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1: Introduction
Clay Chemistry
1: Introduction The group of minerals classed as clays play a centrale role in
2: Fundamental many areas of petroleum technology such as:
Building Units
 Drilling and formation stability
3: Clay Mineral
Groups  Drilling fluid technology
4: Prehydration
 Reservoar productivity
5: Clays in
Drilling Fluids
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.

Physical Phenomena in Clays

.
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Basic Features
Clay Chemistry
1: Introduction There are a number of features of the clay minerals that
2: Fundamental distinguish them as a group:
Building Units
 Fine size (less than 2m)
3: Clay Mineral
Groups  Large surface area
4: Prehydration
 Chemical reactivity of the surface
5: Clays in
 Composed of the same chemical components
Drilling Fluids

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2: Fundamental Building Units

Clay Chemistry
1: Introduction

2: Fundamental
Building Units Clay is composed essentially of silica, alumina and water.
3: Clay Mineral Lesser quantities of iron, magnesium, sodium and potassium.
Groups

4: Prehydration

5: Clays in
Drilling Fluids

Fundamental building units of clay minerals:

Octahedral layer Tetrahedral layer

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Tetrahedral Layer
Clay Chemistry
1: Introduction In each tetrahedral unit, a silicon atom is located in the
2: Fundamental centre of a tetrahedron, eqidistant form four oxygen atoms,
Building Units
or hydroxyls, if needed to balance the structure.
3: Clay Mineral
Groups

4: Prehydration
The silica tetrahedral groups are arranged to form a
5: Clays in
Drilling Fluids hexagonal network, which i repeated infinitely to form a
sheet of composition Si4O6 (OH)4.

The figure is viewed from below, to show the hexagonal

structure with a ”hole” in the centre .

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Octahedral Layer
Clay Chemistry
1: Introduction This unit consists of two sheets of closely packed oxygens or
2: Fundamental hydroxyls in which aluminium, iron or magnesium ions are
Building Units
embedded in octrahedral coordination
3: Clay Mineral
Groups

4: Prehydration

5: Clays in
Drilling Fluids

When Aluminium is present, only two thirds of the possible

positions are filled to balance the structure –
gibsonite – Al(OH)3
When magnesium is present, all the positions are filled and
the structure is brucite – Mg(OH)2
Often in clays, this layer contains more than one metal ion.

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Structures of Clay Minerals

Clay Chemistry
1: Introduction
The fundamental units of tetrahedral sheets and octahedral
2: Fundamental
sheets can combine with the hydroxyl group of the
Building Units tetrahedral layer contributing to the octahedral layer.
3: Clay Mineral
Groups
Different combinations of these units and chemical
4: Prehydration modification of the basic structure give rise to the range of
5: Clays in clay minerals with different properties.
Drilling Fluids

Structure

Tetrahedron and
Layers
octahedral units

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3: Clay Mineral Groups

Clay Chemistry
1: Introduction
There are over 400 mineral and rock names to describe clay
2: Fundamental
minerals. We will restrict our attention only to a few minerals
Building Units that are most common and most applicable minerals to
3: Clay Mineral
Groups
petroleum technology:
4: Prehydration  Montmorillonite
5: Clays in
Drilling Fluids
 Kaolin
 Micas
 Chlorite

These clay minerals are built up by different ratios of silica

layer to octahedral layer.
The most important groups is:
 2:1 layer
 2:1:1 layer
 1:1 layer

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Kaolin
Clay Chemistry
1: Introduction
The origin of Kaolin is often hydro-termal alternation of
2: Fundamental
feldspars, or from volcanic ash, and is extensively found in
Building Units Shales and marine deposits.
3: Clay Mineral
Groups
 1:1 structure
 balanced charges within the structure
4: Prehydration
 very strong hydrogen bonding between the basic building units:
5: Clays in
Drilling Fluids
- no swelling occurs
- natural crystals consist of about 100 unit layers stacked one upon the other

Diagrammatic sketch of
the structure of Kaolin.
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Micas
Clay Chemistry
1: Introduction Micas are a 2:1 lattice type mineral.
2: Fundamental ion substitution is mainly in the tetrahedral layer where si is replaced with Al
Building Units
the charge deficiency is ballanced by potassium ions
3: Clay Mineral
Groups - successive sheets are strongly bound together
4: Prehydration - non expanding structure
5: Clays in Different types of micas are Muscovite, Biotite and Illite
Drilling Fluids
The micas found in sedimentary
shale sections is normally
classed as Illite

Diagrammatic sketch of
From http://mineral.galleries.com
the structure of Muscovite.
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Chlorite
Clay Chemistry
1: Introduction Clorite are a 2:1:1 lattice type mineral
2: Fundamental the charge deficiencies in mica layer is ballanced by kations
Building Units
- successive sheets are strongly bound together
3: Clay Mineral
Groups - non expanding structure
4: Prehydration

5: Clays in
Drilling Fluids
Chlorite tends to be
associated with old
sediments

Diagrammatic sketch of
From http://mineral.galleries.com the structure of Chlorite.
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Montmorillonite
Clay Chemistry
1: Introduction Montmorillonite is the most common mineral in the group of
2: Fundamental
minerals called the smectites.
Building Units The essential feature is expandable (swelling) structure:
3: Clay Mineral -very large surface area
Groups
-ionic substitution in the octahedral layer
4: Prehydration -negative ionic character at the mineral surface
5: Clays in -attractive forces for the adsorption of polar molecules such as water
Drilling Fluids
Expandable montmorillonite can exist
in substantial quantities in shales as a
result of volcanic ash falling into a
marine environment.

From http://cms.lanl.gov/ Diagrammatic sketch of the structure of

Smectite 5m
Montmorillonite-Bentonite (Smectite).
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Bentonite
Clay Chemistry
1: Introduction
Bentonite is a soft clay substance composed essentially
2: Fundamental
of clay minerals of the smectite (montmorillonite) group.
Building Units

3: Clay Mineral
Groups

4: Prehydration

5: Clays in
Drilling Fluids

Bentonite is remains of Bentonite is mined throughout

volcanic materials. the world but is abundant in
Wyoming, USA and Greece.
Uses of Bentonite:
well-drilling mud
binder and digestive aid in animal feed
absorbent material for cat litter
sealing agent for reservoirs, lagoons and other engineering projects
binder in foundry sand
ceramic
cosmetics, facial/body masks
and more

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4: Prehydration
Clay Chemistry
1: Introduction Clay in dry state exist in face-to-face stacks like a deck of
2: Fundamental playing cards, the packets begins to change when the clay is
Building Units
exposed to water.
3: Clay Mineral
Groups  negative ionic character at the mineral surface provides attractive forces
4: Prehydration
for adsorpsion of polar water molecules
5: Clays in
 Na+ at the mineral surface will associate with a charge deficient area on
Drilling Fluids one sheet and dispersion in water will create separated sheets
 Ca2+ cannot effectively assosiate with two negative charge sentres on
one sheet and must bind 2 sheets together

The volume of the clay will increase, and the clay minerals
will disperse into the water phase.

Click
here
to
watch
video
Hydration of Calcium Montmorillonite and Sodium Montmorillonite.

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Video
Clay Chemistry
1: Introduction

2: Fundamental
Building Units

3: Clay Mineral
Groups

4: Prehydration

5: Clays in
What does
Drilling Fluids

this
experiment
shows
?

Left Beaker Right Beaker

Montmorillonite clay (Bentonite) Montmorillonite clay (Bentonite)
exposed to fresh water. exposed to sea water.

Total time is 5 hours

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The Experiment Shows

Clay Chemistry
1: Introduction In fresh water clay sheets will seperate and as a
2: Fundamental result the clay swells.
Building Units

3: Clay Mineral
In sea water the hydration of the montmorillonite
Groups reduces due to the effect of salt.
4: Prehydration

5: Clays in
Drilling Fluids

The force causing the sheets to seperate are electrostatic

repulsive force between negatively charde particles. These
forces are decreased as the conductivity of the water is
increased by the addition of salts.

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5: Clays in Drilling Fluids

Clay Chemistry
1: Introduction
Clays play a significant role in drilling fluids, particularly the
2: Fundamental
water based.
Building Units  They may be added intentionally to control viscosity and fluid loss.
3: Clay Mineral
Groups
 In most water based drilling fluids there is a rapid build up of clay
minerals from the formation.
4: Prehydration

5: Clays in
Drilling Fluids

The association between clay particles are important as they

affect important properties (viscosity, yield, fluid loss). The
mechanisms are deflocculation, flocculation, aggregation and
dispergation.

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Dispersed System
Clay Chemistry
1: Introduction A system in which the breakdown of the aggregates is
2: Fundamental complete is called a dispersed system.
Building Units

3: Clay Mineral
Groups

4: Prehydration

5: Clays in
Drilling Fluids

Effect of Clays in Drilling Fluids:

Viscosity normal
Yield normal
Fluid loss normal

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Flocculated System
Clay Chemistry
1: Introduction A system may be described as flocculated when there are
2: Fundamental net attractive forces for the particles and they can associate
Building Units
with each other to form loose structures.
3: Clay Mineral
Groups

4: Prehydration

5: Clays in
Drilling Fluids

Effect of Clays in Drilling Fluids:

Viscosity High
Yield High
Fluid loss High

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Deflocculated System
Clay Chemistry
1: Introduction A system of suspended particles is described as deflocculated
2: Fundamental when there is an overall repulsive force between the
Building Units
particles.
3: Clay Mineral
Groups This is normally achieved by creating the conditions in which
4: Prehydration the particles carry the same charges. In clay systems this is
5: Clays in
Drilling Fluids
normally a net negative charge.

Effect of Clays in Drilling Fluids:

Viscosity normal
Yield Low
Fluid loss Low

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Aggregated System
Clay Chemistry
1: Introduction A clay aggregate is an assemblage of clay sheets.
2: Fundamental
Building Units
The aggregate may be disaggregated by hydration and or
3: Clay Mineral
mechanical shear.
Groups
The aggregates themselves may be flocculated or
4: Prehydration
deflocculated.
5: Clays in
Drilling Fluids

Effect of Clays in Drilling Fluids:

Viscosity Low
Yield Low
Fluid loss High

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