•

CLAY
CHEMISTRY
 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)

Silicon Atom
Oxygen Atom
 CLAY CHEMISTRY
Building Blocks

Silica
(tetrahedral)
layer

Octahedral
layer

Aluminums Silicons Hydroxyls Oxygens

 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

 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
 CLAY CHEMISTRY
HYDRATION

17 A0
Ca++ Ca++ Ca++ Ca++
o
12.1 A
 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+
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 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
– 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+ 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
 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
 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
 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
H

- -
d CATION d
H H
-
d

H H

Hydrated Ionic Diameter

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
 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 Montmorillonite Mica (Illite)

Later Charge Low Intermediate High

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

Swelling in None High None

Water
 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
+ + - - - ++ - - - - -
- + - add alkali (OH-) - - - - -
- - -
- - add acid (H+) - - - - -
-
- + - - - - -
+
+ - -+ - +
< ~ pH 6.5 > ~ pH 8
FLOCCULATED 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
Absorption of low M.W. polymer
creates overall negative charge
+ + - + acting as bridge
resulting in deflocculatin
- +- between particles
to form layer
aggregate
 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
 CLAY CHEMISTRY
Table of Viscosities vs Clay Concentration

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
 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 CMC’s become less

effective so only starches and PAC’s 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