CLAY CHEMISTRY

AND
CLAYS IN DRILLING FLUIDS
Why Are Clays Important ?
The elements that go to make up clay minerals make up 80%
of the mass of the earth (Al 8.1%, Si 27.7%, O 46.6%)
Clays in Rocks :
In shales / mud rocks / clays causing possible drilling problems
In reservoirs giving possible formation damage
Clays in the Fluid :
Bentonite (gel, sodium montmorillonite) for viscosity and fluid loss
control in some WBM
Organophilic bentonite for viscosity and fluid loss control in OBM
Attapulgite for viscosity in salt & very high temperature WBM
Drilled solids help with fluid loss control but can give unwanted
viscosity
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
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 oxygen or

hydroxides in which aluminum (Gibbsite), iron or
magnesium (brucite) ions are embedded.
Building blocks
The tetrahedral Layer

(A) (B)

In each tetrahedral unit, a silicon atom is located in the

center of the tetrahedron, equidistant from the four oxygen
atoms.
Note that when viewed from above this gives a hexagonal
opening.
Building blocks

Tetrahedral and octahedral sheets may

combine in different combinations to form
over 26 different clay minerals
The type of clay mineral will depend on
the ratios of the silica to octahedral layer .
The nature of ions inbeded in these
structures.
Other ions associated with the structures.
 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

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 Little or none Flocculates
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
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
 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+
e.g.. 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
 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
 Cation exchange
Different cations have different attractions for the exchange
sites

Assuming all the cation concentrations are the same, the

order of increasing replacing power of cations is generally :
Li+ < Na+ < K+ < Mg2+ < Ca2+ < H+

e.g. : 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.
e.g. : It is possible for high concentrations of potassium to displace
calcium
Hydration of Cations
The 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 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
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.
Edge charges
Sign of edge charges depends on solution pH

O OH O OH O OH

Si Si Si

H+ OH-
O O O

AlOH 2 + AlOH Al O-

OH OH OH
Clay Mineral Groups
There are over 400 mineral and rock names to
describe clay minerals. Only the following are
common and applicable to drilling fluids
chemistry
Kaolin
Composed of single tetrahedral sheet and single
octahedral sheet
Charges within structure are balanced with few
substitutions
Strong hydrogen bonding between layers limits
swelling
Edge charges are sensitive to pH
Clay Mineral Groups

Micas
2:1 lattice with 2 silica sheets sandwiching an
octahedral layer
Ion replacement occurs in the TETRAHEDRAL
layer
Charge deficiency is balanced by potassium ions
The Potassium fits neatly in the hexagonal holes
made by the silica tetrahedral and securely binds
the separate layers together.
Clay Mineral Groups
Montmorillonite
A 2:1 lattice structure very similar to mica
Ionic substitution occurs in the OCTAHEDRAL layer
Cations are unable to approach close enough to completely loose
their ionic character
The residual ionic character provides attractive forces for
adsorbing water.
Sepiolite and Attapulgite
Both consist of long needles.
They cannot swell but have a large surface are and can bind water
strongly. This means that they are effective viscosifiers
Chlorite
 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 sandstone (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 Swelling :
Nature of Exchangeable Cation

Swelling promoted by highly hydrated, low charge

exchangeable cations

e.g.. Li+ , Na+

Swelling reduced by high charge, less hydrated cations

e.g.. Al3+

K+ reduces swelling because poorly hydrated even

though low charge.

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

highly hydrated.
 Clay Swelling
High Salinity Solutions Reduce Clay Swelling
relative distribution of particles relative distribution of particles
with a given spacing, % with a given spacing, %
100 100

K+
78 78
K+
Ca2+ Ca2+
60
Na+
60

25
Na+ 25

0 0
0 10 20 30 40 50 0 10 20 30 40 50

space between sheets A space between sheets A

Effect of Low Salt Concentration on Effect of High Salt Concentration on

space between sheets space between sheets
Clay Dispersion / Deflocculation

Clay particles in a fluid can be :

Deflocculated

Flocculated

Aggregated

Dispersed

Degree of dispersion / deflocculation of clays will

affect viscosity, fluid loss control and shale
inhibition.
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.
Colloidal states

Dispersed and
deflocculated Aggregated but
deflocculated

Edge to face Edge to edge

flocculated flocculated
but dispersed but dispersed

Edge to face Edge to edge

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

2. Add chemical deflocculants

+
add deflocculant - -
+ - - - + -
- - - - - - -
+ - -
- - - -
- -
-
-
+ + - - - - -
+ - - - + -
Clay Deflocculation (cont)
3. Double layers

+ + + + Add salt + + + +

+ + + +
+ + + +
Remove salt + +
+ + + +
+ + + +
+ +
LOW SALINITY HIGH SALINITY summation curve
DEFLOCCULATED FLOCCULATED
energy of
repulsion
0

energy of
attraction

WITHOUT SALT - NO FLOCCULATION distance of separation

0
 Clay Deflocculation
(Double Layers)

2000 ppm of Na+

200 ppm of Na+

2% Na+
energy of energy of
repulsion repulsion
0 0

energy of energy of
attraction attraction

0 distance of separation 0 distance of separation

Intermediate Concentration High Salt Concentration

- Slow Flocculation - Rapid Flocculation
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 Flocculation

High Salt Concentration

Polyvalent Cations
Polymeric Flocculants
Low pH
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
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.
 Bentonite Mud Systems
Instructions for prehydrating bentonite
Treat out any hardness 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.
Grades of Bentonite

API Non-Treated bentonite

Pure sodium montmorillonite. This is the best
grade of bentonite
API Treated bentonite
Is montmorillonite that reaches certain standards
on viscosity and filtration control as set out by
API. It may be treated with polymers and/or soda
ash to attain the API grade.
OCMA Bentonite
Treated Calcium montmorillonite, commonly used
in Europe
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
Spud Mud
Use bentonite as high viscosity mud for top hole drilling. Can
be the whole circulating system or just as sweeps.

PROPERTIES - Yield Point should be higher than 30-40

lb/100ft2

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.
 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.
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.
 Problems Associated 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 eqpt. 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