5/21/2010

Global Research & Technology Centre/ GRTC

Training Department

CLAY
CHEMISTRY

SCOMI OILTOOLS

Introduction

Clays play a major role in drilling fluid tech.

Every stage of drilling a hole brings in contact with
the Clays.
Chemical & Mechanical properties of the rock
depend on the type & quantity of clay minerals.
Understanding of clay chemistry is essential in
selection of drilling fluid system & bore hole
stability.

SCOMI OILTOOLS

1
 5/21/2010

Clays - Origin

Clays originate from the Rocks due to weathering

process.

Sedimentary rocks are the most abundant rock type

on the Earths Surface and Crust.

Shale is one most abundant rock type and clay

minerals, its chief constituents.

SCOMI OILTOOLS

Genesis and Composition

Chemically Clays are Aluminosilicates.
Clay minerals are a part of a general group within
the phyllosilicates (layered silicates).
Most clays are chemically and structurally analogous
to each other but contain varying amounts of water
and allow varying levels of substitution in their
cations
Shales are classified by age, water content, clay
content, and type o hardness of the shale.

SCOMI OILTOOLS

2
 5/21/2010

Composition of Clays
Major Constituents
Silica, Aluminum and Oxygen
(The above 3 elements constitute >80% of earths
mass)

Minor Constituents
Iron, Magnesium, Sodium and Potassium.

SCOMI OILTOOLS

Composition of Clays
Physical Properties (structural details)

Size- Fine to Very Fine (0.1-5)

Surface area- Large to Very Large (12-
300M2/g)
Chemically Reactive Surface.

SCOMI OILTOOLS

3
 5/21/2010

Building Blocks
There are two basic building units from which all the
different clay minerals are constructed :
Tetrahedral Layer
In each tetrahedral unit a silicon atom is located in the
centre of the tetrahedron, equidistant from the four
oxygen atoms.

SCOMI OILTOOLS

Building Blocks
The Tetrahedral Unit

The OH groups replace the oxygen atoms to electrically

balance the structure.

(a) (b)

Oxygen Atom Silicon Atom

SCOMI OILTOOLS

4
 5/21/2010

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.

SCOMI OILTOOLS

Building Blocks
The Octahedral Layer
This consists of two sheets of closely packed hydroxoyl ions
in which aluminum, iron or magnesium ions are
embedded.

SCOMI OILTOOLS

5
 5/21/2010

Building Blocks

Silica
(tetrahedral)
layer

Octahedral
layer

Hydrox Oxyge
Aluminums Silicons yls ns

SCOMI OILTOOLS

Groups of Clay
There are > 400 reported clay mineral names due to
different combination of the basic building blocks and 26
different clay mineral groups.

Clay minerals are divided into 7 major groups for drilling

fluid purpose:

1.Kaolinite, 2.Illite, 3.Chlorite, 4.Mica,

5.Montmorillonite, 6. Attapulgite

SCOMI OILTOOLS

6
 5/21/2010

Groups of Clay

Each clay mineral type 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.

SCOMI OILTOOLS

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
SCOMI OILTOOLS

7
 5/21/2010

Why are Clays Important

Clays in Rocks :

In shales / mud rocks / clays causing possible

drilling problems

In reservoirs giving possible formation

damage

SCOMI OILTOOLS

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

SCOMI OILTOOLS

8
 5/21/2010

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 () 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

SCOMI OILTOOLS

Hydration

0
17 A
Ca++ Ca++ Ca++ Ca++
o
12.1 A

Limited separation between clay platelets

due to divalent charge of calcium.
Divalent charge cations will hold the clay
platelets closer together.
SCOMI OILTOOLS

9
 5/21/2010

Hydration
Na+

Na+ Na+

Na+

Na+ Na+ Expansion from 17 A

+
Na+ Na+ water to infinite separation
o
9.8 A
Na+

Na+ Na+
Infinite separation between clay platelets,
Na+
due to monovalent charge of sodium.
Monovalent charge cations will not create a
bonding power between platelets.

SCOMI OILTOOLS

Hydration of Sodium and Calcium

Montmorillonites

SCOMI OILTOOLS

10
 5/21/2010

Charges on Clay Particles

Clay charges 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)

SCOMI OILTOOLS

Broken Edge Charges

Clay sheets can be broken due to mechanical action.

When a clay sheet is broken, the exposed edges will have
unbalanced charges which can either be +ve or -ve.
In an acidic environment the charges will tend to be +ve. In an
alkaline environment charges tend to be -ve.
One reason for keeping an alkaline pH in the drilling mud is to
keep all the clay charges -ve.
The -ve charges will repel each other thus reducing the
tendency for flocculation.

SCOMI OILTOOLS

11
 5/21/2010

Charges Due to Ion Substitution

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

Tetrahedral Layer : Some Si4+ can be replaced by Al3+ or Fe3+

Octahedral Layer : Some Al3+ can be replaced by Mg2+ or Fe2+

SCOMI OILTOOLS

Charges Due to Ion Substitution

Not All Si Charges
Not All Al

Not All Si
} Not Balanced :
Net Charge

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

SCOMI OILTOOLS

12
 5/21/2010

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
SCOMI OILTOOLS

Cation Exchange
Factors Affecting Substitution of Exchangeable Cations:
Nature of Clay Mineral
Montmorillonite : Easy
Mica / Illite : Difficult
Chlorite : Impossible

Nature of original and substituted cations

Concentration of exchange solution

SCOMI OILTOOLS

13
 5/21/2010

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+

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.

It is possible for high concentrations of potassium to

displace calcium

SCOMI OILTOOLS

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

Adsorption is the attachment of water molecules to the

external surface of clay particles, causing interlayer swelling.
It is either physical or chemical adsorption.

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

particles, either by osmosis or by capillary action. It is only
physical and weak forces.

SCOMI OILTOOLS

14
 5/21/2010

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

SCOMI OILTOOLS

Clay Hydration
The important diameter is the hydrated ionic diameter.

H
H
CATION
Hydrated Ionic Diameter
- -

H - H

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

SCOMI OILTOOLS

15
 5/21/2010

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
SCOMI OILTOOLS

Clay Swelling
Cations Exchange Capacity / Layer Charge

Kaolinite Montmorillonite Mica (Illite)

Layer Charge Low Intermediate High

CEC Low (3-15) Intermediate (80-150)Low (10-40)

Swelling in None High None

Water

SCOMI OILTOOLS

16
 5/21/2010

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.
SCOMI OILTOOLS

SCOMI OILTOOLS

17
 5/21/2010

SCOMI OILTOOLS

SCOMI OILTOOLS

18
 5/21/2010

SCOMI OILTOOLS

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.

SCOMI OILTOOLS

19
 5/21/2010

Clay Dispersion / Deflocculation

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.

SCOMI OILTOOLS

SCOMI OILTOOLS

20
 5/21/2010

Clay Dispersion
Mechanical energy causes DISPERSION of aggregates

MECHANICAL

ENERGY

MECHANICAL

ENERGY

Mechanical energy can also break individual mineral grains

Leads to increased surface area of solids
SCOMI OILTOOLS

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
SCOMI OILTOOLS

21
 5/21/2010

Clay Deflocculation

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

2. Add chemical deflocculants

+ - -
add deflocculant
+ - - - + -
- - - - - - -
+ - -
- - - -
- -
-
-
+ + - - - - -
+ - - - + -
SCOMI OILTOOLS

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

SCOMI OILTOOLS

22
 5/21/2010

Effect of Clay Dispersion/Deflocculation

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

SCOMI OILTOOLS

Clay States
Flocculated clay
- -+-+
+- - + - +- +
+- -
+ + -+
Deflocculant - + -+- +- Flocculant

- - - - - - - - -

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

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

SCOMI OILTOOLS

23
 5/21/2010

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
SCOMI OILTOOLS

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
SCOMI OILTOOLS

24
 5/21/2010

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.

SCOMI OILTOOLS

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

SCOMI OILTOOLS

25