200  Mineral Processing Technology (MPT 2007)

Zeta Potential Characteristic of Limestone from New

Umrangshu, North Cachar Hills, Assam
Pinaki Sengupta, Bhaskar J. Sarmah,
Sekh Mahiuddin and Prakash C. Borthakur
Material Science Division, Regional Research Laboratory
(Council of Scientific & Industrial Research)
Jorhat-785 006, Assam

ABSTRACT: North East region of India is endowed with vast deposits of limestone. Due to lack of
systematic characterization, beneficiation and utility studies, limestones from the NE region do not find use
in high value applications except for cement manufacturing. The limestone deposit of New Umrangshu,
North Cachar Hills, Assam, India (25°31'51" to 25°32'8" N latitude and 92°48'1" to 92°48'7" E longitude) is
of high grade and contains the impurities in a finely disseminated state. The physicochemical characteristics
of the limestone from the deposit and its amenability to beneficiation by dry and wet methods have been
reported earlier [Saikia et. al. 2005, Sarmah et. al. 2006]. Liberation of the gangue minerals by fine grinding
and separation by selective dispersion is possible for removing the impurities. Zeta potential characteristics of
the minerals play significant role in this regard. This paper reports the zeta potential characteristic of a
limestone sample collected from the New Umrangshu deposit. The isoelectric point of the limestone is ~6.28.
The lower value of isoelectric point of the limestone, compared to pure calcium carbonate (~9.8), is attributed
to the assimilation of fine clay minerals on the calcite particles as evidenced by FTIR, XRD, DTA and SEM-
EDXA studies.

1. INTRODUCTION significant role in this regard. This paper reports

Limestone has been located in many places in
North Eastern region of India. In Assam, it is
mainly found in Karbi Anglong and North Cachar
Hills District. New Umrangshu (25° 31' 51" to 25
°32'8" N latitude and 92° 48'1" to 92°48'7" E
longitudes) in North Cachar Hills of Assam
(India) is endowed with a vast deposit of
limestone. The detail of the deposit is already
reported earlier [Sarmah et. al. 2006]. The
limestone is used presently for cement
manufacturing. No systematic study to
characterize the limestone and its amenability for
beneficiation to obtain grades required for various
other applications has since been made. In an
earlier communication, the preliminary
characterization of the limestone sample and
some of its beneficiated fractions were reported
[Saikia et. al. 2005, Sarmah et. al. 2006].
Liberation of the gangue minerals by fine
grinding and separation by selective dispersion is
possible for removing the impurities. Zeta
potential character-istics of the minerals play
the zeta potential characteristic of a limestone
sample collected from the New Umrangshu
deposit.
2. MATERIALS AND METHODS
About 10 tones of limestone sample from the
Umrangshu deposit was procured through Assam
Mineral Development Corporation, Govt. of
Assam, Guwahati. It was subjected to size
reduction in a jaw crusher and then separated into
–25 +18.75 mm, –18.75 +12.50 mm and
–12.5 mm size fractions. A representative sample
(ULR) was prepared by mixing the different size
fractions in the same proportions as obtained
during crushing by following Indian standard
method of mixing (Indian Standard Specification
IS 2840, 1965). The representative sample (ULR)
was ground to –150 µm for the zeta potential
studies. A part of the ground sample was leached
with 0.1N HCl at ~28oC to completely
decompose the carbonates. The acid insoluble
201  Mineral Processing Technology (MPT 2007)
fraction was washed several times with distilled
water, dried and collected. A laboratory reagent
grade synthetic CaCO3 supplied by M/s Nice
Chemicals, Cochin was also used in the
investigation.
The chemical analyses of the samples were
done by following standard methods of analysis
[Vogel, 1961.]. The CaO, MgO and Fe2O3
contents were determined volumetrically using
EDTA for the former two and potassium
dichromate as oxidant for the later. The amount of
SiO2 and Al2O3 were estimated gravimetrically.
Mineralogical characteri- zation of the samples
were performed using XRD analysis of random
powder samples (Philips X-ray Diffractometer,
Type PW1710, UK and Brucker D8 advance
XPS, Germany) using Cu Kα X-radiation; FTIR
(Perkin Elmer System 2000 spectrophoto-meter,
USA) using KBr pellet method; SEM (model
LEO S430) coupled with EDXA (LINK ISIS,
OXFORD INSTRUMENTS, UK). Zeta
potentials were measured by Zetasizer 3000 HS
(Malvern, UK).
3. RESULTS AND DISCUSSION
The assay of the representative limestone and its
various size fractions are given in Table 1. The
composition of the synthetic CaCO3 is also
included. The limestone is of high grade
Table 1: Chemical constituents of the Umrangshu limestone and its fractions
Sample
CaO MgO
(CaCO3)
ULR 51.75 2.57
(92.41)
-25 +18.75 mm 51.79 2.70
(92.48)
-18.75 +12.5 mm 51.41 2.73
(91.92)
-12.5 mm 50.92 2.16
(90.92)
Synthetic CaCO3 54.80 - -
(98.00)
Peaks at ~470 and 537 cm-1 are assigned to
Si–O vibrations for silicate minerals. The FTIR
containing 91.0-92.5% CaCO3 corresponding to ∼
51-52% CaO. The amount of gangue constituents
(SiO2, Al2O3 and Fe2O3 except MgO) is
maximum in –12.5 mm fraction indicating that
the gangue minerals are mostly concentrated in
the finer fraction. Therefore, fine grinding is
possibly required for liberation of gangue
minerals embedded in the limestone. Nayak and
Bhattacharya based on petrographic study also
reported that the limestone from New Umrangshu
is of high grade and contains small amount of
gangue minerals, which are mostly of fine grain
size [Nayak and Bhattacharya, 2006].
The XRD pattern of parent limestone sample
ULR exhibits strong peaks due to calcite (d =
3.84, 3.02, 2.81, 2.48, 1.91, 1.59 Å) indicating
calcite is the major component (pattern not
shown). The XRD pattern of the acid insoluble
fraction shows the presence of kaolinite (d = 7.14,
3.57, 1.49 Å) as the major and illite (d = 4.47,
3.34, 2.55 Å) as the minor clay mineral
component (pattern not shown). The pattern also
exhibits small peaks due to pyrite (d = 3.13, 2.71,
2.42, 2.21, 1.91,1.61, 1.45 Å) in the sample
[Powder diffraction file, PC-PDF, File No 5-0586,
International Center for Diffraction Data].
The FTIR spectra of the parent limestone
sample ULR shows the most prominent band at
1427 cm-1 and the other bands at ~713, 876 cm-1,
which are characteristics of carbonate mineral
calcite (pattern not shown).
Constituents (wt. %)
SiO2 Al2O3 Fe2O3 LOI
1.70 0.83 0.81 41.50
1.53 0.79 0.68 41.98
1.55 0.77 0.90 41.72
2.25 0.93 1.32 41.78
- - -
spectra of acid insoluble fraction (pattern not
shown) exhibit sharp peaks at ~470, 537, 753,
Zeta Potential Characteristic of Limestone from New Umrangshu… 202
913, 1032, 1108, 3694 and 3620 cm−1,
characteristics of the clay mineral kaolinite
[Russel and Fraser, 1994].
The SEM-EDXA of the ULR sample (Fig. 1)
also reveals the presence of granular sized and
rhombohedral shaped particles of calcite as the
major phase in the limestone sample [Dana and
Ford, 1959]. The white spots residing with the
calcite crystals are attributed to clay minerals. The
SEM-EDXA pattern of acid insoluble part (Fig. 2)
shows combination of plate like, layered and
irregular shaped flaked particles characteristics of
clay minerals. The EDXA data also suggests that
the material is composed of aluminosilicate.

Fig. 2: SEM-EDXA pattern of acid insoluble

part of ULR

The zeta potential of the synthetic CaCO3

Fig. 1: SEM-EDXA pattern of ULR
and Umrangshu limestone as a function of pH is
presented in Fig. 3 & 4 respectively. The
isoelectric point of the synthetic CaCO3 and
Umrangshu limestone is 9.8 and 6.2, respectively.
Under the same experimental conditions
Umrangshu limestone shows negative zeta
potential in the pH range 6.2 to 10.5, whereas,
synthetic CaCO3 shows negative zeta potential in
the pH range 9.8 to 10.5. Below pH 9.8, the zeta
potential of synthetic CaCO3 is positive in
contrast to the limestone sample, which showed
negative zeta potential. The chemical analysis,
XRD pattern, FTIR spectra and SEM-EDXA
investigations showed that the limestone contains
kaolinite clay minerals as the major impurity. The
fine kaolinite particles coat the calcite crystals in
203  Mineral Processing Technology (MPT 2007)
the sample. Kaolinite clay minerals have negative contains calcite (CaCO3) as the major mineral and
zeta potential (Worral W.E 1975). Coating of clay small to trace amount of kaolinite clay minerals,
minerals on the calcite crystals changes the quartz, pyrite etc. as impurity. The fine kaolinite
surface character and electro-kinetic behaviour, particles coat the calcite crystals in the sample.
resulting in negative zeta potential of the Coating of clay minerals on the calcite crystals
limestone sample in wide range of pH. changes its surface character and electro-kinetic
behaviour, resulting in negative zeta potential in
wide range of pH.

5. ACKNOWLEDGEMENTS

The authors are grateful to the Department of

Mines, Ministry of Coal and Mines, Govt. of
India, New Delhi for financial grant and also to
Directorate, Geology and Mining, Govt. of Assam
and Assam Mineral Development Corporation for
their help in procurement of the sample. The
authors also thank to Mr. O.P. Sahu and Mr. P.
Khound for the IR spectra. The authors are also
grateful to Dr. P. G. Rao, Director, RRL, Jorhat
for his interest and support.
Fig. 3: Zeta potential Vs pH: Synthetic calcium
carbonate
REFERENCES
[1] Dana and Ford, 1959. A textbook of
Mineralogy, Asia Publishing House, pp-513.
[2] IS 1504: 1980 Indian Standard Specification,
ISI, New Delhi.
[3] IS 3204: 1978, Indian Standard Specification,
ISI, New Delhi.
[4] Nayak, B., Bhattacharya, K.K., 2006.
Characterization of limestone sample from
northeast India and its implication on
beneficiation. Proc. International Seminar on
Mineral Processing Technology, pp 157-162.
[5] Powder diffraction file, PC-PDF, File No 5-
0586, International Center for Difraction Data.
[6] Russell J.D., Fraser A.R., 1994. Infrared
methods. In: Wilson, M. J. (Ed), Clay
Mineralogy: Spectroscopic and chemical
Fig. 4: Zeta potential Vs pH: Umrangshu determinative methods, Chapman and Hall,
limestone
London, pp. 1-67.
[7] Saikia, P., Sarmah, B. J., Mahiuddin, S.,
4. CONCLUSIONS Sengupta, P., Saikia, P. C. Borthakur, P. C.,
2005. Limestone from New Umrangshu,
The isoelectric point of the Umrangshu limestone Assam, India: Characterisation and utilisation
is 6.2. The limestone shows negative zeta prospects. Proc. International Seminar on
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6.2 it shows positive zeta potential. The limestone
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