Clay Mineralogy “G 421”

Kaolinite

Prepared And Compiled

by
Dr. Hana Salem
Cairo University
 Clay Mineralogy

Objectives:
❖ The aim of this course is to study the basic mineralogy and
classification; physical and chemical properties (including aqueous
solubility and ion exchange); X-ray powder diffraction methods for
the identification and quantification of clay mineral assemblages;
formation of clay minerals and geologic origin.

❖ By the end of the course the students will gain the basic knowledge
needed as well as will be taught the scientific way of thinking to be
able to identify and characterize the main types of clay minerals
and their role in oil-gas industry.

Dr. Hana Salem

Learning Outcomes:

❖ Students are able to identify major silicate clay minerals.

❖ Students are able to differentiate clay minerals by using

different techniques such as XRD, SEM …etc.

❖ Students are able to determine the type of clays to be used

in oil and building industry.

Dr. Hana Salem

COURSE CONTENTS:
1- INTRODUCTION TO CLAY MINERALOGY
Clay, identity of clay minerals, occurrence of clay
2- STRUCTURE AND COMPOSITION OF THE CLAY MINERALS:
Types of clay minerals; Fundamental building units; Clay mineral Classification.
3- PHYSICAL AND GEOCHEMICAL PROPERTIES OF CLAYS AND CLAY MINERALS:
The main properties of particular clay minerals; The Geochemistry of clay minerals;
Measurement of Cation Exchange Capacity; Swelling properties of smectite.
4- METHODS OF CLAY MINERALS INVESTIGATION:
Identification of clay minerals by XRD; IR; SEM; TEM.
5- FORMATION AND ALTERATION OF CLAY MATERIALS:
The clay cycle; Geological origin of clay minerals
6- THE IMPORTANCE OF CLAYS IN INDUSTRY:

Dr. Hana Salem

INTRODUCTION

Dr. Hana Salem

INTRODUCTION

WHAT IS A CLAY?
❖ In geology and soil classification, the term clay includes all particles that
are <2 µm irrespective of their mineralogy

❖ In mineralogy and soil chemistry, clay minerals are layered structures

and they were called phyllosilicates.

❖ 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.

Dr. Hana Salem

WHAT IS A 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
when dried or fired.

Clay and sand both indicate a

specific grain size; however, it is
often used to refer to a specific
mineralogical composition of
sediments, Fig.1.
Figure 1. shows the classification of siliciclastic sediments (unconsolidated, loose)
that are based on average grain size.
Dr. Hana Salem
PHYSICAL AND CHEMICAL PROPERTIES OF CLAYS
Clay minerals refers to a group of hydrous
aluminosilicates that predominate the clay-sized (<2
µm) fraction of soils.

These minerals are similar in chemical and structural

composition to the primary minerals that originate
from the Earth's crust; however, transformations in
the geometric arrangement of atoms and ions within
their structures occur due to weathering, thus
forming secondary minerals.

Dr. Hana Salem

PHYSICAL AND CHEMICAL PROPERTIES OF CLAYS

The resultant secondary minerals are the result of either

alteration of the primary mineral structure (incongruent
reaction) or neoformation through precipitation or
recrystallization of dissolved constituents into a more
stable structure (congruent reaction).

These secondary minerals are often referred to as

phyllosilicates because, as the name implies (Greek:
phyllon, leaf), they exhibit a platy or flaky habit, while one
of their fundamental structural units is an extended sheet
of SiO4 tetrahedra.

Dr. Hana Salem

 OCCURRENCES OF CLAY:
• Clay minerals are an important group of minerals
because they are among the most common
products of chemical weathering, and thus are
the main constituents of the fine-grained
sedimentary rocks called mudrocks (including
mudstones, claystones, and shales).
• Understanding of clay minerals is also important
as the main constituents of soils and from am
engineering point of view, as some minerals
expand significantly when exposed to water.
• Clay minerals are used extensively in the ceramics
industry and are thus important economic
minerals

Dr. Hana Salem

OCCURRENCES OF CLAY:

Sedimentary rocks only make up 5% of the

Earth's crust but cover about 80% of the
surface of the earth in which clays
(including shales) form well over 40% of
the sedimentary rocks.

The raw material for sedimentary rocks

comes from weathering.

The volume of material at the earth's surface

Dr. Hana Salem

 PHYSICAL AND CHEMICAL PROPERTIES OF CLAYS

• Clay minerals are composed of

layers. Water and cations (positive-
charged ions) can be stored between
these layers.
• This schematic shows the atomic
structure of the smallest units that
make up the layers and interlayer
region of clay minerals.

Dr. Hana Salem

PHYSICAL AND CHEMICAL PROPERTIES OF CLAYS
The characterististics common to all clay minerals
derive from their chemical composition, layered
structure, and size.

In cool, dry, or temperature climates, clay minerals

are fairly stable and are an important component of
soil.

Clay minerals have a great ability to attract water

molecules. Because this attraction is a surface
phenomenon, it is called adsorption (which is
different from absorption because the ions and
water are not attracted deep inside the clay grains).

Dr. Hana Salem

 PHYSICAL AND CHEMICAL PROPERTIES OF CLAYS

• Clay minerals, which have micropore to mesopore structures

and large surface areas, are the main components of soil,
shale, coal, and conventional reservoir rock.
• 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.
• Water, as a natural solvent or as a transport medium for
chemical species, is considered ubiquitous in clay minerals.
• Water–clay interaction plays a dominant role in the
phenomena of adsorption, dissolution, precipitation,
diffusion, and growth in clay minerals.

Absorbed and Adsorbed Water in Clay-Water System

Dr. Hana Salem

What is the main difference between
adsorption and absorption?

Absorption is the process in which a

fluid is dissolved by a liquid or a solid
(absorbent). Adsorption is the process in
which atoms, ions or molecules from a
substance (it could be gas, liquid or
dissolved solid) adhere to a surface of
the adsorbent

Dr. Hana Salem

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, in which some surfaces are
positively charged (and thus attract
negatively charged ions), while other
surfaces are negatively charged (attract
positively charged ions).

Dr. Hana Salem

Clay minerals resemble the micas in
chemical composition, except they are
very fine grained, usually under
microscope. Like the micas, clay
minerals are shaped like flakes with
irregular edges and one smooth side.
“Hydrous Micas (Illites)

Dr. Hana Salem

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, e.g. a 10 Å
thick clay mineral can expand to 19.5
Å in water.

Dr. Hana Salem

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.
Dr. Hana Salem
Clay minerals form an important group of
the phyllosilicates or sheet silicate family of
minerals, which are distinguished by
layered structures composed of polymeric
sheets of SiO4 tetrahedral linked to sheets
of (Al, Mg, Fe)(O,OH)6 octahedral.

The geochemical importance of clay

minerals stems from their ubiquity in soils
and sediments, high specific surface area,
and ion exchange capacities.

Dr. Hana Salem

Cation Exchange Capacity (CEC) and the effect of pH

Dr. Hana Salem

Cation Exchange Capacity (CEC) and the effect of pH

Dr. Hana Salem

Clay minerals tend to dominate the surface
chemistry of soils and sediments. Furthermore,
these properties give rise to a wide range of
industrial applications throughout the history of
mankind.

The use of clay for mainly clay figures, pottery

and ceramics was already known by primitive
people about 25000 years ago (Shaikh and Wik,
1986).

Today clay is an important material with a large

variety of applications in ceramics, oil drilling,
liners for waste disposal, and the metal and
paper industry.
Dr. Hana Salem
Clay is furthermore used as adsorbent,
discoloration agents, ion exchanger, and
molecular sieve catalyst (Murray, 1991).

Despite their importance, the clay minerals

form a difficult group of minerals to study
due to their small size, variable structural
composition, and relative slow kinetics of
formation and alteration.

Dr. Hana Salem

 The group of minerals classed as clays play a central
role in many areas of petroleum technology such as:

❖ Drilling and formation stability

❖ Drilling fluid technology
❖ Reservoir productivity

Dr. Hana Salem

• Since the elements that constitute the clays account
for more than 80% of the mass of the earth (Al 8%,
Si 27.7%, O 46.6%), it can be readily realized that
every stage of drilling a hole brings contact with
clays.

• There are over 400 mineral and rock names to

describe clay minerals.

Dr. Hana Salem

 Clay mineral-rich deposits can be formed in
two other principal ways:
❖ by weathering of parent minerals in situ to
form a clay rich residual soil in which the clay
mineral kaolinite frequently predominates,
especially common in landscapes undergoing
tropical weathering,
and

❖ by ascending fluids, i.e. by hydrothermal

alteration of the host rock. Cornish china clay
is a good example, the feldspar of the local
granite having been converted mainly into clay
minerals of the kaolinite group.

Dr. Hana Salem