INDEX

INTRODUCTION
IMPORTANCE OF CLAY MINERALS:
ORIGIN OF CLAY MINERALS.
CHARGE DEVELOPMENT ON CLAYS.
SILICATE CLAYS.
TYPE OF CLAY MINERALS.
CARBONATE AND SULFATE MINERALS
USE OF CLAY MINERALS.
PROPERTIES
OCCURRENCE
CLASSIFICATION
INFORMATION CLAY MINERALS & SOILS
DEFINITION OF CLAY MINERALS
HISTORY
CLAY MINERALS
FORMATION
DIAGENESIS
HYDROTHERMAL ALTERATION
USES
CERAMICS AND BRICKS
WORLD PRODUCTION AND CONSUMPTION
MINING AND PROCESSING
HYDROTHERMAL

CLAY MINERALS

0 | Page

Introduction
Soils are made up of a complex mixture of solids, liquids and gases.
The solid fraction of soils are made up of organic and inorganic
components. The inorganic component of the soil makes up more
than 90% of the soil solids.
Inorganic components occur mainly in limited number of
compounds with definite crystalline structure called minerals. The
inorganic component includes both primary and secondary
minerals.
The secondary minerals normally are found in the clay fraction of
the soil which is the fraction of the soil solids which is less the 2
micron or 0.002 mm. Clay minerals are minerals which mainly occur
in the clay sized fraction of the soil.
Clay minerals are hydrous aluminum phyllosilicates, sometimes
with variable amounts of iron, magnesium, alkali metals, alkaline
earths, and other cations found on or near some planetary surfaces.

Clay minerals form in the presence of water and have been important
to life, and many theories of abiogenesis involve them. They have

1 | Page

been

useful

to

humans

since

ancient

times

in agriculture and manufacturing.

Importance of Clay Minerals:
The clay minerals and soil organic matter are colloids.
The most important property of colloids is their small size and large
surface area. The total colloidal area of soil colloids may range from
10m2/g to more than 800 m2/g depending the external and internal
surfaces of the colloid.
Soil colloids also carry negative or positive charges on their external
and internal surfaces. The presence of charge influences their ability
to attract or repulse charge ions to or from surfaces.
Soils colloids play a very important role in the chemical reaction
which take play in soil and influence the movement and retention of
contaminants, metals, and nutrients in the soil.
Origin of Clay Minerals.
Clay minerals are formed weathering a variety of minerals.
The two main processes may involve slight physical and chemical
alteration or decomposition and recrystallization.
Clay mineral types are normally determined by the types of
minerals and acidity of the leaching water.
Based on their origins clays may classified as Inherited, Modified,
Transformed or Neoformed

Charge Development on Clays.

Two main sources of charge in clay minerals are isomorphous
2 | Page

substitution and pH-dependent charges.

Charge development of on silicate clays is mainly

due to

isomorphous substitution. This is the substitution of one element for

another in ionic crystals with out change of the structure. It takes
place during crystallization and is not subject to change afterwards.
It takes places only between ions differing by less than about 10%
to 15% in crystal radii.. In tetrahedral coordination, Al3+ for Si4+
and in octahedral coordination Mg2+, Fe2+, Fe3+ for Al3+. Charges
developed as a result of isomorphous substitution are permanent
and not pH-dependent.
In allophanes, some silicate clays e.g. kaolinite, and the metal
oxides the main source of charge are termed pH -dependent
charges because these charges depend on the pH of the soil. pH
depend charges are variable and may either be positive or negative
depending on the pH of the soil. In the metal oxides acid soils tend
to develop positive charges because of the protonation of the oh
ggoud on the oxide surfaces.

Type of Clay Minerals.

There are four major types of Clay minerals ( see Table 5-1).
These include the layer silicates, the metal oxides and hydroxides
and oxy-oxides, amorphous and allophanes, and crystalline chain
silicates.

Silicate Clays.
3 | Page

The silicate clays are layers of tetrahedral and octahedral sheets.

The basic building blocks of tetetrahedral and octahedral sheets are
the silica tetrahedron and the aluminum octahedra.
The Si+4 cation occurs in fourfold and tetrahedral coordination with
oxygen whilst the Al3+ is generally found in sixfold or octahedral
coordination.
Layer silicate minerals are sometimes defined on the basis of the
number of certain positions occupied by cations. When two-thirds of
the octahedral positions are occupied , the mineral is called
dioctahedral; when all 3 positions are occupied it is called
trioctahedral.
When one octahedral sheet is bonded to one tetrahedral sheet a 1:1
clay mineral results. Presence of surface and broken - edge OH
groups gives the kaolinite clay particles their electronegativity and
their capacity to absorb cations.
In 2:1 clay mineral an octhehedral sheet is bonded to two
tetrahedral sheets. The octahedral sheet is generally sandwiched
between the two tetrahedral sheets. The 2:1 clays can be classified
into expanding (smectites) and non-expanding clays (Illite and
micas) on the basis of the sheet where isomorphous susbstitution is
taking predominantly taking place (Refer to Figure 5-3).
In the 2:1:1 lattice clays, a positively charge brucite sheet
sandwiched between layers restricts swelling, decreases effective
surface area, and decreases the effective CEC of mineral. The
Idealized

formular

of

half

cell

is

Al

Mg2(OH)6)K

(Mg3(Si4-

x Alx)O10(OH)2. Substitution occurs is in the tetrahedral layer and

the layer change is variable but similar to mica. It occurs commonly
4 | Page

in sedimentary rocks.
Silicate Clay Mineral Groups:
Group

Lay

Layer

er

Charge

Typ

(x)

Type of Chemical Formula

e
Kaolinite

1:1

<0.01

Illite

2:1

1.4-2.0

[Si4]Al4O10(OH)8.nH2O (n= 0 or 4)

Mx[Si6.8Al1.2]Al3Fe.025Mg0.75O20(OH)
4

Vermiculit 2:1

1.2-1.8

Mx[Si7Al]AlFe.05Mg0.5O20(OH)4

Smectite

2:1

0.5-1.2

Chlorite

2:1:1 Variable

Mx[Si8]Al3.2Fe0.2Mg0.6O20(OH)4

(Al(OH)2.55)4[Si6.8Al01.2}Al3.4Mg0.6)20(
OH)4

Adapted from Sposito1989. The Chemistry of Soils. Oxford University

Press.
Sesquioxide Clays (Metal Oxides and Hydrous Oxides)
Also found in finer component. These tend to form in soils as Si is
depleted by leaching.
Gibbsite is the most common Al oxide mineral and is often found in
5 | Page

highly weatherd sois such as oxisoils in tropical areas and ultisols

found predominatly in the southeastern U.S.
The most commn iron oxides are Goetihte (FeO(OH) and Hematiite
(Fe2O3) Thess are also found in highly weathered soils and gives
many red soils their color.
The metal oxides gibbsite and goethite tend to persist in the
environment because Si is readily leached than Al, or Fe and
significant amount of soluble organic
matter is present.
Manganese oxides are also quite common in soils. Apart from being
an essential plant nutrient, they are an nutrural oxidant to certain
metals such as As3+ and Cr3+. Birnessite(MnO2) is the most comon
Mn oxide found in soils.
Most of the charges developed on the metal oxides are pHdependent.

Allophanes and Imogolite

These are structurally disordered aluminosilicates.
They are normally derived from volcanic ash materials and
constitute a major component of volacnic soils.
Allophane is is often associated with clay minerals of the kaolinite
group.
Imogolite has the empirical formula SiAl4O10.5H2O.
Carbonate and Sulfate Minerals
The carboate and sulfate minerals are highly soluble compared to
6 | Page

the alumino-silicates and are more prevalent in arid and semi arid
regions.
The major carbonate minerals are calcite (CaCO 3) and Dolomite
(CaMg(CO3)2.
The major sulfate mineral is gypsum.
Use of Clay Minerals.
Clay minerals have many industrial uses in the chemical and oil
industries.
Organoclays, which have the metals in the clay replaced by large
surfactant cations, such as long chain alkyl amine cations can be
been used as liners in
landfills to reduce transport of contaminants. Organoclays also
could be used in wastewater treatment and spill control situations.
Properties

Clays form

flat

Clay minerals are

weathering
7 | Page

hexagonal

sheets

similar

common weathering products

of feldspar)

and

to

the micas.
(including

low-temperature hydrothermal

alteration products.

Clay

minerals

are

very

common

in

fine-

grained sedimentary rocks such as shale,mudstone, and siltstone and

in fine-grained metamorphic slate and phyllite.
Clay minerals are usually (but not necessarily) ultrafine-grained
(normally considered to be less than 2 micrometres in size on
standard particle size classifications) and so may require special
analytical techniques for their identification and study. These
include x-ray

diffraction, electron

diffraction methods,

various

spectroscopic methods such as Mssbauer spectroscopy, infrared

spectroscopy, Raman
mineralogy processes.

spectroscopy,
These

and

methods

SEM-EDS
can

or automated

be

augmented

by polarized light microscopy, a traditional technique establishing

fundamental occurrences or petrologic relationships.
OCCURRENCE
Given the requirement of water, clay minerals are relatively rare
in the Solar System, though occur extensively on Earth where water
has interacted with other minerals and organic matter. Clay minerals
have been detected at several locations on Mars including Echus
Chasma and Mawrth

Vallis and

the Memnonia

quadrangle and

the Elysium quadrangle. Spectrography has confirmed their presence

on Ceres and Europa.
CLASSIFICATION

8 | Page

Clay minerals can be classified as 1:1 or 2:1, this originates because

they are fundamentally built of tetrahedral silicate sheets and
octahedral hydroxide sheets, as described in the structure section
below. A 1:1 clay would consist of one tetrahedral sheet and one
octahedral sheet, and examples would be kaolinite and serpentine. A
2:1 clay consists of an octahedral sheet sandwiched between two
tetrahedral

sheets,

and

examples

are

talc,

vermiculite

and

montmorillonite.
Clay minerals include the following groups:

Kaolin group

which

includes

minerals kaolinite, dickite, halloysite,

the

and nacrite (polymorphs of

Al2Si2O5(OH)4).

Some sources include the kaolinite-serpentine group due to

structural similarities (Bailey 1980).

Smectite group which includes dioctahedral smectites such

as montmorillonite, nontronite and

beidellite

and

trioctahedral

smectites for

example saponite.

In 2013, analytical tests by the Curiosity

rover found results consistent with the presence of smectite clay

minerals on the planet Mars.

9 | Page

Illite group which includes the clay-micas. Illite is the only

common mineral.[5]

Chlorite group includes a wide variety of similar minerals with

considerable chemical variation.

Other 2:1 clay types exist such as sepiolite or attapulgite, clays

with long water channels internal to their structure.

Mixed layer clay variations exist for most of the above groups.
Ordering is described as random or regular ordering, and is further
described by the term reichweite, which is German for range or
reach. Literature articles will refer to a R1 ordered illite-smectite, for
example. This type would be ordered in an ISISIS fashion. R0 on the
other hand describes random ordering, and other advanced ordering
types are also found (R3, etc.). Mixed layer clay minerals which are
perfect R1 types often get their own names. R1 ordered chloritesmectite is known as corrensite, R1 illite-smectite is rectorite.
HISTORY

Knowledge of the nature of clay became better understood in the

1930s with advancements in x-ray diffraction technology necessary
to analyze the molecular nature of clay particles. Standardization in
terminology arose during this period as well with special attention
given to similar words that resulted in confusion such as sheet and
plane.

10 | P a g e

Structure

Like all phyllosilicates, clay minerals are characterised by twodimensional sheets of

corner

sharing

SiO4 tetrahedra

and/or

AlO4 octahedra. The sheet units have the chemical composition

(Al,Si)3O4. Each silica tetrahedron shares 3 of its vertex oxygen atoms
with other tetrahedra forming a hexagonal array in two-dimensions.
The fourth vertex is not shared with another tetrahedron and all of
the tetrahedra "point" in the same direction; i.e. all of the unshared
vertices are on the same side of the sheet.
In clays, the tetrahedral sheets are always bonded to octahedral
sheets formed from small cations, such as aluminium or magnesium,
and coordinated by six oxygen atoms. The unshared vertex from the
tetrahedral sheet also forms part of one side of the octahedral sheet,
but an additional oxygen atom is located above the gap in the
tetrahedral sheet at the center of the six tetrahedral. This oxygen
atom is bonded to a hydrogen atom forming an OH group in the clay
structure. Clays can be categorized depending on the way that
tetrahedral and octahedral sheets are packaged into layers. If there is
only one tetrahedral and one octahedral group in each layer the clay
is known as a 1:1 clay. The alternative, known as a 2:1 clay, has two
11 | P a g e

tetrahedral sheets with the unshared vertex of each sheet pointing

towards each other and forming each side of the octahedral sheet.
Bonding between the tetrahedral and octahedral sheets requires
that the tetrahedral sheet becomes corrugated or twisted, causing
ditrigonal distortion to the hexagonal array, and the octahedral sheet
is flattened. This minimizes the overall bond-valence distortions of
the crystallite.

Depending on the composition of the tetrahedral and octahedral

sheets, the layer will have no charge, or will have a net negative
charge. If the layers are charged this charge is balanced by interlayer
cations such as Na+ or K+. In each case the interlayer can also contain
water. The crystal structure is formed from a stack of layers
interspaced with the interlayers.

12 | P a g e

INFORMATION CLAY MINERALS & SOILS

Clay minerals are layer silicates that are formed usually as
products of chemical weathering of other silicate minerals at the
earth's surface. They are found most often in shales, the most
common type of sedimentary rock. In cool, dry, or temperate
climates, clay minerals are fairly stable and are an important
component of soil. Clay minerals act as "chemical sponges" which
hold water and dissolved plant nutrients weathered from other
minerals. This results from the presence of unbalanced electrical
charges on the surface of clay grains, such that some surfaces are
positively charged (and thus attract negatively charged ions), while
other surfaces are negatively charged (attract positively charged
ions). Clay minerals also have the ability to attract water molecules.
13 | P a g e

Because

this

attraction

is

surface

phenomenon,

it

is

called adsorption (which is different from absorption because the ions

and water are not attracted deep inside the clay grains). Clay
minerals resemble the micas in chemical composition, except they
are very fine grained, usually microscopic. Like the micas, clay
minerals are shaped like flakes with irregular edges and one smooth
side. There are many types of known clay minerals. Some of the more
common types and their economic uses are described here:
Kaolinite: This clay mineral is the weathering product of
feldspars. It has a white, powdery appearance. Kaolinite is named
after a locality in China called Kaolin, which invented porcelain
(known as china) using the local clay mineral. The ceramics industry
uses it extensively. Because kaolinite is electrically balanced, its
ability of adsorb ions is less than that of other clay minerals. Still,
kaolinite was

used as the main ingredient for the original formulation of the

diarrhea remedy, Kaopectate.
Illite: Resembles muscovite in mineral composition, only finergrained. It is the weathering product of feldspars and felsic silicates.
It is named after the state of Illinois, and is the dominant clay mineral
in midwestern soils.
14 | P a g e

Chlorite: This clay mineral is the weathering product of mafic

silicates and is stable in cool, dry, or temperate climates. It occurs
along with illite in midwestern soils. It is also found in some
metamorphic rocks, such as chlorite schist.
Vermiculite: This clay mineral has the ability to adsorb water,
but not repeatedly. It is used as a soil additive for retaining moisture
in potted plants, and as a protective material for shipping packages.
Smectite: This clay mineral is the weathering product of mafic
silicates, and is stable in arid, semi-arid, or temperate climates. It was
formerly known as montmorillonite. Smectite has the ability to adsorb
large amounts of water, forming a water-tight barrier. It is used
extensively in the oil drilling industry, civil and environmental
engineering (where it is known as bentonite), and the chemical
industry. There are two main varieties of smectite, described in the
following:
Sodium Smectite: This is the high-swelling form of smectite,
which can adsorb up to 18 layers of water molecules between layers
of clay. Sodium smectite is the preferred clay mineral for drilling
muds, for creating a protective clay liner for hazardous waste landfills
to

guard

against

future

groundwater

contamination,

and

preventing seepage of groundwater into residential basements.

15 | P a g e

for

Sodium smectite will retain its water-tight properties so long as

the slurry is protected from evaporation of water, which would cause
extensive mud cracks. As a drilling mud, sodium smectite mixed with
water to form a slurry which performs the following functions when
drilling an oil or water well: 1) lubricates the drill bit to prevent
premature wear, 2) prevents the walls of the drill hole from collapsing
inwards, 3) suspends the rock cuttings inside the dense mud so that
the mud may pumped out of the drill hole, and 4) when the dense
mineral barite is added to drilling mud, it prevents blowouts caused
by internal pressure encountered during deep drilling. Sodium
smectite is also used as commercial clay absorbent to soak up spills
of liquids. High-grade deposits of sodium smectite are found in South
Dakota.
Calcium smectite: The low-swelling form of smectite adsorbs
less water than does sodium smectite, and costs less. Calcium
smectite is used locally for drilling muds. Much of the domestic
supplies of calcium smectite are mined from the state of Georgia.
Attapulgite: This mineral actually resembles the amphiboles
more than it does clay minerals, but has a special property that
smectite lacks - as a drilling fluid, it stable in salt water environments.
When drilling for offshore oil, conventional drilling mud falls apart in
the presence of salt water. Attapulgite is used as a drilling mud in
these instances. Incidentally, attapulgite is the active ingredient in
the current formula of Kaopectate.
16 | P a g e

Soils
Soil is produced by the weathering of rocks at the earth's surface,
usually requiring thousands of years. Many of our present day
agricultural soils date back to the last ice age, more than 10,000
years ago. Ideally, a soil has four components, and an idealized
percentage for a "good" agricultural soil would be:
1. Mineral (45%)
2. Organic matter (5%)
3. Water (25%)
4. Air (25% void space)
Within the mineral fraction, soils are usually divided into three size
fractions: sand, silt, and clay. An ideal balance between a soil that is
100% sand ("too loose") vs. 100% clay ("too tight") has a roughly
equal sand:silt:clay ratio, and this type of soil is termed a "loam."
(The term "soil" as used in engineering refers to "any unconsolidated
material" and
definition.)

does

not

necessarily

match

the

geologist's

Organic matter comes from products of soil microbes

which promote the decay of dead plants and animals. One of these
organic materials is known as humus, which mimics the adsorptive
properties of clay minerals. Organic matter is generally dark in color,
17 | P a g e

and a layer of topsoil rich in organic matter is said to be the "O"

Horizon.
Tropical Weathering Breaks Down Clay Minerals
In humid tropical climates, clay minerals are unstable and break
down under intense chemical weathering to become hydrated
oxides of aluminum (bauxite) and

iron (goethite), which are very poor substitutes for clay minerals in
retaining soil nutrients. As a result, jungle soil relies on the presence
of humus, an organic substance produced by microbes that cause
dead plants to decay; humus mimics the ability of clay minerals to
retain soil moisture and nutrients. However, humus is much more
fragile than clay minerals to chemical weathering, and is protected by
the tall rainforest canopy, which softens the torrential rainfall into a
gentle sprinkle. When rain forest trees are cut down, the humus is
quickly washed away, leaving a barren landscape that bakes to a
hard, brick-like consistency under the tropical sun. This "soil" is
virtually useless for western style agriculture, and cannot be
converted into useful farmland due to the lack of clay minerals. Even
adding chemical fertilizers is useless - the soil cannot absorb it, and it
runs off the land and pollutes the rivers.
Why There Is High Biological Diversity In Tropical Rain
Forests
18 | P a g e

It is important to note that the apparent abundance of greenery

in the tropics is deceiving - there is no abundance of any single
species; instead there is an abundance of different species. This is
known asbiological diversity. Biological diversity may be likened
to nature's efficiency plan - it allows a limited resource (soil nutrients)
to be shared by a large number of different plants with different diets.
The warm, mild climate of tropical rain forests has the highest species
diversity

in

the

world.

It

is

from

this

diversity

that

most

pharmaceutical herbs and drugs are obtained.

How Fertile Soils Facilitate Mono-Crop Agriculture

Since ancient times, farmers have noticed that growing the same
crop year after produced sucessively poorer harvests. This is caused
by the removal of nutrients from the soil by that same crop. By
alternating a different crop each season, the soil is less depleted of
nutrients than by growing the same crop every year.. Despite the
soundness of crop rotation, for the sake of efficiency, modern U.S.
agriculture practices mono-crop agriculture, where field upon field
of the same crop (corn, wheat, soybeans, etc.) is grown year after
year. This is only possible because of the rich agricultural soil of the
American midwest, which contains abundant clay minerals, and has
19 | P a g e

an optimum soil consistency. Still, mono-crop agriculture would not be

possible without the intensive use of chemical fertilizers to replenish
an already rich soil. A side-effect of mono-crop agriculture is that it
encourages the establishment of agricultural pests. Insects which
feed on a particular crop will return in greater force with a steady
annual supply of food. Consequently, chemical pesticides and pestresistant seeds are also required to support mono-crop agriculture.

DEFINITION OF CLAY MINERALS

Definition: Clay minerals are the characteristic minerals of the
earths near surface environments. They form in soils and sediments,
and by diagenetic and hydrothermal alteration of rocks. Water is
essential for clay mineral formation and most clay minerals are
described as hydrous alumino silicates.

Structurally, the clay

minerals are composed of planes of cations, arranged in sheets,

which may be tetrahedrally or octahedrally coordinated (with
oxygen), which in turn are arranged into layers often described as 2:1
20 | P a g e

if they involve units composed of two tetrahedral and one octahedral

sheet or 1:1 if they involve units of alternating tetrahedral and
octahedral sheets.

Additionally some 2:1 clay minerals have

interlayers sites between successive 2:1 units which may be occupied

by interlayer cations, which are often hydrated. The planar structure
of clay minerals give rise to characteristic platy habit of many and to
perfect cleavage, as seen for example in larger hand specimens of
micas.
The classification of the phyllosilicate clay minerals is based
collectively, on the features of layer type (1:1 or 2:1), the
dioctahedral or trioctahedral character of the octahedral sheets (i.e. 2
out of 3 or 3 out of 3 sites occupied), the magnitude of any net
negative layer charge due to atomic substitutions, and the nature of
the interlayer material.
The basis on which clay minerals are classified is shown below;
see Hillier (2003) for a more detailed introduction to clay mineralogy.

LAYER
TYPE
1:1

21 | P a g e

Layer charge
(q)
q0

Group

Subgroup Species
(e.g.)
KaolinKaolin
Kaolinite
Serpentine Serpentine Berthierine

2:1

Variable

q0
q1

Increasi Pyrophyllite Pyrophyllite Pyrophyllite

ng layer -talc
Talc
Talc
charge Smectite
Di-smectite Montmorillonit
(q0.2-0.6)
e
Tri-smectite Saponite
Vermiculite DiDi-vermiculite
(q0.6-0.9) vermiculite
TriTri-vermiculite
vermiculite
Mica
Di-mica
Illite,
(q1.0)
Muscovite
Tri-mica
Biotite
q variable
Chlorite
Di-chlorite Sudoite
Tri-chlorite Chamosite
SepioliteSepiolite
Sepiolite
Palygorskite Palygorskite Palygorskite
q variable
Mixed-layer Di-mica-di- Rectorite
smectite
Tri-chlorite- Corrensite
tri-smectite

The buttons only work when the model has been activated

22 | P a g e

Analyses: Some types of clay minerals such as mixed-layered clay

minerals can only be identified precisely by techniques such as XRD.
Although it is not unusual to have to use a variety of techniques such
asXRD, infrared

spectroscopy,

and electron

microscopy to

characterise and more fully understand types of clay minerals

present in a sample.

We have extensive experience of the

identification of clay minerals in both soils and rocks. Our XRD work
is based is backed up by our ability to compare clay mineral
diffraction data with calculated diffraction data. This is a particularly
important technique for the precise identification of mixed-layer clay
minerals.

Our track record in the Reynolds Cup round robin on

quantitative clay mineral analysis is testimony to the quality of our

work on the identification and quantification of clay minerals. We also
have wide experience of the use of electron microscopy to study the
texture and petrographic relationships of clay minerals.

23 | P a g e

You can get a 3-dimensional model of the structure that you can
manipulate. It uses the Jmol applet. This may take quite a time to
download if you do not already have it in cache.

HISTORY
Clay has been used in bricks and pottery for millennia.
Sundried bricks were used from possibly over 10,000 years ago and
kiln-fired bricks were used in the construction of a temple in the
Euphrates region, considered to be more than 5000 years old.
Sumerian and Babylonian builders constructed ziggurats, palaces,
and city walls of sun-dried bricks and covered them with more
durable kiln-baked bricks, often brilliantly glazed and arranged in
decorative pictorial friezes. The earliest form of pottery was
earthenware (porous and coarse), which has been made for at least
9000 years. The earliest pottery yet discovered in the Middle East
comes from atal Hyk, in Anatolia (near modern umra, Turkey),
24 | P a g e

and dates from 8500 years ago. Stoneware, a vitrified or glassy

product, dates to the Shang dynasty in China around 3400 years ago.
The oldest porcelain, a vitrified ware that rings when tapped and is
usually translucent, originated in China during the Tang dynasty
(618-907 AD), but the porcelain best known in the West (where it is
called chinaware) was not produced until the Yuan dynasty (12781368 AD). This hard-paste porcelain was made from petuntse, or
china stone (a crushed kaolinised granite consisting of a mixture of
kaolinite, sericite, feldspar and quartz), ground to powder and mixed
with kaolin, and fired at a temperature of about 1450oC. Porcelain
imported from China was considered a great luxury in Europe and
attempts to imitate it led to the discovery in Florence during 1575 of
soft-paste porcelain (or frit porcelain), a mixture of clay and ground
glass fired at about 1200o C. The secret of hard-paste porcelain was
discovered in about 1707 at the Meissen factory in Saxony (Germany)
by Johann Bttger and Ehrenfried von Tschirnaus. English bone china
was first produced around 1800, when Josiah

Spode added calcined bones to the hardpaste porcelain formula. The

use of clays (probably smectite) as soaps and absorbents was
reported in Natural History by the Roman author Pliny the Elder (c. AD
77). The use of a kaolin-bearing surface on paper began in China
about 400 AD when powdered kaolin was added to the pigment of
paper coating. In New Zealand, brickmaking and pottery were among
25 | P a g e

the first established industries. Small brick works were established in

many parts of New Zealand. There were 37 in 1867, but the total
number expanded to 127 by 1880. Most of these works ceased
production after WWII, when road transport improved. In addition to
bricks and clay pipes, many of the brick works produced a limited
range of domestic pottery and tableware, for example Amalgamated
Brick and Pipe eventually had a Specials Department for pottery
manufacture, which was later formed into a subsidiary company,
Crown Lynn Potteries (1948-1989) (Bathurst, 1999). These companies
were the original producers of the legendary railway cups. Other
major pottery manufacturers were based in Christchurch, Milton and
Temuka, of which the factory in Temuka is the only survivor. Studio
pottery was established from the 1960s in Nelson (e.g. Crewenna and
Waimea) and Coromandel (Driving Creek), and has developed into a
large number of small operations, reviewed by Grzelewski (1999).

ORIGIN OF NAMES
Attapulgite (palygorskite) is for Attapulgus, Georgia, USA.
Ball clay is from the tradition of extracting clay by cuffing it into 126 | P a g e

cubic-foot blocks, which became rounded to form balls while rolling

the clay to the cart. The resulting ball had a diameter of about 25 cm
and weighed 13-22 kg. Bentonite is named after the Benton Shale
Formation in Wyoming, USA, in which the first bentonite mine in 1897
was located. The Benton Shale drew its name from Fort Benton,
Montana, USA. Ceramic is from the Greek keramos for potters clay.
China clay is a commercial term for kaolin, and was derived from its
origin in China. Clay is derived from Latin and Old English words
meaning to stick. Fullers earth originated from the practice of
textile workers (or fullers) who cleaned raw wool by kneading it in a
clay-water mixture that adsorbed oil, dirt, and other contaminants
from the fibres. Halloysite was named after Baron Omalius dHalloy
(1707-1789), a Belgian geologist who first noted the mineral.
Hectorite is named after Hector, California, USA. Illite is for the State
of Illinois, USA. Kaolinite is named after kaolin, from the Chinese Kauling (or Gaoling), for a high ridge near the town of Jingdezhen in
northwest Jiang Xi Province, China, where deposits of white kaolin
were probably first worked over 2200 years ago. Meerschaum is from
the German for sea-froth, which it resembles, because its low density
allows the mineral to float on water. Montmorillonite was named in
1897 after Montmorillon, Vienne, France. Natronite for the locality in
the Arrondissement of Norton, near the village of Saint Paradoux,
France. Palygorskite is from Palygorskaja, Urals, Russia. Porcelain is
from porcellana, used by Marco Polo to describe the pottery he saw in

27 | P a g e

China. Pyrophyllite is from the Greek pyr meaning fire and phyllite, a
rock or stone.

Saponite is from the Latin sapo (-idos) = soap for its soaplike
appearance. Sepiolite is from the Greek sepion = bone of the cuttlefish, which is light and porous, similar to the clay mineral, and the
Greek lithos for stone. Vermiculite is from the Latin word meaning to
breed worms, alluding to the worm-like shape resulting from its
expansion on heating.

28 | P a g e

CLASSIFICATION AND PROPERTIES

Clay structure an important factor contributing to the
properties of the different clay minerals is their molecular structure.
Most clay minerals are based on two types of structure, the silica
tetrahedral sheet and the alumina-magnesia octahedral sheet. Silica
tetrahedral sheets are each about 4.7 thick, consist of silica
tetrahedra arranged in a plane and have a composition of Si4 O6
(OH)4 . The sheets are bound together by aluminium and/or
magnesium. Alumina-magnesia octahedral sheets are each about
5.05 thick, consist of octahedra arranged in a plane, and have
compositions of either A12(OH)6 (gibbsite) or Mg3(OH)6 (brucite),
depending on whether aluminium or magnesium are incorporated in
the structure. The tetrahedral and octahedral structural units can be
joined or stacked in several configurations of composite layers,
producing various hydrated aluminosilicates that form layer-lattice
minerals with a plate-like shape (e.g. kaolinite, smectite, illite and
vermiculite) or chain-lattice minerals with an elongate shape (e.g.
palygorskite and sepiolite). The layerlattice structures are grouped as
1:1 layer structures containing one tetrahedral sheet linked with one
29 | P a g e

octahedral sheet, and 2:1 layer structures with two tetrahedral sheets
linked with one octahedral sheet. Less common clay minerals are
either amorphous (non-crystalline; allophane) or have a structure
based on double tetrahedral chains similar to that of amphibole
minerals.

CLAY MINERALS
Clay minerals may be classified into eight main groups on the
basis of variations in structure and composition: (1) kaolinite, (2)
smectite, (3) vermiculite, (4) illite, (5) pyrophyllite, (6) chlorite, (7)
palygorskite, and (8) allophane (Table 1). Some clay minerals are
intermediate between the clay mineral groups, formed by mixtures of
the different clay structural layers, resulting in mixed-layer clay
minerals

such

as

interlayered

illite-smectite

and

interlayered

chloritekaolinite. The clay minerals are very similar in physical

properties (Table 2), and many can be distinguished only by X-ray
diffraction, infrared spectroscopy, electron microscopy, or differential
thermal analysis. Kaolinite group includes the minerals kaolinite,
halloysite, dickite and nacrite, which are all dioctahedral 1:1 layer
silicates. Kaolinite is by far the most common mineral of the group.
Halloysite is much less common, and dickite and nacrite are
30 | P a g e

comparatively rare. All of these minerals have essentially the same

composition, apart from a hydrated form of halloysite, which differs
from the more common metahalloysite by having an extra two water
molecules per unit cell. On heating to 100oC, hydrated halloysite
dehydrates to metahalloysite irreversibly. Halloysite crystallises as
elongated tubular or, in some cases, spheroidal shapes, whereas the
other kaolinite group minerals form pseudohexagonal platelets or
stacks of platelets. Kaolinite group minerals are the principle
constituents of kaolin. Smectite group clays have a 2:1 sheet
structure and include the dioctahedral minerals smectite (also known
as montmorillonite), beidellite and nontronite, and the trioctahedral
minerals hectorite (Li-Mg-smectite) and saponite (Mg-smectite; also
known as bowlingite and soapstone). These are expanding lattice
clays that swell in water, are thixotropic and possess high cation-

exchange capacities. Smectites are the principal constituents of

bentonite and fullers earth. Vermiculite is similar to smectite in
structure and, in some cases, composition. When heated rapidly
above 400o C, interlaminar water turns to steam and causes the
mineral layers to exfoliate or separate into worm-like pieces. The
increase in bulk volume is typically 8-20 times in commercial grades,
but individual flakes can expand by as much as 30 times. Its specific
gravity may be reduced to as low as 0.09.

31 | P a g e

Illite group clays have a dioctahedral 2:1 mica-like sheet

structure, but differ from true mica by having more water and fewer
inter-layer cations (mostly potassium), resulting in weak forces
between

layers

and

irregularity

of

stacking.

Illite

clays

are

intermediate in composition and structure between muscovite and

smectite. Palygorskite group (also known as palygorskite-sepiolite
group; formerly hormite group) includes the minerals, palygorskite,
also known as attapulgite, and sepiolite, also known as meerschaum.
These minerals have a chain-like structure and form fibrous, lath- or
needle-like

crystals.

The

structure

incorporates

channels

of

approximately 6 and features a high surface area (sepiolite has the

highest surface area of all the clay minerals), porosity, surface charge
and cation exchange capacities, resulting in excellent sorptive,
colloidal and thixotropic (gelling) properties in water. Amorphous
clays are formless to X-ray diffraction because of their fine grain size
or irregularity in the arrangement of their layers. Allophane is a
hydrous aluminosilicate (SiO2 )1- 2Al2 O3 (H2 O)+ 2.5-3.0 gel,
formed from volcanic glass, but transforms to halloysite with time. It
consists of hollow, irregular spherical particles with diameters of 35 to
50. The walls of the spheres are 7 to 10 thick and contain openings
that permit the passage of water molecules

(Wada and Wada, 1977). The space within the walls is filled with
water (10% by weight) which is strongly retained.
32 | P a g e

Clay rocks
Clay rocks are classified and named on the basis of their
dominant constituent clay mineral (e.g. palygorskite, smectite, as
listed above) or other names based on their use (as listed below).
Kaolin, also called China clay, is principally kaolinite, with lesser
quantities of illite, smectite, quartz, feldspar, muscovite and other
non-kaolinite minerals, and has a low total iron content. It is a soft
white clay of variable but usually low plasticity and dry strength, that
retains its white colour when fired. Ball clay, flint clay and refractory
clay (also known as fire clay) are varieties of kaolin. Ball clay has high
plasticity and strength, but inferior whiteness compared with kaolin.
Flint clay is a compact microcrystalline to crystalline clay that breaks
with a pronounced conchoidal or flinty fracture, resists slaking, and
has almost no plasticity. Refractory clay has a high temperature
fusion point, typically above 1425o C. It is non-white burning.
Generally the higher the level of alumina, the more refractory the
clay. In some instances, this level can be enhanced to as much as
60% by the addition of bauxite minerals such as gibbsite, diaspore, or
pure alumina. Chamotte is a refractory clay formed by calcining clay
such as kaolin, flint clay or fireclay. Bentonite is a clay consisting
predominantly

of

smectite

(montmorillonite)

minerals.

It

is

characterised by exchangeable Na+, Ca2+ or Mg2+ cations which

greatly influence the properties of the clay (and therefore its
commercial applications). There are two types of naturally occurring
bentonite: a swelling bentonite which has a high sodium-to-calcium
33 | P a g e

ratio (sodium bentonite or Wyoming bentonite) and is typically

associated

with marine sediments, and a non-swelling bentonite with a low

sodium to calcium ratio (calcium bentonite) that is typically
associated with freshwater sediments. The swelling variety has the
ability to absorb water and swell many times its original volume to
form gel-like masses. Calcium bentonite can be converted to a
sodium-type (termed sodium exchange bentonite) by treatment with
soda ash to improve swelling capacity. It can also be used to produce
acid-activated bentonite by treatment with inorganic acids to replace
divalent calcium ions with monovalent hydrogen ions and to leach out
ferric, ferrous, aluminium and magnesium ions, thus altering the
crystal structure, and increasing the specific surface area and
porosity. Fullers earth is a group of clays that have a substantial
ability to adsorb impurities or colouring bodies from fats, grease, or
oils. In the United Kingdom, the term was introduced for clay in which
the principal clay mineral is calcium smectite, but other minerals
such as kaolinite, palygorskite and sepiolite may also be present and
account for its variable chemical composition. In the USA, clays that
are termed fullers earth are predominantly palygorskite or sepiolite.
Fullers earth is fine-grained, found in a wide range of natural colours,
from brown or green to yellow and white, and has a high water

34 | P a g e

content. It crumbles into mud when mixed with water, so it has little
natural plasticity.

FORMATION
Formation process Clay minerals are formed by the processes
of weathering, diagenesis and hydrothermal alteration (Table 3).
Weathering and soils Soils and other residual clay deposits are
formed by in situ weathering. Controlling factors include the nature of
the parent rock, climate, topography, vegetation, and the time period
during

which

these

factors

operated.

Different

environments,

particularly different climatic and hydrologic regimes, may produce

different clay minerals from the same parent rock type. Large
kaolinite deposits formed by weathering are common around the
world. Commercially exploited resources occur in the United States,
Brazil, Guyana, Surinam, Ghana, Australia, and Europe. Clays in
sediments

Clay

minerals

occur

widely

in

sedimentary

rocks,

particularly those with fine particle size such as mudstones and

shales (argillaceous or clay-rich rocks). Illite and smectite, including
mixed-layer clay minerals, kaolinite and chlorite are the principal clay
35 | P a g e

mineral components of recent deep-sea sediments. Smectite and

kaolinite are less abundant in pre-Devonian argillaceous sediments,
which are composed largely of illite and chlorite. Kaolinite and illite
are found in some coal measures. Most ball clays are Eocene to Lower
Oligocene in age and formed in swampy sedimentary environments
under subtropical to tropical conditions, assisted by post-depositional
diagenesis and the presence of organic components. Palygorskite and
sepiolite clay deposits are mostly associated with mid-Tertiary or
younger shallow lagoonal sediments formed in sub-tropical to tropical
environments.

DIAGENESIS
As temperature and pressure increase with the progression of
diagenesis, clay minerals in sediments change to those stable under
given conditions. Therefore, certain sensitive clay minerals may serve
as indicators for various stages of diagenesis. Typical examples are
the crystallinity of illite, the polytypes of illite and chlorite, and the
conversion of smectite to illite. With deeper and longer burial, ball
clay becomes lithified to form fireclay. Fireclay is a sedimentary clay
found in coal measures as underclays, situated immediately
beneath a coal seam. Coal measures may consist of alternating
sequences of coal and clay. Whereas ball clays are associated with
36 | P a g e

lignite, fireclays are usually associated with higher rank coals,

reflecting the greater lithification of their formation. Flint clay is
typically sedimentary kaolin that has been subject to prolonged
leaching and recrystallisation (e.g. most USA examples; Missouri,
Kentucky) or metamorphism (e.g. some European flint clays).

HYDROTHERMAL ALTERATION
Clay minerals are formed as alteration products associated with
geothermal

areas

and

hot

springs,

and

as

aureoles

around

hydrothermal ore deposits. There is typically a zonal arrangement of

the clay minerals around the source of the alteration as a result of
decreasing temperature and changes in fluid composition along the
fluid flow and reaction path. The zonal arrangement varies with the
type of parent rock and the nature of the hydrothermal fluid. For
37 | P a g e

example, in epithermal ore deposits, near-neutral hydrothermal fluids

alter rocks to illite, chlorite, and smectite, whereas acid hydrothermal
fluids result in the formation of kaolinite, dickite and pyrophyllite.
Furthermore, there is typically a temperature dependent zonation of
illite, interlayered illite/ smectite and smectite with decreasing
temperature in many epithermal/geothermal systems. Pyrophyllite is
mainly found associated with hydrothermally altered volcanic rocks,
particularly in Japan and Korea. Bentonite deposits typically originate
through the hydrothermal alteration and/or weathering of tuffaceous
material rich in volcanic glass, particularly ash falls, which provide the
open macro-structure (high-surface area) necessary for efficient
devitrification. This includes the alteration of volcanic ash deposited
in lacustrine environments, alteration by groundwater of deeply
buried tuffs, the surface weathering of tuffs, and hydrothermal
alteration, either at depth or in hot springs.

USES
Commercially, the most important clays are kaolin (mainly
kaolinite) and bentonite (smectite), with palygorskite, sepiolite, and
vermiculite constituting small, more specialised markets (Table 3).
Illite, the most abundant clay mineral in nature, is unimportant
38 | P a g e

commercially as an individual mineral, but it is a prime constituent of

common clay and shale.
CERAMICS AND BRICKS
Whiteware ceramics may be classified as: porcelain, including
hard porcelain, soft porcelain, vitreous china (largely used for making
tableware) and technical porcelain (such as electrical or insulator
porcelain, and high alumina porcelain); stoneware (e.g. rustic
tableware and art ware); and earthenware. Kaolin is used extensively
in the ceramics industry, because of its high fusion temperature and
white burning characteristics. Kaolin intended for firing as a ceramic
must have a high Al2 O3 content as well as low content of fluxing (K2
O, Na2 O) and colouring (Fe2 O3, FeO, TiO2 ) agents. In the
manufacture

of

whiteware,

the

kaolin

is

usually

mixed

with

approximately equal amounts of silica, feldspar and talc, and a

somewhat smaller amount of ball clay to obtain the proper properties
of plasticity, shrinkage and vitrification, for forming and firing the
ware. Premium-grade halloysite may be utilised to add whiteness and
translucency to porcelain and bone china, and for strength in
technical

ceramics

and

ceramic

catalyst

support

bodies.

The

composition of ceramic pipes is similar to whiteware, but contains

more silica, fluxes and colouring agents. Potters clay is less pure
than pipe clay and sculptors clay or modelling clay consists of a fine
potters clay, sometimes mixed

39 | P a g e

with fine sand. Bricks are made from an admixture of clay and sand
with some ferruginous (iron-containing) matter. The main clay
minerals used in brickmaking are kaolin and illite. Kaolin type clays
are also used in the manufacture of refractory products such as
firebricks and blocks, insulating bricks, refractory mortars and mixes,
and monolithic and castable materials. Refractory clays have little or
no lime, alkaline earth or iron (which act as fluxes), and are therefore
infusible or highly refractory. Plastic clays, like kaolin and ball clay,
are not so refractory as are the flinty, harder varieties, but are useful
for bonding. Where flint clays are scarce, plastic kaolin may be
calcined to form a hard, dense, refractory aggregate known as
chamotte or refractory grog.
WORLD PRODUCTION AND CONSUMPTION
World-wide kaolin production capacity is more than 27 Mtpa
from more than 50 countries. More than half of this total is relatively
low-cost unprocessed common clay used in lightweight aggregate,
cement, brick, civil engineering, sealing, and refractories. The
remainder is the various forms of processed industrial grade kaolin,
including ball clay and refractory clay. Production of commercial
grade ball clay is concentrated in the south-central United States
(Tennessee, Kentucky and northern Mississippi; 1 Mt), the UK (Devon
and Cornwall; 0.8 Mt), Germany (the Westerwald; 2 Mt) and the Czech
Republic (Cheb basin), although many other countries produce plastic
clays of lower quality including France (Provins and Charente),
Portugal, Thailand, China (Pearl River Delta), and Ukraine. Refractory
40 | P a g e

clays are produced in virtually every industrialised country, although

there are four main areas of production, namely the USA, Europe,
China and South Africa. Flint-clay production is restricted largely to
the United States,

France,

South

Africa,

Australia,

Hungary,

Commonwealth

of

Independent States, and China. The commercial development of high

purity halloysite resources is restricted to New Zealand, Korea and
Japan. Lower grade resources are exploited in Japan, USA and, to a
smaller extent, the Czech Republic, France, the Philippines and
Morocco. About half of the worlds bentonite production is from the
USA mainly in Upper Cretaceous and Tertiary rocks.
MINING AND PROCESSING
Clays are generally mined by highly selective open pit
methods using hydraulic excavators, front-end loaders, or draglines.
The clay is processed using either a dry (air flotation) or a wet
process (water washing). The wet process produces a higher cost and
higher quality product than the dry process. The dry process involves
crushing, drying, pulverising, and air flotation, to remove the grit
particles (mostly quartz and feldspar). In the wet process, the first
step is to remove the non-clay minerals, usually by extracting the grit
from a clay slurry in drag boxes, classifiers, and/or hydrocyclones.
The clay slurry is centrifuged and then thickened to about 30% solids
in settling tanks. Further processing may involve ultraflotation and
41 | P a g e

screening/filtering. In some cases flotation or high-intensity magnetic

separation is used to remove iron and titanium impurities. Bentonite
may be further processed or treated. For example, swelling sodium
bentonite, may be produced by treating calcium montmorillonite, the
nonswelling bentonite, with soda ash. Acid-activated smectite is
manufactured through the reaction of inorganic acids with smectite.
The physical effects of acid activation include opening up the edges
of the platelets, increasing pore diameters, and enlarging surface
area. Also some bentonite and kaolinite are surface coated with
organic compounds to make organoclays.
HYDROTHERMAL
alteration Halloysitic and kaolinitic clays produced by
hydrothermal alteration are found in Northland, Coromandel and the
Taupo Volcanic Zone. Halloysite clay, reputed to be the worlds
whitest clay, is produced from deposits at Matauri Bay, Northland, by
NZ China Clays Limited (Townsend, 1989; Harvey et al., 1990; Harvey
and Murray, 1993; Luke, 1997). Two pits are worked on the Matauri
Bay and Mahimahi rhyolite domes respectively, located 2 km apart
(Figs 2 and 3). NZ China Clays Limited also has deposits at Shepherds
Hill, 6.5 km to the west of Matauri Bay, and Maungaparerua, 8 km
west of Kerikeri. The clay is formed by hydrothermal alteration and
subtropical weathering of Pliocene to Pleistocene rhyolite domes
(Putahi Rhyolite) to material comprising approximately 50% clay and
50% quartz, cristobalite and minor feldspar. The clay is predominantly
42 | P a g e

halloysite, but at Maungaparerua, Murray et al. (1977) also noted

allophane and kaolinite. The degree of clay development is generally
greatest at the surface, because of the effects of surficial weathering
superimposed on the hydrothermal alteration. The presence of basalt
flows partly overlying the domes may have been an important factor
in the alteration process. Several other rhyolite domes are present in
Northland, but most do not show extensive development of halloysitic
clays (Bowen, 1974). Matauri Bay clay deposit is derived from the
alteration of a small (about 29 ha in area) rhyolite dome of low relief.
It is completely surrounded and partly onlapped by thick (up to 60 m)
flows of basalt. The raw clay is generally covered by 1 to 3 m of ironstained material, which is removed together with soil and vegetation,
before mining. The deposit is mined

selectively by hydraulic excavators, and the material is transported

by motor scrapers to stockpiles on concrete pads.

43 | P a g e

44 | P a g e

The
Northland
halloysite
deposits
have

been

worked
since 1969.
About
80,000 tpa
of raw clay
is
from

mined
the

Matauri Bay and Mahimahi deposits with 50% of plant feed from
each. Plant capacity is about 25,000 tpa of processed halloysite, with
clay products being exported to more than 20 countries. Sufficient
resources exist at the Matauri Bay and nearby Mahimahi deposits to
sustain production for over 30 years at current rates. Potential
resources are present in other deposits at Shepherds Hill and at
Maungaparerua. In addition to the halloysite deposits of Matauri Bay
and Maungaparerua, kaolin and halloysite deposits formed by
alteration and weathering of volcanic rocks are widespread in
Northland, but are generally of small extent. They include deposits of
weathered and altered Pukekaroro Rhyodacite, Maungarei Dacite and
Putahi Rhyolite.

45 | P a g e

Kaolin deposits have been recorded from Kaeo (Te Pene; Quennell,
1963, 1964), Kauri (Parekiore), Whangarei Heads (Parua Bay and
Ocean Beach), McLeods Bay (Munroe Bay) and Kaiwaka. All are white
clays of low plasticity and approach the clay minerals kaolin and
halloysite in composition. Some are of excellent quality, having low
iron and alkali (Na2O + K2O) content and have been used in the
manufacture of china ware or porcelain ware, and in the case of Kauri
pit,

for

the

manufacture

of

refractory

bricks

(Kamo

Green

Refractories). Bowen (1966, 1974) has given resource estimates for

some of these deposits, based on geological mapping and limited
drilling. Thompson (1989) summarised the result of exploration at
Ocean Beach and Kaiwaka. At Mount Mitchell, potters clay or potters
earth has been recorded from a highly siliceous hot spring deposit.

46 | P a g e