Clay Chemistry State

Clay Chemistry
and
Clay States
5 4
© 2001 PetroSkills LLC, All Rights Reserved
Clay
• Finely divided minerals 2 microns or less

• Crystalline in nature
• Mica-type structure stacked face to face
• Single platelet is a unit layer
• Atoms in close packed octahedral or
tetrahedral configuration
5 4
Octahedral
• Oxygen or hydroxyls form two close

packed rows coordinated to aluminum, iron,
or magnesium ions located at the octahedral
center
5 4
Tetrahedral Layer
• Silicon located equidistant from four

oxygen atoms or hydroxyl ions
• Infinite hexagonal sheet =======> Si4O6(OH)4
Silica Tetrahedron in Hexagonal
network
5 4
Shared Oxygen Bonding
Tetrahedral sheet silica
Octahedral sheet
aluminium
Tetrahedral sheet silica
Hydroxyl Magnesium or aluminum

Oxygen Silicon, occasionally aluminum
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The Sheet Expanding Clay Lattice
• Form platelets by sharing common oxygens

• Stacked face to face to form crystal lattice
Tetrahedral sheet
Octahedral sheet
C spacing Tetrahedral sheet
Exchange cations
and crystalline water
cations and
Basal surface
A B
5 4
Drilling Fluid Clays
• Kaolinite
• Illite
• Chlorite
• Mixed Layer
• Montmorillonite
• Sepiolite
• Attapulgate
5 4
Drilling Fluid Clays
Prototype
• All metal ions in the octahedron are of
one kind, and all the metal ions in the
tetrahedron are of a different kind
True clay minerals
• A few metal ions in the structure are
different from the predominant type and
carry a different ionic charge.
5 4
Isomorphous Substitution
• The pattern of isomorphous substitution

causes variations in the resulting clay
minerals depending on
– Tetrahedral or octahedral
– Extent of substitution
– Exchanged cations, Na+, K+, Ca2+
5 4
Adsorbed Cation Exchange
• Effect of concentration
• Population of exchange sites
• Nature of anion
• Nature of cation
• Nature of clay mineral
Replacing power of cations

Li+ <Na+<K+<Mg2+<Ca2+<H+
5 4
Clay Platelets
• Unbalanced groups of
charges are created at broken edges
• Charge on the edge will vary with pH
• At low pH the edges are more positive
• At high pH the edges are more negative
• Drilling fluids are maintained on the
alkaline side
• Chemical treatments are often aimed at a
reaction with groups at the broken edges
5 4
Kaolinite
• Single tetrahedral and

single dioctahedral alumina sheet
• Hydroxyls on octahedral face are side by
oxygens on face of tetrahedral face
• Charges within the structure are well
balanced with few lattice substitutions
• Strong hydrogen bonding exists between
successive layers preventing water peni-
tration and latice expansion
5 4
Kaolinite
• Charge mainly due to broke edges.

• pH sensitive
• Low cation exchange capacity
• Low viscosity slurries
• Paper and ceramics
• Shales and marine deposits
5 4
Illite
• Micas
• 2:1 lattice
• 2 silica sheets sandwich octahedral sheet
• Silica replaced by alumina or iron
• Charge deficiency balanced by potassium,
calcium, magnesium, or hydrogen ions
• Interlayer hydration and lattice expansion
• Stabilization with potassium ion
5 4
Group 1A Physical Dimensions
In Microns
Group Ion Diameter,  Hydration Energy
1A ion not hydrated* hydrated kcal/mol
+
Li 1.20 14.6 124.4
+
Na 1.90 11.2 97.0
+
K 2.66 7.6 77.0
+
Rb 2.96 7.2 71.9
+
Cs 3.34 7.2 66.1
+2
Ca 1.98 19.2 377.0
+2
Mg 1.30 21.6 459.1
5 4
Illite with Hydrated Cations
+2
Ca Ca +2
10
+
K Mg+2
+ +
K Na +
Rb
+2
Ca
+
+ Li
Na
5 4
Chlorite
• Three sheet clay with brusite layers

• Octahedral has magnesium hydroxide => brusite
• Brucite sheet has net positive charge
• Low cation exchange capacity 10-40
• Brucite layer compensates for the net
negative charge on unit layers
• No interlayer water
• Degraded chlorites
5 4
Mixed Layer
• More than one clay mineral

• Two types
• uniform interstratification
• chlorite, Mica 3 layers plus brucite
• irregular interstratificationNo uniform repetition of layers
• montmorillonite/illite
• illite/kaolinite
• chlolrite/kaolinite
5 4
Montmorillonite
• Young argillaceous formations

• Drilling problems
• Fresh water gel, bentonite
5 4
Montmorillonite Structure
Montmorillonite is the major clay mineral in “bentonite”.
The best known mineral in the smectites.
• Substitutions occur
mainly in the octahedral
layer
• Cations unable to
approach the negative
charge sites close
enough to completely
neutralize either the
positive charge on the
cation or the negative
charge on the clay
surface
5 4
Montmorillonite
• Smectite
• Bentonite, fresh water gel
• Sodium and calcium
• Younger argillaceous formations
• Hole problems
• Mg2+, Fe3+, for Al3+ in octahedral layer
• Al3+ for Si4+ in tetrahedral layer
5 4
Montmorillonite
• Swelling mechanisms
• crystalline - adsorption
• osmotic - absorption
• soluble ions
5 4
Crystalline Swelling
• Mono-molecular layers of water on basal

crystal surfaces
• First layer by hydrogen bonding to
hexagonal network of oxygen atoms
• Bond strength decreases with distance
• Specific volume and viscosity
5 4
Tetrahedral Layer
• Silicon located equidistant from four

oxygen atoms or hydroxyl ions
• Infinite hexagonal sheet =======> Si4O6(OH)4
Silica Tetrahedron in Hexagonal

network
5 4
Crystalline Swelling
• Exchangeable cations
• May be hydrated
exception NH4+ and K+
• Bond to crystal surface in competition
exception Na+ and Li+ which diffuse
5 4
Osmotic Swelling
• Cation concentration between layers

greater than in solution
• C-spacing increase with diffuse double
layers
• Larger bulk volume than crystalline
• Mechanism dependant on cation present
5 4
The Sheet Expanding Clay Lattice
• Form platelets by sharing common oxygens

• Stacked face to face to form crystal lattice
Tetrahedral sheet
Octahedral sheet
C spacing Tetrahedral sheet
Exchange cations
and crystalline water
cations and
Basal surface
A B
5 4
Cation Effects
• Ca2+ associates with two layers

• Limited swelling and dispersion
• less surface area and associated water
Hydrated
17 A
Ca +2
Ca +2
Ca+2 Ca+2
12.1 A
5 4
Cation effects
• Na+ associates with one layer

• High hydration potential
• Encourages hydration and layer
separation
Na+ Hydrated
Na+ Na+
Na+ Na+
9.8 A 17 A to infinite
+
Na+ Na
Na+ Na+
Na+
5 4
Relationship - Size & Surface Area
20 micron solid surface The same solid cut Cut in half again
area 2400 microns in half on each face on each face
5 4
Surface Areas of Clay
(Surface areas of Clay determined by N2 and water vapor adsorption)
2
Surface Area m /g Water Area
Sample
Nitrogen Water Nitrogen
Area
+
Bentonite(Na ) 38 20+/250 5.3/6.6
Kaolinite 16 12+/12 0.8
Illite 56 52+/82 0.9/1.5
5 4
Effect of Salt on Attractive/Repulsive
Forces
5 4
Effect of Salt on Attractive/Repulsive
Forces
5 4
Electrical Double Layer
5 4
Aggregated State
Na+
Na+
Na + Na+
Na+ Na+
Na + Na+
Na+ Na+
+ Na+ -
- - - + +
+ -
Na + + Na+ Na+
Na
+ Na+ -
- - - + +
+ -
Na + + Na+ Na+
+
Na
+ Na -
- - - + +
+ -
5 4
Hydrated Clay W/Water Envelope
+
+ Na
Na
+
- - + + -
+
Na - + - Na
+
+
Na
+
Na
+
Na
+
Na
+
Na
+ - + - - - + + -
5 4
Dispersed Bentonite / Ionized Na+
Na+ +
- Na+
+
-
-
Na+
-
+ + N
+ - + - - - + + - -
- +
+ - +
- - - ++ - - - ++ + -
- -
+ + -
- + + - -
Na+ - +
- - +
+ -
Na
+ Na+
-
+
5 4
Flocculation
+
Cl- Cl-
Na Na+
Cl- Na+
Cl-
Na+ +
+
Cl- - -
+ + +
- Cl - - -
+ - - -
- - - -
+ + + +
- + - + -
- - +
- - + + + -
- + - -
+ - Cl-
+ - +
+ - - - - +
Cl- + Na+
Cl-
- + Cl-
- Na+
Cl Cl-
5 4
Van der Waals Attractive Forces
Two atoms with symmetrical spheres of

electrons and hence no attractive forces
Spontaneous distortion of electron

cloud sets up dipole attraction
5 4
Flocculating Mechanisms
Increase interparticle attractive forces

and decrease repulsive forces.
• High salt concentrations
• Polyvalent cations
• Polymeric flocculants
• Low pH
• High temperature
5 4
Flocculation to Aggregation / 5% NaCl
+ +
- - +
+ -
+ +
- + -
- - +
- - + -
+ - + +
- - - + -
-
+ + - - +
+ - -
- + - - - -
+ +
+ - - + - -
- -
- + + - + - + -
+ - + -
- - + + - + - -
+ - + + + - +
- - - + - -
- - +
+ - + - -
+ + - +
- + - + - +
+ - - - -
+ - - +
+ + + - +
- + + - - -
- - +
+
+ + - +
- -
+ + - +
- - -
+ + + - +
- -
- - - + -
- - +
+ - - + - +
- - + - -
- - + - -
+ + +
- + + - - +
+ + + - -
- + - -
+ + + +
- - - + -
+ + + -
- - - -
- - + -
- - - + + - +
+ + - - -
- - - +
+ - + +
+ + + - +
+ - -
- - - +
- -
+ + - +
+ + -
- - +
- -
- +
- -
- + + + + +
- + - - - -
+ + + + +
+ + -
- - - - -
- - +
+ + - - - - -
- + -
- - - - -
+ -
+ + + +
- -
+
- - - -
+
- + + + +
+
1% NaCl 5% NaCl
1% NaCl - Flocculated
Flocculated 5% NaCl - Aggregated Aggregated
5 4
Agglomerates and Flocculation / 15-26% NaCl
+
- +
+ -
+ - -
- - + -
+ + -
+ - + -
- - -
- - + + +
+ - + +
+ - + - -
- - - + -
- - + +
- + - + + -
+ - + -
- + - -
- - - + - -
- + + +
- + + - +
+ - - - -
- + - - +
- +
+ + -
+ - +
- - +
+ - + +- + +
+ + + + + - +
+ - - - + - -
- - - - + - - ++
+ +- + +
+ + + + - -
+ - - - +- - -
- - - - - + - - +
+ - + +
- - - - - - -
- - - - + - -
- - - -
- - - - + + + + + - - -
- - - + +
+ + - - - + + +
+ + + - - - +
+ + +
- - + - + - - - -
- - - - - -
- - - +
+ + + -+ +
- - + - +
+ - -
+ + - +
+ -
- + -
+ ++ -
- - - +
- - - +
+ - -
- + + -
+ + + +
+ - - + + - - + +
+ - + -
- + - + - - - - - -
+ + - + - +
+ + + + + +
- - - - + + - +
+ - - - - -
- - - - -
- - + -
- - - - - - + -
+ - - - +
- - - -+ - -
- - + -
- + - + + +-
- + + + -+ -
- + - + + +
+ + - - - - - -
15-26% NaCl
- - -
+ - + + - - + - -
- - +
+ + + - - +
+ - + - - +
+ -
+ - + +
+ - +
5% NaCl - Aggregated
- +
Aggregated& Flocculated
5% NaCl 15-30% NaCl
Aggregated Aggregated & Flocculated
5 4
Calcium Flocculation
Ca++
- -
Ca +_ +_
+ +
+
- Ca -
+ - + - ++
+ - -Ca + Ca Ca++
- _+ Ca -
+ + - - + - ++
-
+ + +
+ +
--+_+ +- Ca++
Ca Ca + + Ca+ --
--+_+ +- -Ca + +
Ca + - - +- +
+ Ca+2
- _ -
+ -Ca ++-+ Ca +- Ca- Ca+2
Ca
Ca++ + - + - - + -+ -
Ca+2 Ca++ + +-
Ca
5 4
Sodium to Calcium Clay
Ca Ca++
Na+ Na+ Ca++
Ca++ Ca++
Ca++ Ca++
Na+ Ca++
Ca++
Na+ Ca++ Ca++
Na+ Ca
Ca++ Ca Ca
Na+
5 4
Polymeric Flocculants
_ _
- +- +
+- + _
+ - + - + _
_
_
_
5 4
Low pH and High Temperature
• Low pH
Edge charges are pH dependent
pH less than seven
•High Temperature
Absorbed water tends to desorbs
attractive forces become dominant
5 4
Deflocculation Mechanism
• Maximize electrostatic repulsions

• Maximize the charge on the clay platelets
• Negatively charge polymers
5 4
Polymeric Deflocculants
- +- +
+- +
_ + _
_ -
+
_ _
_
_
+ - + - + _
- +
_
- +
-
5 4
Encapsulated Clay W/ Lignosulfonate
- - -
-
- - - - - - + -
- -
- - +
-
- + - - + -
-
- +
- + +
- -
+ + - +
- -
- + +
+ - -
- - - +
- - -
+ - -
- + - - -
- - - - - - -
- + - - -
- -
- -
+ - -
- -
- - +
- -
- + -
-
- +
-
- +
+ -
- - - + + -
- + - +
- - - - +
- - - - -
-
+
5 4
Inhibited or Aggregated Clays in Seawater
+ -
+
+ - -
+ - -
+ + - +
- -
- + - -
+ + + +
+ - - - - +
- + -
- - - + -
Cl-
+ +
+ - + - - + -
- - - + -
- + - + -
- + -
+ - - +
+ - + + - +
- - + - -
- + - - +
+ - + + -
- - + - +
- + - - +
-
+ + - +
- - -
+ - +
+
-
+
-
+
-
+
-
+
- Cl- - +
+ -
+
Cl + + + +
- - - -
+ -
+ -
+
-
- -
+ -
-
-
-
-
-
-
-
+ -
Cl-
- - +
+ - -
+ + + + + + + - -
+ - - - - - - - -
- + -
+ - + + + + +
+ + + - - -
- - + -
- - +
- + + - +
+ - - -
-
+
Cl +
-
- -
+
-
+
Cl-
- -
+ +
-
+
5 4
Attapulgite
• Double silica chains parallel to long axis

• Aluminum and/or magnesium
• Three dimensional chains
• Channeled wall with every other brick
missing
• Cleavage planes parallel to silica chains
5 4
Sepiolite
• Chains are formed of two silicon chains

giving wider channels
• Filtrate loss control more difficult with
sepiolite than attapulgite.
• Recommended in deep hot wells
5 4
Clay Problems
Swelling
Dispersion
Migration
Polymer coating
Dissolution & Precipitation
5 4
Clay Dispersion / Migration
Smectite
Swelling clay, fresh water sensitive, takes on
water and expands
Mixed layer
Smectite/illite layering, swells, but not same
degree as smectite, will disperse in fresh water
Illite
Disperses in fresh water and readily migrates
Kaolinite
Subject to dispersion and migration, not same
degree as illite
Chlorite
Not fresh water sensitive, doesn’t swell, high iron
content, some times acid sensitive
5 4
Clays in Formations
• Location of clays in sand stones

– Pore filling
– Pore lining
– Grain attachment
– Streaks or laminates
– Structural
5 4
Illite
• Pore filling and pore lining
• Several forms:
– Plates
– Fibers
– Chunks
• Sensitive to dispersive environments
– High pH
– Chemical dispersants
• Migrates readily (“Hairy” illite)
– Breaks off and migrates
– Sensitive to fluid movement
5 4
SEM Micrograph Illite
Q
Q
Q
P
Sample Source: Amoco Red Canyon #1 well, Wyoming

Formation (Age): Nugget Sandstone (Jurassic)
Depth of Sample: 8,951 ft
Detrital quartz grains (Q) coated with filamentous pore-lining and pore-bridging authigenic illite. Open, interconnected
pores (P) lined with ribbons form a mat, coating detrital grain surfaces and also bridging the pores between grains (see
arrows) creating permeability barriers to fluid flow. Neasham (1977) demonstrated that this clay texsture severely
reduces permeability without affecting porosity. Higher magnification view of the bridges reveals that they are
composed of intertwined clay ribbons. EDX analysis yields the major elements Si, Al, and K, with a minor amount of
Mg. The Fe detected here is probably due to amorphous iron oxide coatings.
Magnification: (A) 300x; (B) 500x; (C) 1,000x
5 4
Koalinite
• Found as grain attachments and pore filling

• Found as booklets of plates. May bind water
• Subject to dispersion and migration
• Large relative size of platelets
5 4
Smectite
• Swelling clay
• Takes on water and expands
• Found primarily as pore lining
• Fresh water sensitive
• Stabilize with potassium, ammonium salts
5 4
Mixed Layer Clays
• Smectite/illite alternating layers

• Swells like smectite, but not to the same
degree
5 4
Chlorite
• Occurs as grain attachments or pore lining

• In form of plates or honeycomb arrangement
• Disperses and migrates readily
• Doesn’t swell, but binds water
• May occur as mixed layer with smectite
• Degrades with HCl, releases Fe- and
amorphous silica
5 4
End
5 4

Clay Chemistry State

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Clay Chemistry State

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Clay Chemistry

• Finely divided minerals 2 microns or less

• Oxygen or hydroxyls form two close

• Silicon located equidistant from four

Tetrahedral sheet silica

Tetrahedral sheet silica

Hydroxyl Magnesium or aluminum

• Form platelets by sharing common oxygens

• The pattern of isomorphous substitution

Replacing power of cations

• Single tetrahedral and

• Charge mainly due to broke edges.

• Three sheet clay with brusite layers

• More than one clay mineral

• Young argillaceous formations

• Mono-molecular layers of water on basal

• Silicon located equidistant from four

Silica Tetrahedron in Hexagonal

• Cation concentration between layers

• Form platelets by sharing common oxygens

• Ca2+ associates with two layers

• Na+ associates with one layer

(Surface areas of Clay determined by N2 and water vapor adsorption)

Two atoms with symmetrical spheres of

Spontaneous distortion of electron

Increase interparticle attractive forces

• Maximize electrostatic repulsions

• Double silica chains parallel to long axis

• Chains are formed of two silicon chains

Dissolution & Precipitation

• Location of clays in sand stones

Sample Source: Amoco Red Canyon #1 well, Wyoming

• Found as grain attachments and pore filling

• Smectite/illite alternating layers

• Occurs as grain attachments or pore lining

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