Mufti Ghazali

CLAY CHEMISTRY
Clay
The 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.
Clay minerals are divided into four major groups. The Kaolinite Group This group has three members (kaolinite, dickite and nacrite) The Montmorillonite/Smectite Group This group is composed of several minerals including talc, vermiculite, sauconite, saponite, nontronite and montmorillonite The Illite (or The Clay-mica) Group The mineral illite is the only common mineral represented, however it is a main component of shales. The Chlorite Group This group is not always considered a part of the clays and is sometimes left alone as a separate group within the phyllosilicates.

CLAY CHEMISTRY
Why Are Clays Important ? Clays in the 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 / sepiolite for viscosity in salt & 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

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

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

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)

Oxygen Atom

Silicon Atom

CLAY CHEMISTRY
Building Blocks
Silica (tetrahedral) layer

Octahedral layer

Aluminums

Silicons

Hydroxyls

Oxygens

CLAY CHEMISTRY
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:

TOT or 2:1

CLAY CHEMISTRY
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 Sheet Hexagonal Plate 0.5 - 5

Mica
2:1 Sheet Extensive Plates 0.5 - Large Sheets 50 - 110 10 - 40

Mont
2:1 Sheet Flakes 0.1 - 2

Attap
2:1 Sheet Needles 0.1 - 1

Chlorite
2:1:1 Sheet Plates 0.1 - 5

15 - 20 3 - 15

30 - 80 200 - 800 80 - 150

200 15 - 25

140 10 - 40

Low
Flocculates

Low
Flocculates

High
Flocculates

High
Flocculates

Low
Flocculates

CLAY CHEMISTRY
HYDRATION

0 17 A

Ca++

Ca++

Ca++

Ca++

12.1 A

CLAY CHEMISTRY
HYDRATION

Na+ Na+ Na+ Na+ Na+ Na+ Na+ Na+

+ water 9.8 A
o

Expansion from 17 A to infinite separation

Na+

Na+ Na+

Na+

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 Substitution of Ions in the clay structure

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.

CLAY CHEMISTRY
Charges Due to Ion Substitution
All Si All Al All Si

Charges 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 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

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+ 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

CLAY CHEMISTRY
Cation Exchange

Factors Affecting Replaceability of Exchangeable Cations

Nature of Clay Mineral

Montmorillonite
Mica / Illite Chlorite

: Easy
: Difficult : Impossible

Nature of original and replacing cations Concentration of exchange solution

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+ < Mg++ < Ca++ < 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

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

CLAY CHEMISTRY
Clay Hydration

The important diameter is the hydrated ionic diameter.

H d CATION d H d H

Atom

Dehydrated Ion Hydrated Ion Diameter A Diameter A 1.90 2.66 3.34 1.30 1.90 11.2 7.6 7.6 21.6 19.0

Hydrated Ionic Diameter

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

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

CLAY CHEMISTRY
Clay Swelling

Cations Exchange Capacity / Layer Charge

Kaolinite Later Charge Low CEC Swelling in Water Montmorillonite Intermediate Mica (Illite) High

Low (3-15 meq/100g) Intermediate (80-150) Low (10-40) None High None

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.

CLAY CHEMISTRY

CLAY CHEMISTRY

CLAY CHEMISTRY

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.

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

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

CLAY CHEMISTRY
Clay Deflocculation
-

1. Change pH
+ + - - - ++ + - - - + + + -+ < ~ pH 6.5 FLOCCULATED

add alkali (OH-) add acid (H+) +

> ~ pH 8 DEFLOCCULATED

2. Add chemical deflocculants

+ -

+ +

+ + -

add deflocculant
-

+ - - - +

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 Disperse with low molecular weight polymers Remove calcium by chemical treatment Disperse with higher pH conditions

CLAY CHEMISTRY
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 deflocculatin

+ +- ++

+ - +-

CLAY CHEMISTRY
Clay States
Na+ Na+ Na+ Na+ Na+ Na+ Ca++ Na+ Ca++ Na+

Na+
Na+ Na+

+ Ca++
Ca++

Ca++

Dispersed sodium montmorilonite

Na+

Na+

Ca++

Flocculated system caused by calcium bridges between particles

Na+

Ca++

Ca++ Na+

Aggregated calcium montmorilonite

CLAY CHEMISTRY
Table of Viscosities vs Clay Concentration

20

VISCOSITY (cP)

15

10

A B

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

PPM

SALT CALCIUM

50,000 1500

100,000 3000

150,000 4500

200,000 6000

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.

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

CLAY CHEMISTRY
Bentonite Mud Systems
Instructions for prehydrating bentonite Treat out any hardness (Calcium and Magnesium) with soda ash. Increase pH to 9 - 10. (1/4 - 1/2 ppb caustic) Add 30 - 35 ppb API bentonite, or 40 - 50 ppb OCMA bentonite. Always try to keep one pit for prehydrating bentonite. This avoids contamination. Ideally chlorides should be below 2000 mg/l and hardness levels below 100 mg/l. For maximum cost effectiveness the bentonite needs eight hours to fully hydrate.

For speed the caustic can be added after the bentonite addition.
Bentonite quality may vary greatly so adjust quantities accordingly.

CLAY CHEMISTRY
Spud Mud
Use bentonite as high viscosity mud for top hole drilling. Can be the whole circulating system or just as sweeps. PROPERTIES - Funnel viscosity should be greater than 100 seconds. MIXING INSTRUCTIONS - Add 70% by volume of the prehydrated gel and 30% by volume of sea water or drill water. Add 1 ppb lime just prior to pumping. (Lime can be added through the hopper or over the pits). Check viscosity; if it is too low add a higher percentage of PHG. If too high increase the water concentration.

CLAY CHEMISTRY
Bentonite Muds
1. Fresh water bentonite muds. 2. Sea water bentonite muds.

3. High chloride concentration bentonite muds.

PROPERTIES - as required. Normally PV as low as possible. YP 12 - 20. Fluid loss as required. MIXING INSTRUCTIONS - The bentonite concentration will normally be 15 to 20 ppb. For systems 2 and 3 the bentonite will need to be prehydrated in fresh water and then diluted back with sea water to attain the desired concentration. To increase the viscosity, increase the bentonite concentration. To decrease the viscosity : Decrease the bentonite concentration by dilution or adding new premix. Decrease the solids content.

CLAY CHEMISTRY
Fluid Loss Control May be Required Fresh and sea water systems should use : CMC (up to 2 ppb) - Deflocculates system PAC (up to 2 ppb) - Deflocculates system Starch (up to 6 ppb) - Will not deflocculate system or use a combination of the above

At higher chloride levels the CMCs become less effective so only starches and PACs should be used.

CLAY CHEMISTRY
Problems with Bentonite Muds
Calcium ions (from anhydrite/gypsum or cement) will flocculate the system. A deflocculant may be needed, also remove the calcium ion with soda ash or bicarbonate. Any increase or decrease in the chloride concentration (whether by formation fluids or from drilling salt deposits) will flocculate the system. (This will increase the viscosity and fluid loss. Increase additions of CMC or PAC to deflocculate.) Viscosity may be reduced with a thinner prior to casing runs the reduce surge pressures. High viscosities and gel strengths are usually an indication of excessive solids. Reduce solids conc. by solids removal equipment or dilutions. Prior to drilling out any cement the system should be pretreated with 1/2 ppb sodium bicarbonate.
Note : flocculation due to polymers increases the fluid loss control Note : flocculation due to higher chlorides or multivalent cations reduces the fluid loss control

Compiled from my many source