2.

1 CLAY

The term clay refers to a naturally occurring material composed primarily of fine-grained

minerals, which is generally plastic at appropriate water contents and will harden with dried or

fired. Although, clay usually contains phyllosilicates, it may contain other materials that impart

plasticity and harden when dried or fired. Associated phases in clay may include materials that

do not impart plasticity and organic matter (Guggenheim, et al., 1998).

Clay is a natural mixture that is plastic when wet and hard when dried or fired. Clay comes from

the ground, usually in areas where streams or rivers once flowed. It is made from minerals, plant

life, and animals, all the ingredients of soil (Swapna,2013). Over time, water pressure breaks up

the remains of flora, fauna, and minerals, pulverizing them into fine particles. Larger particles

are filtered out through rocks and sand, leaving silt to settle into beds of clay. How far silt travels

from its source and how pure the silt is, determines the type of clay. Clay minerals are typically

formed over long periods of time by the gradual chemical weathering of rocks, usually silicate-

bearing, by low concentrations of carbonic acid and other diluted solvents. Since ancient times,

clay minerals have been investigated because of their importance in agriculture, ceramics,

building and other uses(Delia-Maria and Andrada, 2014).

Clays and clay minerals have been mined since the Stone Age; today they are among the most

important minerals used by manufacturing and environmental industries. The term clay is

applied both to materials having a particle size of less than 2 micrometers (25,400 micrometers =

1 inch) and to the family of minerals that has similar chemical compositions and common crystal

structural characteristics (Velde, 1995). Having good understanding of the types, formation,
structure and properties of clay, is important so as to know which clay to use when the need

arises.

2.1.1 COMPOSITION OF CLAY

Clay is a, substance which we know as a deposit which is extensively distributed over the

surface ("f, the earth. It is found almost everywhere but differs greatly in its purity. This

deposit has been produced by the decomposition of various rocks. As these decomposed

products have been acted upon by water, the various original materials have been separated,

leaving deposits of various kinds. Some of these we know, as sand, clay and various

mixtures. Clay in its pure condition is comparatively rarely found, the larger Position of the

deposit being composed of impure clay. Pure clay is a silicate of aluminum and when found

in large quantities it is called kaolin. The various changes which take place upon the

minerals present in the earth's crust, in order that clay may be produced is according to the

results Of Forchhammer shown in the formula

A120 3 , 2Si0'2 + 2H20'.

The changes which take place in the original rock to produce the clay substance may he

show by the following equation, as the result of the action of water and carbon dioxide

upon feldspar.

2A12 0'3, 2K20, 2Si02 (Feldspar) + 4H20 + 2G02 = 2AL2O3

3SiD2, 4H20 + K200a + 9Si02 (Clay substance) (Newman, 1987)

2.1.2 USES OF CLAY

The applications of clays and their derivatives in the industries are many and varied. The

suitability of a clay in a particular industry is determined by the properties of clay minerals

present in it, which are in turn determined by the internal structures and chemical compositions
of those clay minerals. General absence or scarcity of transition elements, which have strong

pigmentation properties, facilitate the use of kaolinite-rich clays in production of high-quality

porcelain. Owing to their distinctive structures, clay minerals exist with very fine grain size and

have high surface activity, and are therefore suitable as fillers in rubber industries. In addition to

these properties, the whiteness of kaolinite makes it ideal filler in paper industry. Cation

exchange property of some clay minerals, which is a result of their characteristic totc layer

structure, enables their use as filters and absorbents. The characteristic internal structure imparts

to some clay minerals, esp. smectites, their distinctive lubricating and thixotropic properties,

facilitating the use of bentonite clays in drilling fluids (Swapna, 2013). The easy availability of

clays in almost all inhabitable places on earth and its certain characteristic properties facilitate its

diverse use in the human civilization since prehistoric time. The clays were widely used in

building muddy huts or in the production of bricks, potteries etc. even in the most primitive

forms of cultures. In the present age, the uses of clays and clay minerals are increasing day by

day, and they are gradually replacing metals in various fields as cheaper, better and environment-

friendly alternatives (Swapna, 2013).

2.1.2 Physical and Chemical Properties of Clay

The characteristics common to all clay minerals derive from their chemical composition,

layered structure, and size. Clay minerals all have a great affinity for water. Some swell

easily and may double in thickness when wet. Most have the ability to soak up ions

(electrically charged atoms and molecules) from a solution and release the ions later

when conditions change.

Water molecules are strongly attracted to clay mineral surfaces. When a little clay is

added to water, a slurry forms because the clay distributes itself evenly throughout the

water. This property of clay is used by the paint industry to disperse pigment (color)

evenly throughout a paint. Without clay to act as a carrier, it would be difficult to evenly

mix the paint base and color pigment. A mixture of a lot of clay and a little water results

in a mud that can be shaped and dried to form a relatively rigid solid. This property is

exploited by potters and the ceramics industry to produce plates, cups, bowls, pipes, and

so on. Environmental industries use both these properties to produce homogeneous liners

for containment of waste.

The process by which some clay minerals swell when they take up water is reversible.

Swelling clay expands or contracts in response to changes in environmental factors (wet

and dry conditions, temperature). Hydration and dehydration can vary the thickness of a

single clay particle by almost 100 percent (for example, a 10-thick clay mineral can

expand to 19.5 in water (Velde, 1995). Houses, offices, schools, and factories built on

soils containing swelling clays may be subject to structural damage caused by seasonal

swelling of the clay portion of the soil.

Another important property of clay minerals, the ability to exchange ions, relates to the

charged surface of clay minerals. Ions can be attracted to the surface of a clay particle or

taken up within the structure of these minerals. The property of clay minerals that causes

ions in solution to be fixed on clay surfaces or within internal sites applies to all types of

ions, including organic molecules like pesticides. Clays can be an important vehicle for

transporting and widely dispersing contaminants from one area to another (Davis, et al.,

1996).
2.1.3 Classes of Clays

Clays are generally divided into three classes:

a) Porcelain clays; this set of clays are purely kaolin. This burns to white or light-cream

color.
b) clays; this class of clays, contains more impurities than the porcelain clay. It burns to a

yellow-red color and is used for ordinary earthenware.

Fire clays; these clays approach very close to the porcelain clays in composition, however

they contain a large quantity of iron, also more silica as quartz.

2.1.3 CLASSIFICATION OF CLAY MINERALS

I. Amorphous
Allophane group
II. Crystalline
A. Two-layer type (sheet structures composed of units of one layer of silica tetrahedrons and one
layer of alumina octahedrons)
1. Equidimensional
Kaolinite group
Kaolinite, dickite and nacrite
2. Elongate
Halloysite
B. Three-layer types (sheet structures composed of two layers of silica tetrahedrons and one
central dioctahedral or trioctahedral layer)
1. Expanding lattice
a. Equidimensional
Smectite group
Sodium montmorillonite, calcium montmorillonite, and beidellite
Vermiculite
b. Elongate
Smectite
Nontronite, saponite, hectorite
2. Non-expanding lattice
Illite group
C. Regular mixed-layer types (ordered stacking of alternate layers of different types)
Chlorite group
D. Chain-structure types (hornblende-like chains of silica tetrahedrons linked together by
octahedral groups of oxygens and hydroxyls containing Al and Mg atoms)
Sepiolite
Palygorskite (attapulgite) (Murray,1958).
2.1.4 Beneficiation of Clay Material

The clay material, if obtained directly from the mines usually requires some purification

(Beneficiation) treatment to separate the various impurities present.

One method most frequently used is that of sedimentation which aims at separation of

minerals on a morphological and gravity basis. It is broadly defined as the separation of a

suspension into a supernatant fluid and rather dense slurry containing a higher

concentration of solid. It is most commonly defined as the gravitational settling of solids

in liquids (Kirk Othmer, 1997). The use of sedimentation in the industry fall into the

following categories: solid-liquid separation (2); solid-solid separation (3); and other

operations such as mass transfer, washing, etc. In solid-liquid separation, the solids are

removed from the liquids either because the solids or the liquids are valuable, or because

these have to be separated before disposal. If the primary purpose is to produce the solid

in highly concentrated slurry, the process is called thickening. If the purpose is to clarify

the liquid, the process is called clarification. In solid-solid separation, the solids are

separated in fractions according to size, density, shape or other particulate properties.

Sedimentation is also used for size 43 separation (qv), i.e. classification of solids. One of

the simplest ways to remove the coarse or dense solids from a feed suspension is by

sedimentation. Successive decantation in a batch system produces closely controlled size

fractions of the product. Generally, however, particle classification by sedimentation does

not give sharp separation.

Another method of purifying clay material is by combining sedimentation with sieving.

Sieving, which also separates materials on a size basis is sometimes preferred to the

sedimentation technique because it is much faster to accomplish. Sieving is achieved by

 soaking clay in water, blunging and sieving through the appropriate sieve. The choice of

sieve size is guided by the knowledge of the particle size distribution of the clay (Ahmed,

1986).

Another method also used for purifying clay (for alum/alumina production) is by

calcination. This method helps in removing some components which would otherwise not

dissolve in the solvent (in this case water) but will decompose under the influence of high

temperatures (this includes some carbonates, chlorides, oxides and other organic

compounds present in the clay). This further concentrates the wanted. Clay is reported to

lose between 12-15%wt when heated to above 500 0C in furnaces (Ahmed, 1986; Ahmed

and Onaji, 1987).

2.3 KAOLIN

Kaolin is a clay mineral with the chemical composition of Al 2SiO5(OH)4. It is a layered

silicate mineral, with one tetrahedral sheet linked through oxygen atoms to one

octahedral sheet of alumina octahedral. Rocks that are rich in kaolinite are known as

China Clay, white clay or kaolin. Geologically kaolin comes from decomposition of

feldspar in soft, disintegrating granite, gneiss and porphyritic rocks (Deer, et al., 1992,

Belloto, et al., 1995, Stanley, 2006).

Kaolin is used in many consumer products and as a functional additive and process

enabler in manufacturing. It is typically extracted from open-pit mines that range from

small to very large scale (tens to hundreds of thousands of dry metric tons produced per

year). Ore processing consists of removing impurities, engineering particle size and

shape, and enhancing certain properties through thermal and chemical treatment. In

addition to the technical aspects of mining and processing, the social, environmental, and
 economic impacts of kaolin production are managed at each stage of the mining life

cycle. Discussed herein are aspects of the history of kaolin mining, the classification of

kaolin mines, the processing of kaolin, and the life cycle of mining (Kogel, et al., 2014).

2.3.1 HISTORICAL VIEW OF KAOLIN MINING, PROCESSING, AND USES

Kaolin, a highly versatile industrial mineral, is mined and processed for diverse end-use

markets. Its versatility derives from its naturally occurring range of crystal shapes, sizes,

and layer structures. These attributes, along with desirable rheological, chemical, and

optical properties, give kaolin its value as an industrial raw material. Kaolin has limited

utility in its raw form, and the majority of end-use applications require a refined product

derived from a combination of controlled mining and selective processing to engineer

specific properties. Kaolin mining began in the Neolithic when early humans discovered

that the material could be used as a white pigment for painting and decoration. These

miners devised a simple process to transform the raw mineral into a form that could be

more readily applied to surfaces. The process started with digging kaolin from river

banks, drying it, grinding it into a fi ne powder, and finally mixing it with various

binders, including animal fat, saliva, water, and blood. For thousands of years after the

first kaolin-based paint was placed in the hands of prehistoric artists, kaolin mining and

processing barely changed. Small advances were made as new applications were

discovered, but the basic process remained more or less the same. In some parts of the

world, the same small-scale mining methods that provided clay for cave art are still

employed today to extract clay for mud huts, earthenware pottery, and handmade tile.

About 2000 years ago, the Chinese exploited kaolin for higher-tech, small-scale porcelain
production (Schroeder and Erickson, 2014). It wasnt until the industrial revolution that

the first significant technological changes took place and large-scale mechanized methods

became available. These new technologies led eventually to the development of the most

important commercial kaolin mining districts in operation today. They are in the

southeastern United States, northern Brazil, and the United Kingdom (Cornwall). Kaolin

from these regions is shipped worldwide. Many small kaolin mining operations can be

found on most every continent. The vast majority of these small mines serve local

markets.

Over the past 50 years there have been continuous advances in the way we mine and

process kaolin. Much of this has been market driven as more technically demanding uses

for kaolin have evolved. The most significant markets today in terms of value and volume

are paper, ceramics, fiberglass, and paint. Recently the use of kaolin as a raw material for

ceramic prop pants has emerged as a rapidly growing market that will likely surpass

paper, which has declined over the last decade. In addition to these commodity markets,

there are new highly technical applications such as specialty packaging, energy-efficient

building materials, and lightweight paper coatings. On the mining side, many of the

advances have been driven by sustainable development and corporate social

responsibility principles. These principles incorporate social, environmental, and

economic considerations into each phase of the mining life cycle. There are many ways to

define sustainable development (SD); in the context of mining, however, its meaning is

not always clear. This is because SD is a broad and complex concept especially as it

applies to mining. The most universally accepted definition is development that meets
 the needs of the present without compromising the ability of future generations to meet

their own needs (Brundtland Commission United Nations, 1987).

In 2003, the International Council of Mining and Metals took this concept and drafted 10

SD principles to provide a roadmap for implementing SD practices into mining including

those that mine kaolin, have integrated SD into their business models and new

management strategies have emerged as a result (Boltin 2009). These include improving

mine efficiency and process recovery. Efficient use of energy and water are also key

aspects of sustainable mining operations (Kogel et al. 2014).

2.3.2 STRUCTURE OF KAOLIN

Kaolinite is the main constituent of kaolin. Its chemical structure is Al 2Si2O5(OH)4 (39,8

% alumina, 46,3 % silica, 13,9 % water) which represents two-layer crystal (silicon-

oxygen tetrahedral layer joined to alumina octahedral layer exist alternately). The

theoretical formula for kaolinite is Si2Al2O5(OH)4 (other formulas are Al2O32SiO22H2O

and Al2O7Si2.2H2O), which has a molecular weight of (258.071g/mol). Kaolinite is build

up from pseudo hexagonal triclinic crystals with diameter (0.210m), with thickness

(0.7nm) its density is 2.6g/cm3 (http://webmineral.com, 2017,

http://www.chemicalland21.com, 2017, Novk and Horvth, 1981).

Kaolinite has a 1:1 sheet structure composed of SiO4 tetrahedral sheets and Al-(O, OH)6

octahedral sheets (or, expressed in other way, [Si2O5]2- sheet and [Al2(OH)4]2 sheet) with

pseudo-hexagonal symmetry. The sheets are created from planes, which are occupied as

follows: O6Si4O4(OH)2Al4(OH)6. The morphology of the kaolin crystals is plate-

like. The c-axis of the kaolinite crystal is perpendicular to the basal plane. A crystal

system of the kaolinite is triclinic, the space group is P1, and lattice parameters are a=
 0,515nm, b= 0,895nm, c = 0,740nm, = 91,68, = 104,87, = 89,9. An ideal cell of the

kaolinite is electrically neutral. Its crystal-chemical formula is Al4Si4O10(OH)8

Figure 2.1: Structure of kaolinite designed by Brindley Nakahra, viewed from the a-axis

Direction

Figure 2.2: Crystallochemical structure of kaolinite (Brindley and Nakahra.,1959)

Figure 2.3: The change of the tetrahedrical (light) and octahedral (dark) sheets (Brindley and
Nakahra.,1959)

2.3.3 METAKAOLINITE AND STRUCTURE OF METAKAOLINITE

Dehydroxylation is a reaction of decomposition of kaolinite crystals to a partially

disordered structure. This change is followed with a smaller shrinkage of the dimensions

of the sample and the porosity rise (Norton, 1970). The first present of dehydroxylation

were identificated by changes of mechanical (Kozk and uba, 1981), electrical (Kozk,

1992) properties and also by weight loss. The results of isothermal fi ring show that the

dehydroxylation begins at ~420 C. The chemical equations describing this process is

Al2O3.2SiO2.2H2O Al2O3.2SiO2 + 2H2O (g).

The result of dehydroxylation is a new phase called a metakaolinite. During this reaction,

as XRD showed, the higher-order reflections lost their intensity and vanished in the XRD

background. This result led to the opinion, that the metakaolinite can be amorphous, now

a conception of the short-range order crystalline structure of metakaolinite predominates

(Sujeong, et al., 2003, Chin-Yi and Wei-Hsing, 2002, and Brindley and Nakahira, 1959).

The loss of high-order reflections indicates that dehydroxylation results in structural

disturbances through the breaking of unstable bonds. As a result, the degree of ordering

became lower than that in kaolinite as dehydroxylation progressed.

4 Industrial Applications of Kaolin

Paper Industry: To increase the whiteness and smoothness of a paper, and also to

make it print better, kaolin is used and is a major application of it (kaolin) in the

USA. Kaolin used to coat the surface of the paper sheet makes possible sharp

photographic illustrations and bright printed colors. Kaolin constitutes nearly one-

third the weight of today's slick sheet magazines. The significant properties of
 kaolin of greatest value to the paper industry are whiteness, low viscosity, non-

abrasiveness, controlled particle sizes, and flat hexagonal plates.

Rubber Industry: Kaolin is used as a filler in many rubber goods. It adds strength,

abrasion resistance, and rigidity to both natural and synthetic rubber products. In

general, most rubber products extrude more easily after kaolin filler is added. The

major reason that kaolin is used in rubber compounds is its whiteness and low

cost. Although kaolin costs less than most other rubber pigments, it has excellent

functional properties.

Figure 2.4: Lattice of metakaolinite supposed by Brindley and Nakahira

A metakaolinit kristlyrcsa Brindley and Nakahira felttelezse szerint Oxign

ionok klnbz pozcikban (alumnium, szilcium).

Ceramics Industry: Kaolin is used in ceramic whiteware products, insulators, and

refractories. In whitewares, kaolin aids accurate control of molding properties,

and adds dry and fired strength, dimensional stability, and a smooth surface finish

to the ware. The excellent dielectric properties and chemical inertness of kaolin

make it well suited for porcelain electrical insulators. In refractory applications,

 the dimensional stability, high fusion point, and low water content, along with

high green strength, make kaolin an important constituent.

Paint Industry: Kaolin is used in paint because it is chemically inert and insoluble

in the paint system has a high covering power, gives the paint desirable flow

properties, and is low in cost.

Plastic Industry: The addition of kaolin to thermosetting and thermoplastic mixes

gives smoother surfaces, a more attractive finish, good dimensional stability, and

high resistance to chemical attack. In addition, the flat hexagonal kaolin plates

hide the reinforcing fibers and give the mix flowability to simplify tile molding of

complex shapes.
Other Industrial Applications Includes:
i ink
ii cement
iii detergents
iv adhesives
v fertilizers etc.

5 Kaolinite in Nigeria
Table 2.1: Locations of Kaolin Deposit in Nigeria and their Chemical Composition.

(Onaji andAhmed,1995)
6 Formation of Kaolin
Kaolinite formation is favored by the presence of dilute acidic solutions such as those
present in soils undergoing intense leaching. These conditions are mainly found in wet

tropical environments where kaolinite is a major component of lateritic soils. Kaolinite

can also form in hydrothermal environments e.g. the void spaces of sand stones during

burial digenesis, around hot springs and as a by-product of the alteration of smectite to

illite. Feldspar component of granitic masses are kaolinized by loss of alkali content and

some silica and gain of water of constitution (Eberl, 1997).

Some of this potassium salt is washed away by water, while some of the silica are

retained as free silica and in more complex forms like mica, thereby serving as impurities

in the ore.

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of Environmental Physics, Chemistry and Technology, Babe-Bolyai University, Cluj-Napoca,
Romania.

Murray, H.H. and Smith, J.M. (1958) Lightweight Aggregate Potentialities of Some Indiana
Shales. Indiana Geological Survey Report of Progress No. 12, 42pp. Newman, A.C.D., ed.
(1987) Chemistry of Clays and Clay Minerals. Mineralogical Society Monograph No. 6, London,
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Newman, A.C.D., ed. (1987) Chemistry of Clays and Clay Minerals. Mineralogical Society
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