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Global Research & Technology Centre/ GRTC Training Department

CLAY CHEMISTRY

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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.

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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.

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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.

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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.

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Composition of Clays
Physical Properties (structural details) Size- Fine to Very Fine (0.1-5) Surface area- Large to Very Large (12300M2/g) Chemically Reactive Surface.

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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.

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Building Blocks
The Tetrahedral Unit
The OH groups replace the oxygen atoms to electrically balance the structure.

(a)

(b)

Oxygen Atom
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Silicon Atom

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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.

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

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Building Blocks
Silica (tetrahedral) layer Octahedral layer

Aluminums

Silicons

Hydrox yls

Oxyge ns

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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

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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.

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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
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Why are Clays Important

Clays in Rocks : In shales / mud rocks / clays causing possible drilling problems

In reservoirs giving possible formation damage

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Clay Structures
KEY:
SILICATE SHEET (T) KAOLINITE:
TO or 1:1

ALUMINA SHEET (O)

MONTMORILLONITE AND MICA (INCLUDE ILLITE) :

TOT or 2:1

CHLORITE:

TOT :0: TOT or 2:1:1

ATTAPULGITE/SEPIOLITE:
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TOT or 2:1

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Comparison of Structures
Property Layer type Crystal Structure Particle Shape Particle Size () Surface Area BET-N2-m2/g BET-H2O-m2/g CEC-meq/100g Viscosity in Water Effects of Salts Kaolin 1:1 Mica 2:1 Mont 2:1 Attap 2:1 Chlorite 2:1:1

Sheet Hexagonal Plate 0.5 - 5

Sheet Extensive Plates 0.5 - Large Sheets

Sheet Flakes

Sheet Needles

Sheet Plates

0.1 - 2

0.1 - 1

0.1 - 5

15 - 20 3 - 15

50 - 110 10 - 40

30 - 80 200 - 800 80 - 150

200 15 - 25

140 10 - 40

Low

Low

High

High

Low

Flocculates

Flocculates

Flocculates

Flocculates

Flocculates

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Hydration

0 17 A

Ca++

Ca++
o

Ca++

Ca++

12.1 A

Limited separation between clay platelets due to divalent charge of calcium. Divalent charge cations will hold the clay platelets closer together.
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Hydration
Na+ Na+ Na+ Na+ Na+ Na+ Na+ Na+ Na+

+ water
9.8 A
o

Expansion from 17 A to infinite separation

Na+

Na+ Na+

Infinite separation between clay platelets, due to monovalent charge of sodium. Monovalent charge cations will not create a bonding power between platelets.
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Hydration of Sodium and Calcium Montmorillonites

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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)

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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.

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Charges Due to Ion Substitution

All Si All Al All Si

Charges 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+

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Charges Due to Ion Substitution

Not All Si Not All Al Not All Si

Charges 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
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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+ Na+ K+ K+ K+ K+

eg. KCl solution

+
Na+

Cation exchange capacity of clay can be measured by methylene blue test (MBT) or chemical analysis of displaced cations
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Cation Exchange
Factors Affecting Substitution of Exchangeable Cations: Nature of Clay Mineral Montmorillonite Mica / Illite Chlorite : Easy : Difficult : Impossible

Nature of original and substituted cations Concentration of exchange solution

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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
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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.

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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

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Clay Hydration
The important diameter is the hydrated ionic diameter.

CATION

Hydrated Ionic Diameter

H

Atom

Dehydrated Ion Diameter A 1.90 2.66 3.34 1.30 1.90

Hydrated Ion Diameter A 11.2 7.6 7.6 21.6 19.0

Na - Sodium K - Potassium Cs - Cesium Mg - Magnesium Ca - Calcium

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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
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Clay Swelling
Cations Exchange Capacity / Layer Charge Kaolinite Layer Charge Low CEC Swelling in Water Low (3-15) None Montmorillonite Intermediate Mica (Illite) High

Intermediate (80-150)Low (10-40) High None

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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.
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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.

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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.

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

2. Add chemical deflocculants

+
+ + add deflocculant
-

+ +
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+ - - - +

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

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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

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Clay States
Flocculated clay

-+-+ +- + - +- + +-+ + + - + -+- +Deflocculant Flocculant

-

+- +

+-

+ + -

- + + - + + -+ + +- + + High M.W. polymer + - + acting as bridge

between particles to form layer aggregate

Absorption of low M.W. polymer creates overall negative charge resulting in deflocculation

+ +- ++-

+ - +-

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Clay States
Na+ Na+ Na+ Na+ Na+ Na+ Na+ Na+ Na+ Ca++ Na+ Ca++ Na+ Ca++ Na+

+ Ca++
Ca++

Ca++

Dispersed sodium montmorilonite

Na+

Flocculated system caused by calcium bridges between particles

Na+

Ca++

Ca++ Na+

Aggregated calcium montmorilonite

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Table of Viscosities in Different Solutions

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VISCOSITY (cP)

15

10

A B

Dry bentonite in salt solution Dry bentonite in calcium solution A B

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

PPM
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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.
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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
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