Structure & Properties

of Bentonite

How does bentonite viscosify

water at <3% solids?
Why does it form filter cakes?
What Are the Special Properties of
Bentonite Used in AMCOL
Applications?

• Creates viscosity at low

concentrations in water

• Builds filter cake

 What Are the Special Properties of
Bentonite Used in AMCOL Applications?
• Creates viscosity at low concentrations in water
• Forms low permeability filter cakes
• Has very high surface area per unit mass
• Absorbs very large amounts of water
• Holds onto water very strongly
• Swells in contact with water/creates swelling pressure
• Water does not flow through a confined layer of bentonite
• Forms stable colloid in water; doesn’t settle over reasonable time
• Has very high aspect ratio (l/w)
• Platelets impermeable to gases
• Has high ion-exchange capacity
• Undergoes specific selectivity reaction with K+ ion
• Oxide/hydroxide surfaces interact with many adsorbents
• Slippery
• Available in large quantities; mined
• Cheap
• Comes in many grades
• Can derivatize with cationic molecules
Structure and Properties
of Bentonite
1. Diagenesis of volcanic ash
2. Mined from sedimentary layers
3. Platelet structure
4. Embedded negative charge
5. Colloidal size
6. Importance of counter-ions, Na+ vs. Ca2+
• Sodium clays vs. sodium-activated calcium
clays
• Risks and pitfalls
Structure and Properties of
Bentonite

7. Adsorption of water and swelling

8. Dispersion into colloidal particles in
fresh water
9. Viscosity production at 2-3 vol%
solids
– Suspension of solids at rest
10.Comparison to other common clays
Manufacturing of Bentonite
• Core samples taken and testing done to map
reserves

• Overburden removed from top of bentonite ore

with bulldozers

• Bentonite ore loaded into 10-ton haul wagons

and piled near the plants

• Bentonite ore ground and dried

– Control of grit only by size of screens that material
passes through
 Stages of Mining
• Exploration
– Geological mapping
– Drill trucks
– Lab testing
• Mapping
– Surveying (GPS)
– CAD
• Permitting
– Vegetation, soils, wildlife, cultural resources
• Mining
– Topsoil removed & stockpiled, overburden removal,
transport
• Reclamation
– Backfill Pit or Build Pond
– Re-apply Soils
– Seed With Native Grasses
– Monitor Revegetation
– Apply For Bond Release
 Chemical Structure of
Bentonite
• Complicated, non-stoichiometric structure
– 2[(Al1.67Mg0.33)(Si3.5Al0.5)O10(OH)2]

• It is a 3-layer clay with 1 aluminum oxide sheet

surrounded by 2 silicon oxide sheets

• The internal aluminum sheet and external silicon oxide

sheets share oxygen atoms

• Such an arrangement would be electrically neutral, but

Mg2+ ions often substitute for Al3+ ions, resulting in net
negative charge
– Chemical “double negative”
– Deficiency of positive charge leads to net negative
charge
2:1 Layer Structure of Bentonite
3-Layer Clay Platelets with Net
Negative Charge

1. The negative charge in platelet is balanced by

counter-ions, usually Na+ and Ca2+ , located
between the platelets
2. The source of net negative charge is buried in the
platelet structure
3. The charge is dispersed over the clay surface
(external silicon oxide layers on both sides of the
platelet)
4. Resulting diffusively charged bentonite surfaces
adsorb huge amounts of water
‰ Bentonite clay platelet is < 1 nm thick
‰ Adsorbed water 10 to 20 nm, maybe 40 nm,
thick
 Important Properties of
Sodium Bentonite
• Mined bentonite is comprised of crystalline
packets of montmorillonite platelets

• Packets may expand/disperse to individual

platelets in fresh, soft water

• Na+ has a single charge and associates with one

platelets and allows complete dispersion

• Ca2+, with 2 charges, associates with two

platelets and prevents/slows down dispersion
– Addition of soda ash is to replace Ca2+ with Na+
– Ca2+ + 2 Na+ + CO32- → 2 Na+ + CaCO3↓
Hydration & Dispersion of
Sodium Bentonite

o
 Cation Exchange of
Bentonite
• Ions can change positions with other ions

• Particular ions have a higher affinity for the exchange sites

• Divalent ions exchange monovalent ions

• High concentrations of monovalent ions can displace

divalent ions

• Divalent ions can be removed chemically

– Soda ash
– Sodium hydroxide

• Cationic surfactants ion-exchange to make organophilic

bentonite
 Calcium Bentonite
Calcium ion has a special effect on bentonite
• The Ca2+ ion can bridge negative charges between two
bentonite faces

• Can prevent dispersion

• Calcium bentonite is much less effective viscosifier than

sodium bentonite

• Can lead to face-to-face flocculation

• High temperature and shear can collapse the flocculated

structure to calcium bentonite

• The +2 charge is much more effective than +1 in

shielding - charges between particles
Hydration of Calcium
Bentonite

0
 Potassium Ion Has a
Special Effect
• Its hydrated ionic diameter is the perfect
size to fit into the depression of silicon
oxide layer
– Hydrated K+ smaller than hydrated Na+
– NH4+ has similar size and effect

• Bentonite in K+ form is resistant to further

hydration, swelling and dispersion
– KCl often used in drilling fluids to reduce
swelling and dispersion of formation
clay
 Stability of Colloidal Clay
System
• In both fresh water and salt water, interparticle attraction and
repulsion operate simultaneously

– The van der Waal’s attraction is independent of salt

concentration

– The electrostatic repulsion decreases with increasing salt

concentration

– In fresh water, the charge repulsion predominates

• Suspension is largely deflocculated
• Only a few particles are interacting

– In salt water, the repulsion is reduced

• Attraction begins to predominate
• Suspension begins to flocculate
 Interactions Between
Bentonite Particles Creates
Viscosity
• Interactions between clay particles give structure or
viscosity to the suspension
– This structure makes the fluid non-Newtonian
– Major effect of structure is to increase Yield Point

• Magnitude of viscosity depends on

– Number of particles
– Overall energy of interaction between particles

• For untreated bentonite fluids (not extended with

polymers), difficult to predict whether number of particles
or energy of interaction is more important

• For flocculated bentonite fluids, number of particles is most

important
 Interactions Between
Bentonite Particles Creates
Viscosity
• Dispersion creates a greater number of
particles and more interactions

• Complete dispersion depends on shear

history, time and chemical interactions
– Quality of the bentonite
– Electrolytes in water
– Caustic
– Soda ash
– Dispersants
 Dispersion Creates Lots of New
Particles with Charged Surfaces
• Water adsorbs onto the new surfaces created
by dispersion

• Surface charges are exposed

• These surface charges keep colloidal clay

particles suspended
– The mud does not settle/separate with time
– No clear layer on top

• The adsorbed water also keeps the clay particles

apart
 Viscosity of Bentonite Slurries
Result from Interparticle
Interactions
• Positive edges are attracted to negative faces
– Edge-to-face interactions
• Face-to-face interactions result from bridging of particles
faces by Ca2+ ions
– Also by shielding of negative charges by salts
• These interactions produce viscosity
– Mechanical energy is required to break them up
 Quiescent and Low Shear
Rates
• At rest, interparticle interactions are high.
– May increase with time
– These interactions produce viscosity
• Low shear rates only break a small fraction of
these interactions
• High viscosity
 High Shear Rates
• Bentonite particles are moving nearly
parallel to each other
– Shearing action has broken up the interactions
– Faces repel, little edge-face interaction
– Low viscosity
 Intermediate Shear Rates
• Not all the interparticle interactions are
broken up
• Intermediate viscosities
 Kaolin Clay
• Simple two-layer structure (1:1)
( – Al – Al – Al – Al – )
( = Si = Si = Si = Si = )

• Strong bonding between successive sheets

• Hexagonal crystals

• Low cation exchange capacity

• Derived from diagenesis of granite

 Mica or Illite
• Two silicon layers to one aluminum
(= Si = Fe = Si = Si =)
(= Al = Al = Al = Al = )
(= Si = Si = Si = Si = )

• Ion substitution in silicon oxide layers

• Layers may be mixed with montmorillonite layers

– Mixed layer clays
– Some swelling in formations
– Low to medium ion-exchange capacity
Summary of Structure and Properties of the most common clay
minerals

Property Kaolin Mica Bentonite Attapulgite Chlorite

Layer type 1:1 2:1 2:1 2:1 2:1:1

Crystal
structure sheet sheet sheet sheet sheet

Particle hexagonal extensive

shape plate plates flake needle plate

Particle
size, large sheets
microns 5-0.5 to 0.5 2-0.1 1-0.1 1-0.1
Surface area

BET - N2,
m2/g 15-25 50-100 30-80 200 140

BET - H20,
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

Effect of
salts Flocculates Flocculates Flocculates Little or none Flocculates
Conversion from Oilfield Units
to Construction Units
lb/100
gal Vol % Wt %
lb/bbl water solids solids
5 11.9 0.6 1.4
10 23.8 1.1 2.9
15 35.7 1.7 4.3
22.5 53.6 2.6 6.4
25 59.5 2.9 7.1
30 71.4 3.4 8.6
Concentration Units
Conversion Table
lb/100
gal Vol % Wt %
water lb/bbl solids solids
15 6.3 0.7 1.8
20 8.4 1.0 2.4
25 10.5 1.2 3.0
30 12.6 1.4 3.6
35 14.7 1.7 4.2 Based on
specific
40 16.8 1.9 4.8
gravity of
45 18.9 2.2 5.4 2.5 for
50 21.0 2.4 6.0 bentonite
55 23.1 2.6 6.6
60 25.2 2.9 7.2
65 27.3 3.1 7.8
70 29.4 3.4 8.4
75 31.5 3.6 9.0