Clay Chemistry

1. Clay Chemical
Minerals
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.
minerals

Clays are usually crystalline in nature.

2. Clay Mineral Properties

 Fine particle size (< 2μm in size)

 High surface area to volume

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

 Exterior
E t i surfaces
f due
d to
t broken
b k bonds
b d
 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)
3. Basic Structural Units

The tetrahedral sheet: In the silica sheet

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
yp ((Si4O10)4- n.
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
h in figures
f .

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

magnesium,
i or both.
b th
Different combinations of these units and chemical modification of
the basic structure give rise to the range of clay minerals with
different properties.
p p

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
h (
(one octahedral
h d l sandwiched
d h dbbetween two tetrahedral
h d l layers).
l )

Tetrahedron and
octahedral units Layers
Structure
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.
4. Clay Mineral Groups

There are over 400 mineral and rock names to describe clay
y
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
t h d l layer.
l
The most important groups are:
y
 1:1 layer
 2:1 layer
 2:1:1 layer
4.1. (1:1 Clay Minerals)
Minerals)

4.1.1. Clay
y Minerals –Kaolinite
 Si4Al4O10(OH)8. Platy shape
The bonding
g between layers
y 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.
4.1.1. Clay Minerals –Kaolinite joined by oxygen sharing

The hydrogen
y g bonding
g is strong g
enough to exclude water from the
layer
clay surface; consequently, kaolinites
are considered non-swelling
g clays.
y

Almost no isomorphous substitution

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

The cation
Th i exchange
h capacity
i off 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.
4.2. (2:1 Clay Minerals)
Minerals)

 Like a sandwich with two slices of bread.

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
p y 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.
Th 2:1
The 2 1 clays
l can be
b broken
b k i t 2 groups
into
 Non-expansive (Slightly-expansive)
 Expansive
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

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

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

interlayer cation).
4.2.1. (2:1 Minerals-Illite )

 Si8(Al,Mg,Fe)4~6O20(OH)4·(K,H2O)2.
Flaky shape.
 Illites
Illit have
h no expanding
di l tti
lattice;
therefore, no water can penetrate
between the layers.
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.
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
h tetrahedral
h d l sheet
h and
d form
f a
strong interlayer bonding.

 Resultant chemical bond is strong

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

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 T-O-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).
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
Van der Waal
Waal’ss
by an interlayer cation,
bond
sometimes Ca+2 and sometimes
Na+. n∙H
H2O+cations
O ti

Th bonding
The b di b t
between l
layers i
is Easily separated by
quite weak, being based only on water

the van der Waals forces,

forces
disposed in water films of
several molecules.
molecules

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

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

 Particularity of this group is

that, in front of a charge g
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
l
layer globally
l b ll neutral.
l

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

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

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,
way or there can be several layers of montmorillinite
with random layers of illite.
4.5. attapulgite and Sepioliete

Two other commercial clays,y , attapulgite

p g and sepiolite,
p , 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
h clays
l are shear
h d
dependent,
d they
h are as effective
ff in
saltwater as in freshwater.

Att
Attapulgite
l it has
h a fibrous
fib texture
t t and
d a chain
h i structure.
t t

Shearing of the particles requires maximum agitation in order to yield

this clay fully.
fully

The disadvantages of attapulgite and sepiolite are, poor filtration

characteristics due to their brush heap structures.
structures
6. Clay Structure Summary
 2. Interaction
of Water
and Clay
y Minerals
1. Origins of Charge Deficiencies

A Imperfections
A. 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 p
physical
y 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.
Isomorphic substitution in 2:1 mineral clay crystal

sheet sheet
charges charges

No
With isomorphic
substitution
substitution
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

Therefore, pH dependent charge
or variable charge.
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
pH dependent Negative charge increases with increasing pH but pH-
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.
environment

 
M  OH  H  M  OH 2 (Pr otonation )

M  OH  OH  M  O   H 2 O ( Deprotonat ion )
Sources of pH-dependent charges on silicate clay (kaolinite)

More acid More acid
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
y since they
y 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)
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.

hydrogen
The case of cation replacement Non‐hydrated  Hydrated 
depends on the: Cations radius (Å) radius (Å)
Li+ 0 68
0.68 38
3.8
 Valence (primarily) : Higher
Na+ 0.95 3.6
valence cations can replace
cations of lower valence.
valence K+ 1 33
1.33 33
3.3
Cs+ 1.69 3.3
 Ion size : Cations with larger Be2+ 0.31
3 4.6
4
non-hydrated radius or smaller
Mg2+ 0.65 4.3
hydrated radius have greater
Ca2+ 0.99 4.1
replacement power.
power
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+.
3. Caption Exchange Capacity (C.E.C)

The q
quantity
y of exchangeable
g cations is termed the cation exchangeable
g
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
20 30
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
cards,
water.

 Negative ionic character

h at the
h minerall surface
f provides
d 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
 Hydrated

17 A
Ca +2
Ca +2
Ca+2 Ca +2
12 1 A
12.1

Na+ Hydrated

Na+ Na+
Na+ Na+
98A
9.8 17 A to infinite
+
Na+ Na
Na+ Na+

Na+
5. Clays in Drilling Fluids

Clays play
Cl l a significant
i ifi t role
l in
i drilling
d illi fl id particularly
fluids, ti l l theth water
t
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,

f f
flocculation, aggregation and
dispergation.
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
k t adsorb
d b water,
t h d t and
hydrate, d swell.
ll Upon
U agitation,
it ti th swollen
the ll
packets disintegrate into individual plates or smaller packets of
plates This is Dispersion.
plates. 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
i il tot a house
h off cards,
d termed
t d Flocculation.
Fl l ti
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,
(NaCl CaSO4, Ca(OH)2, etc.),
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.
surfaces
6. Particle Associations

Dispersed and  Aggregated but 
deflocculated deflocculated

Edge‐to‐face 
fl
flocculated but 
l d b   Edge‐to‐edge flocculated 
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
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 clayy
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
 Na +
+
+
Na Na+
+
- Na
+
+-
-
-
Na+
Na+ + - - - + +- Na+
-
+
+
+
-+ - - - + + - - Na+
- +
+-
- - + +
-+ - - - + + - Na+
+
- -
+- Na+
-+ + - -
Na+ -
-
+
-+
+- - - + + - Na+
Na + - + Na+ +-
+ Na
-
+

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

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. 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 y weight,
g , the
agglomerates flocculate into large edge to face groups.
Effect of Clays in Drilling Fluids:
 Viscosity High
 Yield High
 Fluid loss High
 + +
- - +
+ -
+ +
- + -
- - +
- - + -
+ - + +
- - - + -
-
+ + - - +
+ - -
- + - - - -
+ +
+ - - + - -
- -
- + + - + - + -
+ - + -
- - + + - + - -
+ - + + + - +
- - - + - -
- - +
+ - + - -
+ + - +
- + - + - +
+ - - - -
+ - - +
+ + + - +
- + + - - -
- - +
+
+ + - +
- -
+ + - +
- - -
+ + + - +
- -
- - - + -
- - +
+ - - + - +
- - + - -
- - + - -
+ + +
- + + - - +
+ + + - -
- + - -
+ + + +
- - - + -
+ + + -
- - - -
- - + -
- - - + + - +
+ + - - -
- - - +
+ - + +
+ + + - +
+ - -
- - - +
- -
+ + - +
+ + -
- - +
- -
- +
- -
- + + + + +
- + - - - -
+ + + + +
+ + -
- - - - -
- - +
+ + - - - - -
- + -
- - - - -
+ -
+ + + +
- -
+
- - - -
+
- + + + +
+

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

+
-
+ -
-

-
-
+
-

-
+ +
-

-
+ -
-
-
+
- +
gg egated& Flocculated
Aggregated& occu ated +
-
- - + + - +
+ + - + + -
- + - - -
- - - + - -
- + + +
- + + - +
+ - - - -
- + - - +
- +
+ + -
+ - +
- -
+ - + + - + + +
+ + + + + - + - - + - -
- - - - +
+ -- -
+ +- + ++ +
+ + + + - -
+ - - - + - - -
- - - - - + - -
+ - + + +-
- - - - - -
- - - - + - -
- - - -
- - - - + + + + + - - -
- - - + +
+ + - - - + + +
+ + + - - - +
+ + +
- - + - + - - - -
- - - - - -
- - - +
+ + + -+ +
- - +
+- -
+
-
+ + - - +
+
- + -
+ + + -
- - - +
- - - +
+ - -
- + + -
+ + + +
+ - - + + - - + +
+ - + -
- + - + - - - - - -
+ + - + - +
+ + + + + +
- - - - + + - +
+ - - - - -
- - - - -
- - + -
- - - - - - + -
+ - - - +
- - - -+ - -
- - + -
- + - + + -+ + +-
- + + -
- + - + + - +
+ - + - -
+ - + + -
-
- -
- +- -
- -
-
+ + - +
+ - + + - - - +
+ - +
- -
+ + +
+ - +
- +

5% NaCl - Aggregated
 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
l ( ++) hhas a valence
l off 2, it can hold
h ld two clay
l
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.
 Ca++
- -
Ca
C +_ +_
+ + Ca
+ + - + Ca++
- Ca - + - - + - ++
C
Ca Ca - -
- +
_
+ +
+ + + - - + - ++
+ +
--+_+ +- Ca++
Ca Ca + + Ca+ --
--+_+ +- -Ca + Ca+2+- +
Ca + - C- 2+ +
- _ -
+ -Ca++-+ Ca + - Ca+2
- Ca Ca
Ca++ + - + - - + -+ -
+
Ca+2 Ca++ + -
Ca
Sodium to Calcium Clay

Ca Ca++
Na+ Na+ Ca++ Ca++
Ca++
Ca++ Ca++

Na+ Ca++
Ca++
Na+ Ca++ Ca++

Na+ Ca
Ca++ Ca Ca
Na+
N
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.
edges Most polymers in drilling fluids tend to
be of this type.
 _ _
- +- +
+- + _
- - +
+ +
_ _
_
_
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.
h

 Chemically disperse

 Calcium Precipitation
 Chemically disperse

One way
y to deflocculate,, or chemically
y disperse,
p , a clay
y p
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.

Eff t off Clays

Effect Cl i Drilling
in D illi Fl id
Fluids:

 Viscosity normal

 Yield Low

 Fluid loss Low

 Calcium Precipitation

The most effective way

y to remove the flocculating
g 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

C SO4+Na
CaSO +N 2CO3→CaCO
C CO3+Na
+N 2SO4

In the previous chemical equation, calcium is precipitated and

rendered inert.
inert

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

 - +- +
+- +
_ + _
_ -
+
_ _
_
_
+ - + - + _
- +
_
- +
-
 - - -
-
- - - - - - + -
- -
- - +
-
- + - - + -
-
- +
- + +
- -
+ + - +
- -
- + +
+ - -
- - - +
- - -
+ - -
- + - - -
- - - - - - -
- + - - -
- -
- -
+ - -
- -
- - +
- -
- + -
-
- +
-
- +
+ -
- - - + + -
- + - +
- - - - +
- - - - -
-
+
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
l aggregate
t is
i an assemblage
bl off clay
l sheets.
h t

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.
When added to freshwater (does not +
-
+

-
+
+

contain a high concentration of chlorides),

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

diffuses of water into the layers

y 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
it volume
l d
decreases.

The aggregates themselves may be flocculated or deflocculated.

Effect
ff off Clays in Drilling Fluids:
 Viscosity Low
 Yield Low
 Fluid loss High
7. Swelling of clays

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

little or no swelling on hydration.
S di
Sodium-montmorillonite,
t ill it on the
th other
th hand,
h d swells
ll in
i water
t tot 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

d
due to
t the
th expansion
i off the
th crystal
t l lattice
l tti itself,
it lf and
d swelling
lli due
d to
t
the adsorption of water on surface of the clays particles.
 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).
platelet)