Training Division - DFSG

CLAY CHEMISTRY

1 DRILLING FLUIDS
CLAY CHEMISTRY

Genesis and Composition

Sedimentary rocks are the most widespread rock type at the earth’s
surface.

Shale is the most abundant sedimentary rock type - clay minerals are
the chief constituent of shales.

2 DRILLING FLUIDS
CLAY CHEMISTRY
What are Clays?

Clay minerals are a part of a general group within the phyllosilicates

that contain large percentages of water trapped between the silicate

sheets.

Most clays are chemically and structurally analogous to other

phyllosilicates but contain varying amounts of water and allow more

substitution of their cations.

3 DRILLING FLUIDS
CLAY CHEMISTRY CLAY CHEMISTRY
Groups of Clay

Clay minerals are divided into 7 major groups:

Kaolinite
Illite
Chlorite
Montmorillonite (Smectite)
Mixed Layer
Vermiculite
Attapulgite

Each exhibits different characteristics and was deposited in a different

environment!

Montmorillonite/Smectite clays are expandable, thus absorb water

Kaolinite, Illite, Chlorite are not expandable, thus do not absorb water.

4 DRILLING FLUIDS
CLAY CHEMISTRY CLAY CHEMISTRY
Why Are Clays Important ?

Clays in the Drilling Fluid :

• Bentonite (gel, smectite, montmorillonite) for viscosity and fluid
loss control in some WBM
• Organophilic bentonite for viscosity and fluid loss control in NAF
system
• Bentonite is a key component of MMH systems
• Attapulgite for viscosity in salt
• Sepiolite for viscosity in very high temperature WBM
• Drilled solids help with fluid loss control but can give unwanted
viscosity
Clays in Rocks :
• In shales / mud rocks / clays causing possible drilling problems
• In reservoirs giving possible formation damage
5 DRILLING FLUIDS
CLAY CHEMISTRY CLAY CHEMISTRY
Chemical Composition of Clays

Major Constituents
• Silica
• Aluminum
• Water
Minor Constituents
• Iron
• Magnesium
• Sodium
• Potassium
Physical Properties (structural details)
• Fine size
• Large surface area
• Chemical reactivity of the surface
6 DRILLING FLUIDS
CLAY CHEMISTRY CLAY CHEMISTRY
Building Blocks

There are two basic building units from which all the different clay
minerals are constructed :

The Octahedral Layer

This consists of two sheets of closely packed hydroxoyl ions in
which aluminum, iron or magnesium ions are embedded.

Aluminium
Hydroxyl ion
7 DRILLING FLUIDS
CLAY CHEMISTRY CLAY CHEMISTRY
Building Blocks
The Octahedral Layer
In each octahedral unit an aluminium (or magnesium) atom is
located in the centre of the octahedron, equidistant from the
six oxygen atoms.

8 DRILLING FLUIDS
 CLAY CHEMISTRY CLAY CHEMISTRY
Building Blocks

The Tetrahedral unit

In each tetrahedral unit, a silicon atom is located in the centre of the
tetrahedron, equidistant from the four oxygen atoms. (The OH
groups may replace the oxygen atoms, if needed to electrically
balance the structure.)

(a) (b)

Silicon Atom
Oxygen Atom
9 DRILLING FLUIDS
 CLAY CHEMISTRY CLAY CHEMISTRY
Building Blocks

Tetrahedral Layer
In each tetrahedral unit a silicon atom is located in the centre of the
tetrahedron, equidistant from the four oxygen atoms.

10 DRILLING FLUIDS
CLAY CHEMISTRY CLAY CHEMISTRY
Building Blocks

Silica
(tetrahedral)
layer

Octahedral
layer

Aluminums Silicons Hydroxyls Oxygens

11 DRILLING FLUIDS
CLAY CHEMISTRY

Building Blocks – Smectite/Illite

12 DRILLING FLUIDS
CLAY CHEMISTRY -SMECTITE

13 DRILLING FLUIDS
CLAY CHEMISTRY CLAY CHEMISTRY
Clay Structures

KEY: SILICATE SHEET (T) ALUMINA SHEET (O)

KAOLINITE: TO or 1:1

MONTMORILLONITE + + + TOT or 2:1

AND MICA (INCLUDE ILLITE) :

CHLORITE: TOT :0: TOT or 2:1:1

ATTAPULGITE/SEPIOLITE: TOT or 2:1

14 DRILLING FLUIDS
CLAY CHEMISTRY
Comparison of Structures
Property Kaolin Mica Mont Attap Chlorite

Layer type 1:1 2:1 2:1 2:1 2:1:1

Crystal
Structure Sheet Sheet Sheet Sheet Sheet

Particle Hexagonal Extensive Flakes Needles Plates

Shape Plate Plates

Particle 0.5 - 5 0.5 - Large 0.1 - 2 0.1 - 1 0.1 - 5

Size (µ) Sheets

Surface Area
BET-N2-m2/g 15 - 20 50 - 110 30 - 80 200 140
BET-H2O-m2/g - - 200 - 800 - -

CEC-meq/100g 3 - 15 10 - 40 80 - 150 15 - 25 10 - 40

Viscosity
in Water Low Low High High Low

Effects of
Salts Flocculates Flocculates Flocculates Flocculates Flocculates

15 DRILLING FLUIDS
CLAY CHEMISTRY CLAY CHEMISTRY
Hydration

17 A0
Ca++ Ca++ Ca++ Ca++
o
12.1 A

16 DRILLING FLUIDS
CLAY CHEMISTRY CLAY CHEMISTRY
Hydration

Na+

Na+ Na+

Na+

Na+ Na+
+ Expansion from 17 A
water to infinite separation
Na+ Na+
o
9.8 A
Na+

Na+ Na+

Na+

17 DRILLING FLUIDS
CLAY CHEMISTRY CLAY CHEMISTRY

18 DRILLING FLUIDS
CLAY CHEMISTRY CLAY CHEMISTRY
Charges on Clay Particles

Charges on clays are important as they determine properties such as :

• Ion Exchange
• Swelling Behavior
• Viscosity of Muds

Charges can arise from :

• Broken edges on clay particles (Induced charges)
• Substitution of Ions in the clay structure (Permanent charges)

19 DRILLING FLUIDS
CLAY CHEMISTRY CLAY CHEMISTRY
Broken Edge Charges

When a clay sheet is broken, the exposed edges will have unbalanced
charges which can be either positive or negative.

In an acidic environment the charges will tend to be positive. In an

alkaline environment charges tend to be negative.

One reason for keeping an alkaline pH in the drilling mud is to keep all the
clay charges negative. The negative charges will repel each other thus
reducing the tendency for flocculation.

20 DRILLING FLUIDS
CLAY CHEMISTRY CLAY CHEMISTRY
Charges Due to Ion Substitution

All Si Charges
All Al
All Si
} Balanced :
Net Charge = Zero

But, commonly (especially in montmorillonite & mica) there are cation

substitutions in both the octahedral and tetrahedral layers
Tetrahedral Layer : Some Si4+ can be replaced by Al3+ or Fe3+
Octahedral Layer : Some Al3+ can be replaced by Mg2+ or Fe2+
• These substitutions produce sheets with net negative charge – satisfied by
adsorption of cations.
• Unlike edge charges, these are permanent and not affected by pH changes
• Isomorphous substitution is the main reason why clays have ion exchange
properties and is the reason why montmorillonite swells in water

21 DRILLING FLUIDS
CLAY CHEMISTRY CLAY CHEMISTRY
Ion Exchange Properties of Clays

The negative charge generated by isomorphous substitution is

balanced by cations held near the clay surface.
+ +

+ +

Common charge - balancing cations are Na, K, Ca, Mg; these cations
are readily exchangeable in montmorillonite
Na+ Na+ K+ K+
eg. KCl solution +
Na+ Na+ K+ K+

Cation exchange capacity of clay can be measured by methylene blue

test (MBT) or chemical analysis of displaced cations

22 DRILLING FLUIDS
CLAY CHEMISTRY CLAY CHEMISTRY
Cation Exchange

Factors Affecting Replaceability of Exchangeable Cations

Nature of Clay Mineral

• Montmorillonite : Easy
• Mica / Illite : Difficult
• Chlorite : “Impossible”
Nature of original and replacing cations
Concentration of exchange solution

23 DRILLING FLUIDS
CLAY CHEMISTRY
Building Blocks

SMECTITE
Al+++ in Octahedral layer iso-morphously substituted
by Mg++
Surplus Negative charge satisfied by a Cation – Na+
EXCHANGEABLE CATION – CEC Cation Exchange
Capacity

ILLITE
Si++++ in Tetrahedral layer iso-morphously
substituted by Al+++
Surplus Negative charge satisfied by a Cation – K+

24 DRILLING FLUIDS
CLAY CHEMISTRY CLAY CHEMISTRY
Cation Exchange

Assuming all the cation concentrations are the same, the order of
increasing replacing power of cations is generally :

Li+ < Na+ < K+ < Mg2+ < Ca2+ < H+

eg : At equal concentrations potassium will displace more sodium

than sodium will displace potassium.

Increasing the concentration of any given cation will increase the

probability that it will displace another cation.
eg : It is possible for high concentrations of potassium to displace
calcium

25 DRILLING FLUIDS
CLAY CHEMISTRY CLAY CHEMISTRY
Hydration of Cations

Hydration of clays is due to adsorption and absorption of water.

Adsorption is the attachment of water to the external surface of

clay particles

Absorption is the entry of water into the structure of the clay

particles, either by osmosis or capillary action.

26 DRILLING FLUIDS
CLAY CHEMISTRY CLAY CHEMISTRY
Hydration of Cations

Hydration properties of the exchange cations have an important

influence on clay properties.

Hydration of cations depends on their charge and size.

High charge & small diameter cations are usually most highly
hydrated

Low charge & large diameter cations are usually least

hydrated

27 DRILLING FLUIDS
CLAY CHEMISTRY CLAY CHEMISTRY
Clay Hydration
The important diameter is the hydrated ionic diameter.

H
H
CATION
Hydrated Ionic Diameter d
- d-

H - H
d

H H
Atom Dehydrated Ion Hydrated Ion
Diameter A° Diameter A°

Na - Sodium 1.90 11.2

K - Potassium 2.66 7.6
Cs - Cesium 3.34 7.6
Mg - Magnesium 1.30 21.6
Ca - Calcium 1.90 19.0

28 DRILLING FLUIDS
CLAY CHEMISTRY CLAY CHEMISTRY
Clay Swelling

The most common swelling clay mineral is montmorillonite.

Montmorillonite (bentonite) is used in some drilling fluids to give

viscosity and fluid loss control.

Montmorillonite is found in many reactive shales.

Montmorillonite is found in some sandstones (including reservoir

sands).

The amount of water taken up by a montmorillonite (& hence the

degree of swelling) depends on :

• Layer charge of the clay / Ion exchange

• Nature of the exchangeable cation
• Nature of the external solution

29 DRILLING FLUIDS
CLAY CHEMISTRY CLAY CHEMISTRY
Clay Swelling

Cations Exchange Capacity / Layer Charge

Kaolinite Montmorillonite Mica (Illite)

Layer Charge Low Intermediate High

CEC Low (3-15 meq/100g) Intermediate (80-150) Low (10-40)

Swelling in None High None

Water

30 DRILLING FLUIDS
CLAY CHEMISTRY CLAY CHEMISTRY
Clay Swelling : Nature of Exchangeable Cation

Swelling promoted by highly hydrated, low charge exchangeable cations

eg. Li+ , Na+

Swelling reduced by high charge, less hydrated cations

eg. Al3+

K+ reduces swelling because poorly hydrated even though low charge.

Ca2+, Mg2+ reduces swelling because high charge, though highly

hydrated.

31 DRILLING FLUIDS
CLAY CHEMISTRY CLAY CHEMISTRY

32 DRILLING FLUIDS
CLAY CHEMISTRY CLAY CHEMISTRY

33 DRILLING FLUIDS
 CLAY
CLAY CHEMISTRY CHEMISTRY

34 DRILLING FLUIDS
CLAY CHEMISTRY CLAY CHEMISTRY

35 DRILLING FLUIDS
CLAY CHEMISTRY CLAY CHEMISTRY
Clay Dispersion / Deflocculation

There are four basic colloidal states of clay particles in a fluid :

• Deflocculated. There is an overall repulsive force between the

particles. This is done by ensuring all the particles have the
same charge. (The particles may be aggregates)

• Flocculated. There are net attractive forces for the particles and
they can associate with each other to form a loose structure.

• Aggregated. The clay sheets are still attached to each other and
hydration has not occurred, or the hydration process has been
reversed.

• Dispersed. This is where the aggregates have all been broken

down. The dispersed clays may be flocculated or deflocculated.

36 DRILLING FLUIDS
CLAY CHEMISTRY CLAY CHEMISTRY

37 DRILLING FLUIDS
CLAY CHEMISTRY CLAY CHEMISTRY
Clay Dispersion

Mechanical energy causes DISPERSION of aggregates

MECHANICAL

ENERGY

Mechanical energy can also break individual mineral grains

MECHANICAL

ENERGY

Leads to increased surface area of solids

38 DRILLING FLUIDS
CLAY CHEMISTRY CLAY CHEMISTRY
Clay Deflocculation

Chemical energy is used to deflocculate clays

chemical energy

FLOCCULATED DEFLOCCULATED

The state of deflocculation is determined by surface charges and

electrical double layers surrounding particles in suspension

39 DRILLING FLUIDS
CLAY CHEMISTRY CLAY CHEMISTRY
Clay Deflocculation

- - - - -
1. Change pH
+ + - - - ++ - - - - -
- + - add alkali (OH-) - - - - -
- - -
- - add acid (H+) - - - - -
-
- + - - - - -
+
+ - -+ - +
< ~ pH 6.5 > ~ pH 8
FLOCCULATED DEFLOCCULATED

2. Add chemical deflocculants

+ add deflocculant - -
+ - - - + -
- - - - - - -
+ - -
- - - -
- -
-
-
+ + - - - - -
+ - - - + -
40 DRILLING FLUIDS
CLAY CHEMISTRY CLAY CHEMISTRY
Effect of Clay Dispersion/Deflocculation on Suspension Viscosity

To increase viscosity
• Increase level of solids
• Add high molecular weight viscosifying polymer
• Flocculate with calcium or other polyvalent cation
• Flocculate with salts
• Flocculate with low pH conditions

To decrease viscosity
• Dilute with water
• Deflocculate with low molecular weight polymers
• Remove calcium by chemical treatment
• Deflocculate with higher pH conditions

41 DRILLING FLUIDS
CLAY CHEMISTRY CLAY CHEMISTRY
Clay States
Flocculated clay
- -+-+
+- - + - +- +
+- +-
+- + - + -
Deflocculant +- +- Flocculant

- - - - - - - - -

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

+- +- + +- + -+
+ - -
+ High M.W. polymer
Absorption of low M.W. polymer
creates overall negative charge
+ + - + acting as bridge
resulting in deflocculation
- +- between particles
to form layer
aggregate

42 DRILLING FLUIDS
CLAY CHEMISTRY CLAY CHEMISTRY
Clay States

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

Na+
Na+ + Ca++ Ca++

Ca++
Na+ Na+
Flocculated system
Dispersed sodium Na+ Ca++ caused by calcium
montmorilonite bridges between particles

Na+ Na+
Ca++
Ca++
Na+
Aggregated calcium montmorilonite
43 DRILLING FLUIDS
CLAY CHEMISTRY CLAY CHEMISTRY
Table of Viscosities in Different Solutions

20
VISCOSITY (cP)

15

10 A Dry bentonite in salt solution

B Dry bentonite in calcium solution

5
A
B

0
SALT 50,000 100,000 150,000 200,000
CALCIUM 1500 3000 4500 6000

PPM
44 DRILLING FLUIDS
CLAY CHEMISTRY CLAY CHEMISTRY
Clays in Drilling Fluids

Clays are added to some water based muds to give :

Viscosity : Bentonite, Sepiolite / Attapulgite
Fluid loss control : Bentonite

Organophilic bentonite added to oil based muds to give

viscosity and fluid loss control.

Clays entrained in mud as drilled solids. These give

viscosity and fluid loss control.

45 DRILLING FLUIDS
CLAY CHEMISTRY CLAY CHEMISTRY
Grades of Bentonite

Wyoming bentonite
Pure sodium montmorillonite. This is the best grade of bentonite

API Bentonite
Is montmorillonite that meets API standards on viscosity and
filtration control. It may be (and usually is) treated with
polymers/extenders (Sodium Polyacrylate) to attain the API grade.

OCMA Bentonite
Calcium montmorillonite

46 DRILLING FLUIDS