variable chemical composition
than that of the bottom fraction. A higher disorder goes in parallel with detected differences of the
generally leads to higher particle charge of the state of order measured by the X-ray profile
kaolinite which influences its behavior in aqueous analyses so that there is a possible explanation of
systems. the difference in stability or flocculation.

Table 3: X-ray reflection profile analysis of the

settled fraction
Air dried Ethylene glycol
treated
78  Mineral Processing Technology (MPT 2007)
Fig. 1: Plot of charge deficiencies of single
particles on (a) settled fraction and
(b) dispersed fraction
In the dispersed fraction, there are no clusters
of fine particles in the grain size range from 1 to
50 nm, while there are significant clusters of
nanoparticles in the settled fraction. By identical
preparation of the samples, it has been shown that
these clusters are not formed by impurities which
come during the preparation of the sample for
analysis.
The microanalysis indicated the presence of
illite (K content), colloidal silicic acid ( spherical
/bunch shaped aggregates of nanoparticles), Ti,
Fe, S, Crandallites (trace elements like Ce, La,
Th, Sr, Pb etc.), Na and chloride particles in both
fractions, but the quantities are much less in the
dispersed fraction.
4. CONCLUSIONS
There are significant differences in the two
fractions which lead to the selective flocculation
of the kaolinite particles. The dispersed fraction
mainly consists of fine grained kaolinite with
significant crystal lattice disorder and Al
deficiency (higher negative charge) and very thin
crystallites of sharp edged pseudo hexagonal
sheets without much intergrowth. The kaolinite
content with smaller CSD (100–125 A) is about
30–40%.
The settled fraction contains kaolinite
intergrowths. The kaolinite has a higher order of
crystallinity and a smaller Al deficiency/negative
charge. The kaolinite content with CSD values
from 220-260 is about 80%. Additionally this
sample contains small but detectable parts of
finely dispersed silicic acid, Na and Cl.
In aqueous system, the behavior of the two
kaolinite groups is different under specific
conditions especially in presence of soluble salts.
The fine grained kaolinite with a higher layer
charge remain dispersed and settle slowly and
under specific concentrations form a stable
structure similar to a sodium montmorillonite or
illite in water. The coarser and mainly neutral
particles form aggregates or flocs in presence of
fine dispersed phases of silicic acid and detectable
quantity of NaCl which enhances quick settling.
5. ACKNOWLEDGEMENTS
The authors are thankful to the Director, RRL, for
giving permission to communicate this paper.
Thanks are also due to Prof. M. Storr, University
of Greifswald, Germany for the carrying out the
XRD and HR TEM analysis. Cooperation from
Prof. E. Gock and Dr. V. Vogt from the Technical
University of Clausthal, Germany is also
gratefully acknowledged.
REFERENCES
[1] Grim, R.E., Clay Mineralogy, 2nd Edition,
McGraw-Hill Book Co, Inc., New York (1968).
[2] Searle, A.B. and Grimshaw, R.W., Chemistry and
Physics of Clays, 3rd Edition, Ernest Benn Ltd,
London (1960).
[3] Van Olphen, H. Particle association in clay
suspensions and their rheological implications.
In Clay water interface and its rheological
implications, Eds. N. Guven and R.M. Pollastro,
CMS Workshop Lectures Volume 4, The Clay
Mineral Society, Colorado (1992).