INTRODUCTION TO CLAY MINERALS

2020

CHAPTER IV

INTRODUCTION TO CLAY MINERALS

Clay minerals are hydrous aluminium phyllosilicates, sometimes with variable amounts
of iron, magnesium, alkali metals, alkaline earths, and other cations found on or near
some planetary surfaces.

Clay minerals refers to a group of hydrous aluminosilicates that predominate the clay-sized (A
soil particle may be a mineral or a rock fragment. A mineral is a chemical compound formed in
nature during a geological process, whereas a rock fragment has a combination of one or more
minerals. Based on the nature of atoms, minerals are classified as silicates, aluminates, oxides,
carbonates and phosphates.

Out of these, silicate minerals are the most important as they influence the properties of clay
soils. Different arrangements of atoms in the silicate minerals give rise to different silicate
structures.

FINE SOIL FABRIC

Natural soils are rarely the same from one point in the ground to another. The content and nature
of grains varies, but more importantly, so does the arrangement of these. The arrangement and
organisation of particles and other features within a soil mass is termed its fabric.

CLAY particles are flaky. Their thickness is very small relative to their length & breadth, in
some cases as thin as 1/100th of the length. They therefore have high specific surface values.
These surfaces carry negative electrical charge, which attracts positive ions present in the pore
water. Thus a lot of water may be held as adsorbed water within a clay mass.

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 INTRODUCTION TO CLAY MINERALS
2020

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 INTRODUCTION TO CLAY MINERALS
2020

COMPOSITION OF CLAY MINERALS

Clay minerals are composed essentially of silica, alumina or magnesia or both, and water, but
iron substitutes for aluminum and magnesium in varying degrees, and appreciable quantities of
potassium, sodium, and calcium are frequently present as well. Some clay minerals may be
expressed using ideal chemical formulas as the following: 2SiO2·Al2O3·2H2O (kaolinite),
4SiO2·Al2O3·H2O (pyrophyllite), 4SiO2·3MgO·H2O (talc), and 3SiO2·Al2O3·5FeO·4H2O
(chamosite). The SiO2 ratio in a formula is the key factor determining clay mineral types.

TYPES OF CLAY MINERALS

These minerals can be classified on the basis of variations of chemical composition and atomic
structure into nine groups: (1) kaolin-serpentine (kaolinite, halloysite, lizardite, chrysotile), (2)
pyrophyllite-talc, (3) mica (illite, glauconite, celadonite), (4) vermiculite, (5) smectite
(montmorillonite, nontronite, saponite), (6) chlorite (sudoite, clinochlore, chamosite), (7)
sepiolite-palygorskite, (8) interstratified clay minerals (e.g., rectorite, corrensite, tosudite), and
(9) allophane-imogolite

Kaolinite is derived from the commonly used name kaolin, which is a corruption of the Chinese
Gaoling (Pinyin; Wade-Giles romanization Kao-ling), meaning “high ridge,” the name of a hill
near Jingdezhen where the occurrence of the mineral is known as early as the 2nd century BCE.

Montmorillonite and nontronite are named after the localities Montmorillon and Nontron,
respectively, in France, where these minerals were first reported.

Celadonite is from the French céladon (meaning grayish yellow-green) in allusion to its colour.

Because sepiolite is a light and porous material, its name is based on the Greek word for
cuttlefish, the bone of which is similar in nature. The name saponite is derived from the
Latin sapon (meaning soap), because of its appearance and cleaning ability.

Vermiculite is from the Latin vermiculari (“to breed worms”), because of its physical
characteristic of exfoliation upon heating, which causes the mineral to exhibit a spectacular
volume change from small grains to long wormlike threads.

Baileychlore, brindleyite, corrensite, sudoite, and tosudite are examples of clay minerals that
were named after distinguished clay mineralogists—Sturges W. Bailey, George W. Brindley,
Carl W. Correns, and Toshio Sudō, respectively.

Finally, there are 4 main classes of clay minerals.

1. Kaolinite - also includes dickite and nacrite; formed by the decomposition of orthoclase feldspar
(e.g. in granite) .The Kaolinite Group consists of polymorphs of formula Al2Si2O5(OH)4.
The repeat unit is a single silicate sheet condensed with alumina octahedra. Kaolinite

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clays have long been used in the ceramic industry, especially in fine porcelains, because
they can be easily molded, have a fine texture, and are white when fired. Kaolinite is the
purest of clays, meaning that it varies little in composition. It also does not absorb water
and does not expand when it comes in contact with water. Thus, kaolinite is the preferred
type of clay for the ceramic industry

2. Smectites or montmorillonites - also includes bentonite and vermiculite; formed by the

alteration of mafic igneous rocks rich in Ca and Mg; weak linkage by cations (e.g. Na+,
Ca++) results in high swelling/shrinking potential. Montmorillonite or smectite is family
of expansible 2:1 phyllosilicate clays having permanent layer charge because of the
isomorphous substitution in either the octahedral sheet (typically from the substitution of
low charge species such as Mg2+ , Fe2+, or Mn2+ for Al3+ ). The most common
smectite is Montmorillinite, with a general chemical formula : (1⁄2Ca,Na)(Al,Mg,Fe)
4(Si,Al) 8 O20(OH) 4.nH2O Montmorillinite is the main constituent of bentonite, derived
by weathering of volcanic ash. Montmorillinite can expand by several times its original
volume when it comes in contact with water. This makes it useful as a drilling mud (to
keep drill holes open), and to plug leaks in soil, rocks, and dams. Montmorillinite,
however, is a dangerous type of clay to encounter if it is found in tunnels or road cuts.
Because of its expandable nature, it can lead to serious slope or wall failures..

3. Illite - also includes glauconite (a green clay sand) and are the commonest clay minerals;
formed by the decomposition of some micas and feldspars; predominant in marine clays
and shales. Illite is similar to muscovite and is the most common clay mineral, often
composing more than 50 percent of the claymineral suite in the deep sea. They are
characteristic of weathering in temperate climates or in high altitudes in the tropics, and
typically reach the ocean via rivers and wind transport. The Illite Group clays have a
general formula (K,H)Al2(Si,Al)4O10(OH)2-xH2O, where x represents a variable
amount of water. The structure of this group is similar to the montmorillonite group with
a sandwich-type structure. The Illite clays have a structure similar to that of muscovite,
but is typically deficient in alkalies, with less Al substitution for Si. Thus, the general
formula for the illites is: KyAl4 (Si8-y,Aly)O20(OH)4 , usually with 1 < y < 1.5, but
always with y < 2. Because of possible charge imbalance, Ca and Mg can also sometimes
substitute for K. The K, Ca, or Mg interlayer cations prevent the entrance of H2O into the
structure. Thus, the illite clays are non-expanding clays. Illite type clays are formed from
weathering of K and Alrich rocks under high pH conditions. Thus, they form by
alteration of minerals like muscovite and feldspar. Illite clays are the main constituent of
shales.

4. The Chlorite Group also contains sandwich-type units. In many of these minerals, there
is another weakly-attached, octahedrally coordinated Mg2+ between sandwiches. The
general formula is X4-6Y4O10(OH, O)8. The X represents either aluminum, iron,
lithium, magnesium, manganese, nickel, zinc or rarely chromium. The Y represents either
aluminum, silicon, boron or iron but mostly aluminum and silicon.

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BASIC STRUCTURAL UNITS

Soil minerals are formed from two basic structural units: tetrahedral and octahedral. Considering
the valencies of the atoms forming the units, it is clear that the units are not electrically neutral
and as such do not exist as single units.

The basic units combine to form sheets in which the oxygen or hydroxyl ions are shared among
adjacent units. Three types of sheets are thus formed, namely silica sheet, gibbsite
sheet and brucite sheet.

Isomorphous substitution is the replacement of the central atom of the tetrahedral or octahedral
unit by another atom during the formation of the sheets.

The sheets then combine to form various two-layer or three-layer sheet minerals. As the basic
units of clay minerals are sheet-like structures, the particle formed from stacking of the basic
units is also plate-like. As a result, the surface area per unit mass becomes very large.

STRUCTURE OF CLAY MINERALS

A tetrahedral unit consists of a central silicon atom that is surrounded by four oxygen atoms
located at the corners of a tetrahedron. A combination of tetrahedrons forms a silica sheet.

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An octahedral unit consists of a central ion, either aluminium or magnesium, that is surrounded
by six hydroxyl ions located at the corners of an octahedron. A combination of aluminium-
hydroxyl octahedrons forms a gibbsite sheet, whereas a combination of magnesium-hydroxyl
octahedrons forms a brucite sheet.

TWO LAYERS SHEET MINERALS

Kaolinite and halloysite clay minerals are the most common.

Kaolinite Mineral

The basic kaolinite unit is a two-layer unit that is formed by stacking a gibbsite sheet on a silica
sheet. These basic units are then stacked one on top of the other to form a lattice of the mineral.
The units are held together by hydrogen bonds. The strong bonding does not permit water to
enter the lattice. Thus, kaolinite minerals are stable and do not expand under saturation.

Kaolinite is the most abundant constituent of residual clay deposits.

Halloysite Mineral

The basic unit is also a two-layer sheet similar to that of kaolinite except for the presence of
water between the sheets.

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2020

THREE LAYER SHEET MINERALS

Montmorillonite and illite clay minerals are the most common. A basic three-layer sheet unit is
formed by keeping one silica sheet each on the top and at the bottom of a gibbsite sheet. These
units are stacked to form a lattice as shown in figure below.

Montmorillonite Mineral

The bonding between the three-layer units is by van der Waals forces. This bonding is very weak
and water can enter easily. Thus, this mineral can imbibe a large quantity of water causing
swelling. During dry weather, there will be shrinkage.

Illite Mineral

Illite consists of thebasic montmorillonite units but are bonded by secondary valence
forces and potassium ions, as shown. There is about 20% replacement of aluminium with
silicon in the gibbsite sheet due to isomorphous substitution. This mineral is very stable and
does not swell or shrink.

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CLAY PARTICLE INTERACTION

Clay-water interaction is an all-inclusive term to describe various progressive interactions

between clay minerals and water. In the dry state, clay packets exist in face-to-face stacks like a
deck of playing cards, but clay packets begin to change when exposed to water. Five descriptive
terms describe the progressive interactions that can occur in a clay-water system, such as a water
mud.
(1) Hydration occurs as clay packets absorb water and swell.
(2) Dispersion (or disaggregation) causes clay platelets to break apart and disperse into the water
due to loss of attractive forces as water forces the platelets farther apart.
(3) Flocculation begins when mechanical shearing stops and platelets previously dispersed come
together due to the attractive force of surface charges on the platelets.
(4) Deflocculation, the opposite effect, occurs by addition of chemical deflocculant to flocculated
mud; the positive edge charges are covered and attraction forces are greatly reduced.
(5) Aggregation, a result of ionic or thermal conditions, alters the hydrational layer around clay
platelets, removes the deflocculant from positive edge charges and allows platelets to assume a
face-to-face structure.

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