Clay Chemistry

1. Clay Chemical
Minerals
Clay

1. Introduction

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

The most common formations that are drilled are clays and shales.
An understanding of clay chemistry is important in the selection of a drilling
fluid system and bore hole stability.

There are over 400 mineral and rock names to describe clay minerals.

Clays are usually crystalline in nature.

Clay

2. Clay Mineral Properties

Fine particle size (< 2μm in size)

 High surface area to volume

Electrostatic charge
Interlayer (between “T” and “O” layers)

Exterior surfaces due to broken bonds

Charge deficiency (ex: Illite)

Result in:
Flocculation: attract other ions and polar molecules
Electrostatic forces may dominate (relative to gravity) the physical
properties of clay mineral-rich systems
Cation exchange capacity (CEC)
Clay

3. Basic Structural Units

The tetrahedral sheet: In the silica sheet, the basic unit is the silica
tetrahedron.

In a silica tetrahedron a silicon atom is at the center of a structure

where the corners are filled with oxygen atoms. Each tetrahedron is
formed by one atom of Si4+ and 4 atoms of O2-, so that its chemical
formula is SiO44-.

The arrangement in a sheet leads to a general averaged formula of

the type (Si4O10)4- n.
Clay

The octahedral sheet: In the alumina or magnesium sheet, the

basic unit is the octahedron.

This unit is usually formed by aluminum or magnesium and

hydroxide ions.

The aluminum or magnesium atom is bonded to 6 oxygen atoms.

Each octahedron shares all 6 oxygen atoms to form a hexagonal

structure, shown in figures .

This is called an octahedral sheet. This sheet may contain aluminum,

magnesium, or both.
Clay

Different combinations of these units and chemical modification of

the basic structure give rise to the range of clay minerals with
different properties.

They combine by sharing oxygen atoms to form a chemically bonded

layer.

Some minerals have layers comprised of two sheets (one tetrahedral

and one octahedral), while others have layers comprised of three
sheets (one octahedral sandwiched between two tetrahedral layers).

Tetrahedron and
octahedral units Layers
Structure
Clay

Basic units are the Si tetrahedron

and the Al (or Mg) octahedron.

Many tetrahedral are linked

together to form a Si tetrahedral
sheet and many octahedral are
similarly linked to from an
octahedral sheet. 

In turn, these different sheets are

bonded together to form
crystalline units.
Clay

4. Clay Mineral Groups

There are over 400 mineral and rock names to describe clay
minerals.

We will restrict our attention only to a few minerals that are most
common and most applicable minerals to petroleum technology:

Kaolin
Montmorillonite
Illite
Chlorite

These clay minerals are built up by different ratios of silica layer to

octahedral layer.
The most important groups are:
 1:1 layer
 2:1 layer
 2:1:1 layer
Clay

4.1. (1:1 Clay Minerals)

4.1.1. Clay Minerals –Kaolinite

 Si4Al4O10(OH)8. Platy shape
The bonding between layers are van
der Waals forces and hydrogen bonds
(strong bonding).
There is no interlayer swelling
Kaolinites are a two-layer clay composed
of a tetrahedral silica sheet and an
octahedral alumina sheet

The most common 1:1 minerals is Kaolinite in which one tetrahedral

and one octahedral sheet are the repeat unit with no layer charge.

The interlayer is occupied by hydroxyl groups and oxygen atoms from

the octahedral and tetrahedral sheets connected by weak hydrogen
bonds (strong bonding) and van der Waals forces.
Clay

4.1.1. Clay Minerals –Kaolinite joined by oxygen sharing

The hydrogen bonding is strong

enough to exclude water from the
layer
clay surface; consequently, kaolinites
are considered non-swelling clays.

Almost no isomorphous substitution

occurs in the minerals of the group,
so that structural electrical charge is
quite close to zero.

The cation exchange capacity of Joined by strong H-bond

Kaolinites is typically 3-15 No easy separation
milliequivalents (meq)/100 g.

Kaolin is used extensively as a raw

material for ceramics.
Clay

4.2. (2:1 Clay Minerals)

 Like a sandwich with two slices of bread. A silica tetrahedral sheet

(bread) joined to an aluminum octahedral sheet (filling) joined to a
silica tetrahedral sheet (bread).

 These sheets are joined by shared oxygen atoms

 Family members are spread into three groups that differentiated
one from the other especially on basis of the amount of the
isomorphous substitution, but also of the type of octahedral layer
present and of the way layers are bounded together into soil
particles.

 The three groups with this structure are Illite, Vermiculite and
Smectite.

In Illite isomorphous substitution (in the silica tetrahedron as well in

the octahedrons) is bigger than in the other two minerals.
The 2:1 clays can be broken into 2 groups
 Non-expansive (Slightly-expansive)
 Expansive
Clay

4.2.1. Slightly-expansive 2:1 Clay Minerals

 Ion substitution is mainly in the tetrahedral layer where Si is

replaced with Al the charge deficiency is ballanced by potassium
ions.

 Layers are held together strongly by interlayer cations.

 Because the interlayer cations are not easily removed, water will
not cause much expansion (swelling) between the layers.

 Illites are one group of non-expansive clays (potassium is the

interlayer cation).
Clay

4.2.1. (2:1 Minerals-Illite )

 Si8(Al,Mg,Fe)4~6O20(OH)4·(K,H2O)2.
Flaky shape.
 Illites have no expanding lattice;
therefore, no water can penetrate
between the layers.
 They are composed of an alumina
octahedral layer sandwiched by two silica
tetrahedral layers.
 In some Illites the substitution of silicon
by aluminum may be lower and the
potassium may be replaced by divalent
cations such as calcium or magnesium.
Clay

4.2.1. (2:1 Minerals-Illite)

 The charge deficiency is balanced by

the potassium ion between layers.

 Note that the potassium atom can

exactly fit into the hexagonal hole in
the tetrahedral sheet and form a
strong interlayer bonding.

 Resultant chemical bond is strong

enough to inhibit water squeezing in
Limits the shrink swell capacity of the
clay.
Clay

4.2.2. Expansive 2:1 Clay Minerals

 The basal spacing is fixed at 10 Å in the presence of polar liquids

(no interlayer swelling).

The cation exchange capacity of Illites is 10-40 meq/100 g.

Layers are bound together by very weak hydrogen bounds (easily

broken) with little binding by interlayer cations.

Water will insert between layers and layers will swell upon wetting.

Smectites (montmorillonite) are one group of expansive clays.

Clay

2:1 Minerals-Montmorillonite

They consist of an alumina octahedral

layer sandwiched between two silica
tetrahedral layers
The most important aspect of the smectite
group is the ability for H2O molecules to be
absorbed between the T-O-T sheets,
causing the volume of the minerals to
increase when they come in contact with
water.
n·H2O and cations exist between unit
layers, and the basal spacing is from 9.6 Å
to  (after swelling).

There is much substitution of Mg+2 for Al+3 in the octahedral layer of

this clay.
Clay

The negative charge produced

by this substitution is balanced Joined by weak
by an interlayer cation, Van der Waal’s
bond
sometimes Ca+2 and sometimes
Na+. n·H2O+cations

The bonding between layers is

Easily separated by
quite weak, being based only on water
the van der Waals forces,
disposed in water films of
several molecules.

It is because of this exchangeability of cations and water molecules in

the interlayer strata that those materials show great swelling
potentials.
Clay

4.3. The 2:1:1 minerals

 Minerals of the kind 2:1:1 are

given by adding to the structure
of a 2:1 mineral an additional
hydroxide interlayer.

 Particularity of this group is

that, in front of a charge
deficiency in the tetrahedral
sheet because of the
substitution of Si4+ with Al3+, in
the octahedral sheet the Al is in
surplus so that that the Gibbsite
is positively charged and the
layer globally neutral.

 There is a strong bonding between layers and for this reason

chlorite is a non-swelling clay.
 The cation exchange capacity for chlorites is 10-40 meq/100 g.
Clay

4.4. Mixed Layer Clay

Different types of clay minerals have similar structures (tetrahedral

and octahedral sheets) so that interstratifications of layers of
different clay minerals can be observed.

Mixed layer clays are common, and consist of clays that change
from one type to another through a stacking sequence.

The sequences can be ordered and regular, or high unordered and

irregular.

For example montmorillinite layers can alternate with illite layers in

an ordered way, or there can be several layers of montmorillinite
with random layers of illite.
Clay

4.5. attapulgite and Sepioliete

Two other commercial clays, attapulgite and sepiolite, are used in

special situations in which montmorillonite will not perform.

These clays differ in structure from the more common clays in that
they are elongated rod-shaped particles. Although there is water
associated with these clays, they do not hydrate.

Since these clays are shear dependent, they are as effective in

saltwater as in freshwater.

Attapulgite has a fibrous texture and a chain structure.

Shearing of the particles requires maximum agitation in order to yield

this clay fully.

The disadvantages of attapulgite and sepiolite are, poor filtration

characteristics due to their brush heap structures.
Clay

5. Resume
Clay

6. Clay Structure Summary

 2. Interaction
of Water
and Clay Minerals
Clay

1. Origins of Charge Deficiencies

A. Imperfections in the crystal lattice -Isomorphous

substitution.

These substitutions occur during formation of the clay mineral

and are permanent to the structure.  Both lead to net negative
Charge within the crystal lattice that is balanced by adsorbed
cations.
The cations in the octahedral or tetrahedral sheet can be
replaced by different kinds of cations without change in crystal
Structure (similar physical size of cations).

For example,
Al3+ in place of Si4+ (Tetrahedral sheet)
Mg2+ instead of Al3+(Octahedral sheet)
 unbalanced charges (charge deficiencies)

This is the main source of charge deficiencies for montmorillonite.

Only minor isomorphous substitution takes place in kaolinite.
Clay

Isomorphic substitution in 2:1 mineral clay crystal

sheet sheet
charges charges

No
With isomorphic
substitution
substitution
Clay

B. Imperfections in the crystal lattice - The broken edge

A second source of charge on the minerals is the broken bonds

found at the mineral edges.

The structure cannot extend infinitely, so at some point there will

be oxygens without all charges satisfied by associating with
cations.

In these cases a hydrogen ion from solution will normally satisfy

the requirement. Whether this can occur will, however, depend on
the solution pH.

Therefore, these charges are called either pH-dependent charge

or variable charge.
Clay

C. Proton equilibria (pH-dependent charges)

Loss of ionizable H+ from certain sites on mineral Colloids or from

certain functional groups in humus leads to negatively charged sites.

Protonation of other sites leads to positively charged sites.

pH-dependent Negative charge increases with increasing pH but pH-

Dependent positive charge increases with decreasing pH.

Kaolinite particles are positively charged on their edges when in a

low pH environment, but negatively charged in a high pH (basic)
environment.

 
M  OH  H  M  OH 2 (Pr otonation )

M  OH  OH  M  O   H 2 O ( Deprotonat ion )
Clay

Sources of pH-dependent charges on silicate clay (kaolinite)

More acid More acid

Clay

2. Cation Replaceability

 Different types and quantities of cations are adsorbed to balance

charge deficiencies in clay particles.

 The types of adsorbed cations depend on the depositional

environment. For example, sodium and magnesium are dominant
cations in marine clays since they are common in sea water.

 In general, calcium and magnesium are the predominant cations.

 The adsorbed cations are exchangeable (replaceable).

For example,

Na Na Na Na Ca Ca
+4CaCl2  +8NaCl
Na Na Na Na Ca Ca
(Lambe and Whitman, 1979)
Clay

The replaceability of cations depends on a number of factors such as :

 Effect on concentration

 Population of exchange site

 Nature of anion

 Nature of cation

 Nature of clay mineral

A high concentration of potassium can replace calcium.

Also in some mineral, such as mica, potassium is particularly strongly

adsorbed and not easily replaced except by hydrogen.

Clay

The case of cation replacement Non-hydrated Hydrated

depends on the: Cations radius (Å) radius (Å)
Li+ 0.68 3.8
 Valence (primarily) : Higher
valence cations can replace Na+ 0.95 3.6
cations of lower valence. K+ 1.33 3.3
Cs+ 1.69 3.3
 Ion size : Cations with larger
Be2+ 0.31 4.6
non-hydrated radius or smaller
Mg2+ 0.65 4.3
hydrated radius have greater
replacement power. Ca2+ 0.99 4.1
 
Ba2+ 1.35
According to rules (1) and (2),
Al3+ 0.5 4.8
the general order of replacement
Fe3+ 0.6  
is:
Li+<Na+<K+<Rb+<Cs+<Mg2+<
Ca2+<Ba2+<Cu2+<Al3+<Fe3+<Th4+

 Relative amount high concentration of Na+ can displace Al3+.

Clay

3. Caption Exchange Capacity (C.E.C)

The quantity of exchangeable cations is termed the cation exchangeable

capacity (CEC) and is usually expressed as milli equivalents (meq) per
100 gram of dry clay.

One equivalent = 6.021023 electron charges.

Mineral Specific surface C.E.C (meq/100g)

(m2/g)
Kaolinite 10-20 3-10

Illite 80-100 20-30

Montmorillonite 800 80-120

Chlorite 80 20-30
Clay

4. Prehydration
Because clay particles are so small, their behavior is dominated by
surface forces.

Clay in dry state exist in face-to-face stacks like a deck of playing

cards, the packets begins to change when the clay is exposed to
water.

 Negative ionic character at the mineral surface provides attractive

forces for adsorpsion of polar water molecules

 Na+ at the mineral surface will associate with a charge deficient area
on one sheet and dispersion in water will create separated sheets

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

 Ca++ can not effectively assosiate with two negative charge sentres
on one sheet and must bind 2 sheets together
Clay

Hydrated

17 A
Ca +2
Ca +2
Ca+2 Ca +2
12.1 A

Na+ Hydrated

Na+ Na+
Na+ Na+
9.8 A 17 A to infinite
+
Na+ Na
Na+ Na+

Na+
Clay

5. Clays in Drilling Fluids

Clays play a significant role in drilling fluids, particularly the water

based.

 They may be added intentionally to control viscosity and fluid loss.

 In most water based drilling fluids there is a rapid build up of clay

minerals from the formation.

The association between clay particles are important as they affect

important properties (viscosity, yield, fluid loss).

The mechanisms are deflocculation, flocculation, aggregation and

dispergation.
Clay

The clay in its dry state has platelets stacked in face-to-face

association, like a deck of cards. This is Aggregation.

When the dry clay is placed into fresh water with no agitation, the
packets adsorb water, hydrate, and swell. Upon agitation, the swollen
packets disintegrate into individual plates or smaller packets of
plates. This is Dispersion.

As long as agitation continues, dispersion will be retained and

further dispersion can occur.

When agitation is stopped, clay platelets will be mutually attracted in

edge-to-edge or edge-to-face association. This forces a structure
similar to a house of cards, termed Flocculation.
Clay

If an anionic chemical thinner (deflocculant) is added, such as

polyphosphate, lignosulfonate or lignite, etc., it neutralizes the
positive edge charges on clay platelets and the flocculated state
is now Deflocculated.

When this deflocculated clay slurry encounters strong ionic

contamination (NaCl, CaSO4, Ca(OH)2, etc.), the deflocculant chemical
is often overpowered - leading again to flocculation and even to a
sort of aggregation where water is lost from the clay surfaces.
Clay

6. Particle Associations

Dispersed and Aggregated but

deflocculated deflocculated

Edge-to-face
flocculated but Edge-to-edge flocculated
dispersed but dispersed

Edge-to-face and edge

to edge flocculated and
Edge-to-face aggregated
flocculated and
aggregated
van Olphen, 1991

Edge-to-edge
flocculated and
aggregated
Clay

A. Dispersed System
The subdivision of particles from the
aggregated state in a fluid (water) to
a hydrated colloid particle is the
dispersing of that particle.
This usually occurs in a static
condition and is termed gel strength
of dispersed day.

When bentonite is in a dispersed

state, the positive ion cloud presents
an effective “shield” around the clay
and sometimes slows this effect.
The ionized Na+ surrounds the clay
to form a weak crystalline barrier.

Effect of Clays in Drilling Fluids:

 High viscosity
 High gel strength
 Low filtrate
Clay

Na +
+
+
Na Na+
+
- Na
+
+-
Na+ + - - - + +-
-
-
Na + Na+
-
+
+
+
-+ - - - + + - -
Na+ Na+
- +
+-
-- + +
-+ - - - + + - Na+
+
- -
+- Na+
-+ + --
Na+
-
- + +- - - + + - Na+
Na + - +
-+
Na+ +-
+ Na
-
+

Dispersed Bentonite / Ionized Na+ Hydrated Clay W/Water Envelope

Clay

B. Flocculated System

Increase interparticle attractive forces and decrease repulsive forces

in: High salt concentrations, Polyvalent cations, Polymeric
flocculants, Low pH and High temperature.

 Flocculation (Sodium Chloride)

The most common cause of flocculation of clays in the field is the
incorporation of NaCl in to a fresh water mud. When the Na+ content
is raised toward 1%, the water becomes more positively charged.
As the NaCl content increases to 5%, the free water is tied up by
the chloride ion, and the ion and the clays collapse and revert to the
aggregated state. The water is removed from the clay platelet body.
When the NaCl content increases to 15% to 30% by weight, the
agglomerates flocculate into large edge to face groups.
Effect of Clays in Drilling Fluids:
 Viscosity High
 Yield High
 Fluid loss High
Clay
+ +
- - +
+ -
+ +
- + -
- - +
- - + -
+ - + +
- - - + -
-
+ + - - +
+ - -
- + - - - -
+ +
+ - - + - -
- -
- + + - + - + -
+ - + -
- - + + - + - -
+ - + + + - +
- - - + - -
- - +
+ - + - -
+ + - +
- + - + - +
+ - - - -
+ - - +
+ + + - +
- + + - - -
- - +
+
+ + - +
- -
+ + - +
- - -
+ + + - +
- -
- - - + -
- - +
+ - - + - +
- - + - -
- - + - -
+ + +
- + + - - +
+ + + - -
- + - -
+ + + +
- - - + -
+ + + -
- - - -
- - + -
- - - + + - +
+ + - - -
- - - +
+ - + +
+ + + - +
+ - -
- - - +
- -
+ + - +
+ + -
- - +
- -
- +
- -
- + + + + +
- + - - - -
+ + + + +
+ + -
- - - - -
- - +
+ + - - - - -
- + -
- - - - -
+ -
+ + + +
- -
+
- - - -
+
- + + + +
+

1 % N a C l 5 % N a C l
F lo c c u la te d A g g re g a te d

+
-

-
+

+
-
-
-
+

+
-
+ -
-
15-30% NaCl
+ - + -
- - -
- - + +

Aggregated& Flocculated
+ + - + +
+ - + - -
- - - + -
- - +
- + + - +
+ - + + -
- + - - -
- - - + - -
- + + +
- + + - +
+ - - - -
- + - - +
- +
+ + -
+ - +
- -
+ - + +- + + +
+ + + + + - + - -+ - -
- - - - +
+ -- -
+ +
- + ++ +
+ + + + - -
+ - - - + - - -
- - - - - + -
+ + + - +-
- - - - - - -
- - - - + - -
- - -
- - + + + - - -
- - + - - - + - +
- - + + + +
+ + + + + - - - - +
+ + +
- - + - + - - - -
- - - - - -
- - - +
+ + -+ +
+ - - + -
+ +
+ - - -
+ + - +
- + -
+ ++ -
- - - +
- - - +
+ - -
- + + -
+ + + +
+ - - + + - - + +
+ - + -
- + - + - - - - - -
+ + - + - +
+ + + + + +
- - - - + + - +
+ - - - - -
- - - - -
- - + -
- - - - - - + -
+ - - - +
- - - -+ - -
- - + -
- + - + + + + +-
- + + - -
- + - + + +
+ - + - - -
+ - - - +- - -
+ - + - - - - +
+ + + - - -
+ - + - - + +
+ -
+ - + +
+ - +
- +

5% NaCl 15-30% NaCl

Aggregated Aggregated & Flocculated
5% NaCl - Aggregated
Clay

 Flocculation (Calcium)

Calcium can cause flocculation in the same manner as salt (NaCl) in

that edge-to-face groupings are formed.

Calcium is a divalent cation, so it holds onto two platelet faces, which

causes large groups to form, and then the edge-to-face grouping to
take hold.

Because calcium(Ca++) has a valence of 2, it can hold two clay

platelets tightly together, and the flocculation reaction starts to
happen at very low concentrations.

To achieve flocculation with salt (NaCl), it takes 10 times the

concentration for the edge-to-face groupings to form.

The divalent calcium ions will still partially hydrated, but the amount
of water is less around the clay platelet.
Clay

Ca++
- -
Ca +_ +_
+ + Ca
+ + - + Ca++
- Ca - + - - + - ++
Ca Ca - -
- +
_
+ +
+ + + - - + - ++
+ +
--+_+ +- Ca++
Ca Ca + + Ca+ --
--+_+ +- -Ca + Ca+2+- +
Ca + - - + +
- _ -
+ -Ca++-+ Ca + - Ca+2
- Ca Ca
Ca++ + - + - - + -+ -
+
Ca+2 Ca++ + -
Ca
Clay

Sodium to Calcium Clay

Ca Ca++
Na+

-
Na+ Ca++ Ca++
- - _ Ca++

- -
Na+

Ca
Ca++ Ca++
-
Na
+ Ca++
Na+ Ca++
Na+ Ca++ Ca++
Ca+2a+

Ca +2 + _ + + -
+- + +-+
N

Ca+2 - - + -+

--
+-+

--+_+ +-
Na+ Ca
Ca++ Ca Ca
Na
+
Na+
-
Clay

C. Polymeric Flocculants

 The reaction between clays and polymers depends on a number of

factors such as the molecular weight of the polymer and the
adsorption of the polymer on the clay particle.

 There is a definite relationship between the weight of a polymer

and its length.

 The strength of the adsorption and the site of the adsorption will
depend on the chemical character of the polymer.

 Generally, negatively charged polymers can adsorb on cationic

sites generated at the edges. Most polymers in drilling fluids tend to
be of this type.
Clay

_ _
- +- + - +- +
_
- -
+ + +
_ _

Ca
_
_
-
Clay

D. Deflocculated System

A system is described as deflocculated

when there is an overall repulsive force
between the particles.

This is normally achieved by creating the

conditions in which the particles carry the
same charges.

 Chemically disperse

 Calcium Precipitation
Clay

 Chemically disperse

One way to deflocculate, or chemically disperse, a clay platelet is

with a large molecule having many carboxyl and sulfonate anions.

The edge-to-face flocculation that occurred becomes virtually

impossible.

In deflocculated the viscosity will be lower than it was in the

flocculated state.

Effect of Clays in Drilling Fluids:

 Viscosity normal

 Yield Low
 Fluid loss Low
Clay

 Calcium Precipitation

The most effective way to remove the flocculating calcium ion from
the system is to chemically precipitate it.

Two common chemicals can be used to accomplish removal of the

calcium ion.

They are Na2Co3 (soda ash) and NaHCO3 (bicarbonate of sodium).

Ca+++2 OH-+Na2HCO3→CaCO3+NaOH+H2O

CaSO4+Na2CO3→CaCO3+Na2SO4

In the previous chemical equation, calcium is precipitated and

rendered inert.

There is no longer a possible flocculating calcium ion to deal with.

Clay

Na -

- +- + - +- + Na
_ + _
_ -
+
_ _
_
_
+ - + - + _
- +-
_
Na -- +
Na -
Clay

- - -
-
- - - - - - + -
- -
- - +
-
- + - - + -
-
- +
- + +
- -
+ + - +
- -
- + +
+ - -
- - - +
- - -
+ - -
- + - - -
- - - - - - -
- + - - -
- -
- -
+ - -
- -
- - +
- -
- + -
-
- +
-
- +
+ -
- - - + + -
- + - +
- - - - +
- - - - -
-
+
Clay

E. Aggregated System

Clays are said to be in the aggregated state when clay is collapsed

and its layers are parallel, the formation is like a deck of cards
stacked in a box.

A clay aggregate is an assemblage of clay sheets.

The aggregate may be disaggregated by hydration and or

mechanical shear.

It may be inferred that the higher the chloride content and the
higher the valence of the cation salts in solution, the more the clay
will be inhibited from swelling.
Clay

When added to freshwater (does not +

-
+

-
+
+

contain a high concentration of chlorides),

- + - +
- - + -
- - +
-
- - -
+ +

diffuses of water into the layers occurs,

- -
- + -
+ - + -
+ - + -
+ - + - -
- + + - +
+

and swelling or dispersion results.

- -
+ - - +
+ -
+ - +
- - +
-
+ - +
+ - - -
- +
+
+ - +
- -
+ - +
-
+ - +
- -

In solutions with high chloride

+ - -
+ + +
- - -
+ - -
+ + +
- -
-

concentrations, the double layer is

- + + -
- + -
+ -
+ - -
+ + - +
- -
- - +

compressed still further, and aggregation

+ -
+ - +
- - +
-
+ - +
- -
- +

occurs.
+
+ + + + - +
- - - -
+ + + +
- - - -
- - - -
- - - -
+ + + +

Consequently, the size of the particle is

- - - -
+ + + +

reduced, and the total particle area per

unit volume decreases.

The aggregates themselves may be flocculated or deflocculated.

Effect of Clays in Drilling Fluids:
 Viscosity Low
 Yield Low
 Fluid loss High
Clay

7. Swelling of clays

Some clays do not swell up on hydration, e.g., kaolinite clay exhibits

little or no swelling on hydration.
Sodium-montmorillonite, on the other hand, swells in water to many
times its dry volume.

Swelling properties of different clays are a function of:

 Structure
 Chemical composition
 The amount and types of exchangeable cations

In swelling due to hydration, there are two types of swelling; swelling

due to the expansion of the crystal lattice itself, and swelling due to
the adsorption of water on surface of the clays particles.
Clay

 Between the layers (osmotic).

The exposure of the clay to water vapor causes the water to

condense between the layers, expanding them.

The lower the concentration of sodium and chloride in the water,

the greater the amount of water that can be absorbed into the
clay lattice structure.

 Around layers (crystalline).

There is a layer of water that surrounds the clay particles (a cloud of

Na+ with water molecules held to the platelet by hydrogen bonding to
the lattice network by the oxygen on the face of the platelet).