The Composition and Physical Properties of

Some Clays of Cross River State, Nigeria

L. E. Attah (PhD)

Abstract
Clay deposits collected from various locations in Cross River
State, Nigeria were studied to determine their physical,
compositional and firing characteristics in order to evaluate
them for industrial uses. The samples were pulverized, sieved,
digested with mineral acids and characterized. Results showed
that the clays are mainly kaolinitic with only occasional illite,
and quartz as the main subsidiary non-clay mineral. The high
plasticity index of the clays corresponds to the more
transported clays of the tertiary- to –recent environment. The
percentage of linear shrinkage varied from 11-16% with the
lowest shrinkage (11%), having the coarsest features. Silica
(SiO2) content of the clays ranged from 47-70% while the
alumina (Al2O3) content which varied from 6-35% was lower
than the theoretical value of kaolinite (39.5%), with high iron
(Fe2O3) and titanium (TiO2) content in some samples along
with trace amounts of fluxing materials. The firing colors
ranged from whitish/pinkish to brownish and reddish
depending on the amounts of iron and titanium oxides
present. Compared to the dark carbonaceous shales of
cretaceous origin in this area, these clays are relatively free
from carbonaceous matter, which makes the clays potentially
suitable for pottery, refractory and brick productions.
Keywords : clay, kaolinitic, plasticity, carbonaceous,
refractory, brick.

Introduction
Clay is an important and abundant raw material and
has amazing variety of uses and properties that depend on the
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composition and other factors as enumerated by Grim (1968).

These factors are clay mineral composition, non-clay mineral
composition, presence of organic material, the type and
amount of exchangeable ions and soluble salts, and texture.
Clays are composed of certain groups of hydrous aluminum,
magnesium, and iron silicates that may contain sodium,
calcium, potassium and other ions. These silicates collectively
make up the clay minerals and the major clay mineral groups
are kaolins, smectites, illites, chlorites, and hormites. The
specific clay minerals are identified by several techniques
including X-ray diffraction (Brindley and Brown, 1980)
,differential thermal analysis ( Smothers and Chiang, 1966),
electron microscopy ( Beutelspacher and Van der Marel, 1968
),and infrared spectrometry (Van der Marel and Beutelspacher,
1976).
Clays have several industrial uses which include the
manufacture of refractories, pottery/ceramic wares and
structural units. They are also used as fillers or extenders in
various products. The identification and quantification of the
clay and non-clay minerals present in a clay material
determines their uses and related industries. Each industrial
process requires certain property specifications that must be
met by either the raw or refined clay. The refining or
beneficiation of clays is an expensive process and it becomes
uneconomical if the composition and properties of the raw clay
differs greatly from the desired specification. Most of the
relevant industrial properties of the raw clay are dependent on
the composition and the particle size distribution of the clay as
well as the grain shape. All these factors control the plasticity
of the clay which plays a very important role in its industrial
application (Akpokodje,et. al, 1991)
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The Composition and Physical Properties of some Clays…

The mineralogical, geochemical and economic

appraisal of some clay and shale deposits of South Western
and North Eastern Nigeria have been discussed by Emofurieta
et.al (1994) . Clays and shales occur abundantly in the
sedimentary basin of South Eastern Nigeria ( Akpokodje, et.
al,1991). Ntekim et.al (1999) reported on the compositional
and industrial assessment of clay deposits of Itu in South
Eastern Nigeria. From available information (Akpokodje, 1986,
1989, Akpokodje, et. al.1991; Ntekim et. al,1999 and Attah,
et. al, 2001), only limited investigations have been carried out
on the clays of South Eastern Nigeria, particularly Cross River
State.
This paper reports the results of studies carried out on the
composition and some physical properties of potential
commercial clays deposited in parts of Cross River State,
Nigeria.

Methodology
Study area
Representative clay samples were collected from 18
known clay deposits in Cross River State of Nigeria. (Fig.1).
Sample preparation
In each case, 20g of clay sample was placed in a 600ml
polyethylene centrifuge bottle and 500ml of distilled water was
added, and allowed to hydrate for 24hrs. The suspensions
were shaken thoroughly and then centrifuged for 6min. at
600rpm in a centrifuge. The supernatant liquid was then
poured into 200ml polypropylene cups, frozen and then placed
in a freeze drier until the ice was sublimated (Constanzo,2001)
sealed containers before taking to the laboratory for analysis.
Particle size determination
Particle size determination was carried out by soaking
the samples for 24hrs and sieving with a mechanical shaker
using mesh sizes ranging from 14mm to 75 micron.

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Plasticity index
Plasticity index was determined using Atterberg liquid
and plastic limit equipments and was calculated as the
difference between liquid and plastic limits. pH and loss-on-
ignition (LOI) tests were carried out using standard methods.
Analysis of samples
The samples were saturated with NH4+ prior to total
elemental analysis, following the general procedure of Brindley
and Ertem (1971). The procedure involved washing the
sample three times with a solution of 1M NH4Cl and then with
50% (V/V) mixture of ethanol and distilled water until the
supernatant was free of Cl- by the AgNO3 method. The
samples were oven dried overnight at 105oC.
The elemental composition of the clays was determined
following digestion with aqua regia and perchloric acid. The
Na, K and Ca contents were determined using Jenway Flame
Emission photometer, PFP-7. All other elements, Si, Al, Fe, Mg
and Ti were determined using Atomic Absorption
spectrophotometer (UNICAM 919). Three replicate analysis
were averaged to obtain a single value.
Mineralogical studies were carried out using a Phillips X- ray
diffractometer model PW1710. All samples were randomly
mounted and analyzed serially using Cu-kα radiation at 45kv
and 20mA.at the scan speed of 20 per minute.

Results and Discussion

The particle size analysis of the clay samples are
presented in Figure 2. On the basis of the clay percentages
passing through the 75 micron sieve, Ekpokpa, Ediba, Akpet,
Ikot Effanga I, Ikot Omin and Atan Okoyong clays appear to
be the finest, with the clay from Abini being the coarsest. The
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The Composition and Physical Properties of some Clays…

other samples are between the two extremes. Apart from the
Abini clay, the other clays are actually very fine, inorganic
plastic clays. Table 1 showed the results of some physical
properties of the various clay samples. The values of the
plasticity index varied from 9-38%, while the linear shrinkage
values ranged from 8-18%, with the higher figures
corresponding to the more transportation clays of the tertiary-
to recent environment.
From the results of the chemical composition of the
clays as shown in Table 2, the highest silica (SiO2) content
(>70%) was found in clay samples from Akpet I and Atan
Okoyong, while clays from Ekpakpa, Betukwel and Nyanya
also contained high amounts of silica (>60%), with the lowest
silica contents found in Bisu (47.20%) and Ikot Effanga II
(49%) samples. The alumina (Al2O3) contents of the clays
ranged from 6-35%. The highest alumina content of 35% was
found in the Bisu clay with the Ikot Effanga I and II samples
having values of 31.45% and 33.45% alumina content
respectively, while lower values of 6.80% were obtained for
clays from Nyanya and Atan Okoyong , and 6.96% for the
Ediba clay. The iron (Fe2O3) content which was generally high
in all the samples ranged from 1.5 - 10.28%, with the Abini
clay having the highest (10.28%) and considerable amount of
titanium oxide (2.62%) than allowed. The higher
concentrations of iron oxides give rise to pinkish, brownish
and reddish firing colors which are objectionable in paper and
some ceramic industries. The high proportions of iron oxides
(>3%), in the clay deposites of Ovonum, Betkuwel, Nyanya,
Ediba, Abani, AkpetI, Aguaguna, Ikot Omin, Ikot Effanga and
Akpap Okoyong render them unsuitable for the paper and
ceramic industries. However, they are suitable for brick and
pottery productions. Although the other clays can be refined to
reduce the iron and titanium oxides,to the desired levels for
paper production, the process may be too expensive for

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industrial purposes. Substantial though variable amounts of

flux materials such as CaO, MgO, Na2O, K2O were also found
in all the clay samples. Generally, clays contain low amounts
of alkalis and magnesia. The slightly higher amount of lime
(CaO) in the sample from Nyanya (3%), could be attributed to
the presence of carbonates. pH values of the clay deposits
vary from 4.4-9.4 with the more acidic varieties attributed to
clays from tertiary- to- recent environment.
Figures 3-6 showed X-ray diffractograms for some
selected clay samples. The dominant clay mineral found was
kaolin with occasional illite and the main non-clay mineral as
quartz. Apart from Ikot Effanga clay, which may be classified
as fire clay by virtue of the high alumina and iron content, the
rest of the clays may be classified as ball clays.
When compared to the dark, carbonaceous shales of
Cretaceous origin in this area, these clays are relatively free
from carbonaceous matter. Although the clay samples are of
sedimentary origin, they seem to have gone through different
amounts of transportation before deposition which does affect
their physical properties such as plasticity index and shrinkage
level. From the ceramic point of view (Worral, 1976; Hegab
et.al 1984, Akpokodje et.al, 1991, Mermunt et.al, 2001, Attah
et. al, 2001), the investigated clays can be considered as low
alumina content with considerable amount of Fe2O3 and other
impurity oxides and can be utilized in ceramic, refractory or
brick industries. Ikot Omin and Ikot Effanga I clays could be
further beneficiated to produce paper clays.

Conclusion
From the properties of the clays obtained, it can be
concluded that the clays contain large amounts of silica,
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The Composition and Physical Properties of some Clays…

alumina, and iron with variable amounts of flux minerals and

are principally kaolinitic with only occasional illite and quartz
as the main contaminant. The high alumina clays are useful in
the production of bricks while the low alumina clays could be
applied in the production of ceramic and pottery wares.

Acknowledgment
LEA would like to thank M I Oden for providing the clay
samples, the University of Uyo consultancy services for the
use of Flame photometer and Atomic Absorption
spectrophotometer, and H H Murray of Indiana University,
USA for the X-ray diffractograms.

Table 1: Some Physical Properties of the Clay Minerals

Sample location Plasticity Index % Shrinkage Firing Color

(%)
Ovonum 21 13 Pinkish
Ikom 16 14 Whitish
Ekpokpa 9 16 Whitish
Adijinkpor 23 15 Brownish
Bisu 17 12 Whitish
Betukwell 24 11 Brownish
Utugwang 20 13 Whitish
Nyanya 21 13 Brownish
Ediba 19 14 Brownish
Abini 13 8 Reddish
Akpet 20 15 Brownish
Agwagune 38 16 Brownish
Ikot Omin 25 16 Reddish
Ikot Effanga I 27 18 Pinkish
Ikot Effanga II 29 15 Pinkish
Atan Okoyong 31 18 Whitish
Akpap Okoyong 23 14 Brownish

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Table 2: Ph and Chemical Composition of the Clay

Minerals (%)

LOI : loss-on-ignition
Sample SiO2 Al2O3 Fe2O TiO2 CaO MgO Na2O K2O LOI TOTAL pH
location 3
Ovonum 51.25 24.50 3.35 0.89 1.19 1.67 1.02 1.03 15.55 100.45 4.5

Ikom 51.25 30.01 2.46 0.74 1.23 0.45 2.01 0.24 11.00 99.39 4.8

Ekpokpa 63.31 9.83 1.52 0.05 1.86 0.70 4.04 6.70 12.10 100.11 7.6
Adijikpor 58.86 12.03 8.06 0.40 1.80 1.60 1.30 1.40 13.56 99.01 5.3
Bisu 47.20 35.11 1.78 0.89 0.06 0.08 0.05 0.71 15.95 101.83 7.5
Betukwel 62.39 9.92 6.41 0.60 2.59 0.77 4.42 0.96 11.10 99.16 7.4
Utunwan 50.50 29.60 2.29 0.63 0.08 0.05 0.19 0.21 16.40 99.95 9.4
g
Nyanya 60.00 6.80 6.86 0.35 3.00 2.25 2.01 2.35 16.67 100.29 8.1
Ediba 60.00 6.96 6.82 0.07 2.16 1.72 1.60 2.20 18.80 100.33 4.7
Abini 58.96 10.56 10. 2.6 2.6 2.1 1.8 1.7 10.00 100.7 5.0
28 2 3 0 6 8 9
Akpet 71.60 12.90 7.4 0.8 0.8 0.4 0.0 1.0 4.60 99.74 7.3
3 1 3 7 5 5
Aguagun 55.60 14.20 6.62 0.48 1.89 2.10 1.60 2.20 15.10 99.79 7.6
e
Ikot 61.82 9.94 9.12 0.98 2.39 1.68 1.46 0.96 11.09 99.44 4.4
Omin

Ikot 50.63 31.45 4.43 0.65 0.69 0.94 0.25 0.42 10.06 99.52 4.0
Effanga I
Ikot 48.65 33.45 4.85 0.49 0.21 0.67 0.36 0.93 10.19 99.8 4.8
Effanga
II
Atan 73.15 6.80 2.23 0.05 2.02 0.03 1.35 0.94 13.21 99.78 7.2
Okoyong
Akpap 57.34 9.89 7.20 0.07 2.70 2.24 2.00 2.13 16.31 99.88 4.4
Okoyong

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 The Composition and Physical Properties of some Clays…

PERCENTAGE OF SAMPLES PASSING FIGURE2 : PARTICLE SIZE ANALYSIS OF CLAY SAMPLES

100%
90%
80% 75µm
70% 150µm
60% 212µm
SIEVE

300µm
50%
425µm
40%
600µm
30% 1.18mm
20% 2.36mm
10% 3.35mm
0% 5mm
6.3mm

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SAMPLE LOCATION

References
Grim, R. E. (1968): Clay mineralogy. 2nd Edition. McGraw-
Hill, New York, 596p
Brindley, G. W. and Brown G. (1980): Crystal structures of clay
minerals and their X-ray identification: Monograph 5,
Mineralogical 500, London, 495p
Smothens, W. J and Chiang, Y (1966): Handbook of
Differential Thermal Analysis: Chem. Pub. Co, New
York, 633p
Beutespacher, H, and Van Der Marel, H. W. C. (1968): Atlas of
Infrared Spectroscopy of clay minerals and their
admixtures, Elservier, Amsterdam, 333p
Van Der Marel, H. W. and Beutespacher, H (1976): Atlas of
Infrared spectroscopy of clay minerals and their
admixtures, Elservier, Amsterdam, 396p
Akpokodje, E.G., Etu- Efeotor, J. O. and Olurufemi, B. N.
(1991): The compositional and physical of some ceramic
and pottery clays of South Eastern Nigeria, J. of Mining
and Geology, vol.27 (1), 1-8
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2008

Emofurieta, W. O; Ogundirim, T. O. and Imeokpai, E. G.

(1994): Mineralogical, Geochemical and Economic
appraisal of some clay and shale deposits of South
Western and North Eastern Nigeria, J. of Mining and
Geology, 30, 157-159
Ntekim, E. E.; Elueze, A. A. and Ekwere, S. J. (1999):
Compositional and industrial assessment of clay deposits
in Itu, S. E., Nigeria; Nig. J. of Min. Geo, vol 2, (1), 23-
Akpokodje, E. G. (1986): Engineering Geological
characteristics and classification of the superficial soils
of the Niger Delta; Engineering Geology, 23,193-211
Akpokodje, E. G. (1989): Preliminary studies on the
geotechnical characteristics of the Niger Delta subsoils;
Engineering Geology, 26, 247-259
Attah, L. E; Oden, M. I and Ibok, U. J. (2001): Brick forming
properties of Odukpani clay deposits from physical,
mechanical and mineralogical studies. West African J. of
Research and Development in Education, vol. 8, (1), 93-
Constanzo, P.M (2001): Clay and clay minerals, 49,372
Brindley, G. W and Ertem, G (1971): Clay and clay minerals,
19, 129
Worrall, W. E. (1976): Clay and ceramics Raw Materials. 2nd
Ed. Elservier Applied Science. 48-87
Hegab, O. A; Serry, M. A. and El-Banna (1984): Effect of
composition of some Egyptian clays on their ceramic
properties, Intercam, 33 (6), 31-33
Mermut, A. R.; Mermunt, A. R. and Cano, A. F. (2001):
Baseline studies of clay minerals society source clays:
Chemical analysis of major elements; Clay and Clay
Minerals, 49 (5), 381-386

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