Unit -3

Clay Chemistry
Content
• Clay chemistry and its application to drilling fluids

• Types of Clay

• Hydration

• Flocculation

• Aggregation

• Dispersion

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Importance of studying clay mineralogy

• Clay provides the colloidal base for all aqueous muds and oil-base mud

• Drilling cuttings from argillaceous formation changes properties of drilling fluid

• Stability of borehole depends on interaction between drilling fluids and exposed

shale

• Clay content on drilling fluid may contaminate the formation and affects
productivity

• Commercial clay used for drilling fluid is Wyoming bentonite (yield 100 bbl/ton
when used with pure water)
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Characteristics of Colloidal System
• What do you mean by Colloids?
• Particle whose size fall roughly between smallest particle seen through
microscope and molecules
• Colloidal system: consist of solids dispersed in liquids (Clay suspensions),
liquid droplets dispersed in liquids (e.g. emulsion), or solids dispersed in gases
(e.g., smoke).

• Aqueous colloidal systems is that particle, so small that they kept in

suspension indefinitely by bombardment of water molecules, a phenomena
known as the Brownian movement.
• The movement of the particle can be seen by light reflected from them and
observed against dark background in the ultramicroscope.

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Brownian motion
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Characteristics of Colloidal System
• The particles are so small that properties like
viscosity and sedimentation velocity are controlled
by surface phenomena.
• Surface phenomena occur because molecules in the
surface layer are not in electrostatic balance
• The surface carries an electrostatic charge, the size
and sign of which depends on the coordination of
the atoms on both sides of the interface.
• Some substances, notably clay minerals, carry an
unusually high surface potential because of certain
deficiencies in their atomic structure

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Characteristics of Colloidal System
• The greater the degree of subdivision of a solid, the greater will be its surface area
per unit weight, and therefore the greater will be the influence of the
surface phenomena.
• For example, a cube with sides one mm long would have a total surface area of
6mm2. If it were subdivided into cubes with one micron sides (1 micron = 1 x 10-3
mm) there would be 109 cubes, each with a surface area of 6 x 10-6 mm2, and the
total surface area would be 6 x 103 mm2.
• Subdivided again into milli-micron cubes, the total surface area would be 6 x 106
mm2, or 6 square meters.
• The ratio of surface area per unit weight of particles is called the specific surface.
Thus if a 1 cm3 cube were divided into micron sized cubes, the specific surface
would be 6 x 106 /72.7 = 2.2 x 106 mm2/g = 2.2 m2/g, assuming the specific gravity of
the cube to be 2.7.

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Characteristics of Colloidal System
• Specific surface versus cube size
• To put the values in perspective, the size of various
particles, expressed in equivalent spherical radii
(esr), are shown at the top.
• The esr of a particle is the radius of a sphere that
would have the same sedimentation rate as the
particle.
• The esr may be determined by applying Stokes'
Law to the measured sedimentation rate.

Figure: Specific surface of cubes. Assuming specific gravity of 2.7 8

9
Clay Minerals
• General Characteristics

• Small particle size

• Plastic across range of water contents

• High dry strength

• Potential for shrink/swell

• High resistance to weathering

• Particle have net negative charge

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Clay Mineralogy
• A science dealing with structure of clay minerals on microscopic,
molecular and atomic scale is called Clay Mineralogy.
• It includes study of the mineralogical composition and electrical
properties of the particles.
• The most significant properties of clay depend upon the type of
mineral.
• There are three types of clay minerals:
• Kaolinite clay
• Montomorillonite Clay
• Illite clay

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Clay Mineralogy
There are three types of clay minerals:
• Kaolinite clay
• Montomorillonite Clay
• Illite clay

Kaolinite clay Montomorillonite Clay Illite clay

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Basic structures of clay minerals
1. Silica tetrahedral sheet
2. Aluminium octahedron sheet or also called as gibbsite

Silica tetrahedral aluminium octahedron

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Basic structures of clay minerals
1. Silica tetrahedral sheet

Silica tetrahedral

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Basic structures of clay minerals
1. Silica tetrahedral sheet
2. Aluminium octahedron sheet
or also called as gibbsite

aluminium octahedron

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Structural arrangement
• The unit layers are stacked together face-
to-face to form what is known as
the crystal lattice.
• The distance between a plane in one layer
and the corresponding plane in the next
layer is called either the c spacing, or the
basal spacing.
• This spacing is 9.2 Angstoms* for the
standard three-layer mineral, and 7.2 A for
a two-layer mineral.

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Example of structural arrangement
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Classification of clays
Ratio- Si: Gi (1:1)
1. Kaolinite Clay
• The basic unit of this type of clay is formed by
atomic bond of the unsatisfied face of silica sheet
and face of aluminum sheet (Gibbsite)
• The bond between two sheets is strong and is
primary bond (H+ Bond).
Kaolinite clay

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Classification of clays
1. Kaolinite Clay
• Atomic structure of Kaolinite

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1. Kaolinite Clay
• The hydrogen bond is very strong bond
because of that, it shows less/no swelling
and shrinkage Behavior
• It is least active clay minerals. Example:
China soil, application paper, rubber,
paint.
• The thickness of one unit is about 7.2
angstrom.
• SEM (Scanning Electron Microscope) SEM image of Kaolinite clay
image of kaolinite clay is illustrated in
Figure.
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2. Montmorillonite Clay Ratio- Si: Gi (2:1)

• A single structural unit of montmorillonite is

composed of two silica sheet and one
Gibbsite sheet.
• The number of structural units are joined
together by very weak water bond.
• The thickness of one unit is about 9.2
Angstrom.
• It is highly active clay mineral due to which
soil shows high swelling and shrinkage
characteristics Montmorillonite clay

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Montmorillonite Clay

Atomic structure of Montmorillionite Clay

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Montmorillonite Clay
• The link is due to natural attraction for the
cations in the intervening space and due to
Vander Waal forces.
• The negatively charged surfaces of the silica
sheet attract water in the space between
two structural units. This results in an
expansion of the mineral.
• The soil containing a large amount of the SEM image of Montmorillonite clay
mineral montmorillonite exhibits high
shrinkage and swelling characteristics.

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Illite Clay
• Basic structure of this clay is the same as the one of
montmorillonite. Ratio- Si: Gi (2:1)
• A single structure unit of illite is composed of two
silica sheet and one alumina sheet.
• The alumina sheet is sandwiched between two silica
sheet.
• The number of structural units are joined together
by Ionic bond (K+ potassium Ion bond)
• The potassium ion bond is weaker then hydrogen
bond
• It shows medium swelling and shrinkage
characteristics
• Medium active Illite clay
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Illite Clay
• Atomic structure

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Illite Clay

• The thickness of 1 unit is 10 Angstrom

• The characteristics of this clay are

classified as in between those of kaolinite
and montmorillonite.

• SEM image is shown in Figure

SEM image of Illite clay

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Brucite is the mineral form of magnesium hydroxide, with
the chemical formula Mg(OH)2. 27
Characteristics comparison
Let, A be Kaolinite
B be illite
C be montmoriollonite

1. Swelling and shrinkage characteristics: A<B<C

2. Strength of bond between structural units: C<B<A
3. Plasticity/plasticity index : A<B<C
4. Grain size: C<b<A

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Clay shapes and surface areas
• Clays are formed in stack of several layers of basic sheet units.
• Clays are generally flat and smaller in size, so, their surface areas per
weight are very large.

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Origin and occurrence of clay minerals
• Clay minerals originate from the degradation of igneous rocks in situ.

• The parent minerals are the micas, the feldspars, [(CaO) (K20)Al2036Si02]; and
ferromagnesium minerals, such as horneblende [(Ca, Na2)2 (Mg, Fe, Al)s (Al,
Si)8022 (OH,F)2]

• Bentonite is formed by the weathering of volcanic ash.

• Bentonite was originally defined as a clay produced by in situ alteration of volcanic

ash to montmorillonite

• The main factors are climate, topography, vegetation, and time of exposure.
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31
Ion Exchange
• Cations are adsorbed on the basal surfaces of clay crystals.

• In aqueous suspension, ions on clay may exchange with ions in

the bulk solution.

• The exchange reaction is governed primarily by the relative

concentration of the different species of ions in each phase, as

expressed by the law of mass action.

• For example, for two species of monovalent ions, the equation

maybe written:

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Ion Exchange

• Where [A]s and [B]s are the molecular concentration of the two species of ions in

the solution, and [A]c and [B]c are those on the clay.

• K is the ion exchange equilibrium constant

• Example: when K is greater than unity, A is preferentially adsorbed.

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Ion Exchange
• When two ions of different valencies are present, the one with the higher valence is
generally adsorbed preferentially.

• The order of preference usually is:

• Note: Hydrogen is strongly adsorbed, and therefore pH has strong influence on the base
exchange reaction.

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Illustration of the cation exchange between
vine roots and surrounding soil particles
(Source: bio1903.nicerweb.com)
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Ion Exchange
• The total amount of cations adsorbed, expressed in milliequivalents per
hundred grams of dry clay, is called the base exchange capacity (BEC), or the
cation exchange capacity (CEC).

• The value of the BEC varies considerably, even within each clay mineral group.

• Within montmorillonite and illite, the basal surfaces account for some 80% of
the BEC.

• With kaolinite, the broken bonds at the crystal edges account for most of the
BEC.
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37
• Vermiculite is a 2:1 clay, meaning
it has two tetrahedral sheets for
every one octahedral sheet.
• It is a limited-expansion clay with
a medium shrink–swell capacity.
• Vermiculite has a high cation-
exchange capacity (CEC) at 100–
150 meq/100 g.
Vermiculite Structure 38
Ion Exchange
• The BEC of a clay and the species of cations in the exchange positions are
a good indication of the colloidal activity of the clay.

• A clay such as montmorillonite that has a high base exchange capacity, swells
greatly and forms viscous suspensions at low concentrations of clay, particularly
when sodium is in the exchange positions.

• In contrast, kaolinite is relatively inert, regardless of the species of exchange

cations.

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Cation Exchange Capacity Significance
• Cation exchange capacity expressed as methylene blue capacity and Bentonite
content in ppb of mud.
• It give the ability of the clay particles to hydrate depends greatly on the loosely
held captions present.
• In formation evaluation, it is the contribution of cation-exchange sites to
the formation electrical properties.

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Clay swelling mechanism

• All classes of clay minerals adsorb water, but montmorillonite take up

much larger volumes than do other classes, because of their expanding
lattice.

• Mechanisms for Clay swellings

• Crystalline

• Osmotic

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Clay swelling mechanism

• Crystalline swelling: (Sometime

called surface hydration)
• Results from the adsorption of non-
molecular layers of water on the
basal crystal surfaces on both the
external, and, in the case of
expanding lattice clays, the inter-
layer surfaces
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Clay swelling mechanism
• The first layer of water is held on the
surface by hydrogen bonding to the
hexagonal network of oxygen atoms.

• Consequently, the water molecules are

also in hexagonal coordination

• The strength of the bonds decreases

with distance from the surface

Combined water layers between layers of partially dehydrated vermiculite

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Clay swelling mechanism
• Osmotic swelling occurs because the concentration of cations between the layers is greater
than that in the bulk solution (CL>CS).

• Consequently, water is drawn between the layers, thereby increasing the c-spacing and
permitting the development of the diffuse double layers

• Osmotic swelling causes much larger increases in bulk volume than does crystalline swelling.
• For example, sodium montmorillonite adsorbs about 0.5g water per g of dry clay, doubling the volume,
in the crystalline swelling region, but about 10 g water per g dry clay, increasing the volume twenty
fold, in the osmotic region.

• On the other hand, the repulsive forces between the layers are much less in the osmotic
region than in the crystalline region
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45
Electrostatic Double Layer
• Particles in colloidal suspension carried a surface
charge. This charge attracts ions of the opposite
sign, which are called counter ions, and the
combination is called the electrostatic double
layer.
• Some counter ions are not tightly held to the
surface and tend to drift away, forming a diffuse
ionic atmosphere around the particle.
• In addition to attracting ions of the opposite sign,
the surface charge repels those of the same sign.
• The net result is a distribution of positive and
negative ions, as shown schematically in Figure

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Electrostatic Double Layer
• The distribution of ions in the double layer
results in a potential grading from a
maximum at the clay surface to zero in the
bulk solution, as shown in Figure
• The layer of cations next to the surface of
the particle, known as the Stern layer, is
bound to and moves with the particle
whereas the diffuse ions are independently
mobile.
• The potential difference from the plane of
shear to the bulk of the solution is known as
the zeta potential
• Water flowing through the pores of a shale,
removes the mobile ions, thereby generating
a potential, which is known as the streaming
potential zeta potential
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Electrostatic Double Layer
• The zeta potential is maximum, and the mobile
layer is most diffuse when the bulk solution is
pure water.
• Addition of electrolytes to the suspension
compresses the diffuse layer, and reduces the
zeta potential.
• The zeta potential decreases greatly with
increase in valence of the added cations,
especially if low valence ions are replaced by
higher valence ones through base exchange, the
ratio being approximately 1 to 10 to 500 for
monovalent, divalent, and trivalent cations,
respectively.
• The zeta potential is also reduced by the
adsorption of certain long-chain organic cations.
• In some cases, it is possible to neutralize and
reverse the zeta potential.
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Electrostatic Double Layer
• The edge charge is less than the basal surface charge, and may be positive or
negative, largely depending on pH
• For example, if kaolinite is treated with HCI, it has a positive charge, and if treated
with NaOH, it has a negative charge.
• The reason for this behavior is that aluminum atoms at the edge react with HCI to
form A1CI3, strong electrolyte which dissociates to Al+3 +Cl- , whereas with NaOH,
aluminum forms aluminum hydroxide, which is insoluble.
• (Remember that ion adsorption in kaolinite takes place almost entirely at the edge,
so that the charge on the particle is determined by the charge on the edge)

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Electrostatic Double Layer
• The existence of positive sites on
the edges of kaolinite has also
been demonstrated by an
experiment in which a negative
gold sol was added to a kaolinite
suspension.
• An electron micrograph showed
the gold particles adsorbed only at
the crystal edges

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Electron micrograph of a mixture of kaolinite and a gold sol
 Particle association

https://www.youtube.com/watch?v=kFS1GwaqR4g

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Flocculation and Deflocculation
• When an electrolyte is added, the double
layers are compressed, and if enough
electrolyte is added, the particles can
approach each other so closely that the
attractive forces predominate, and the
particles agglomerate. This phenomenon is
known as flocculation,
• The critical concentration of electrolyte at
which it occurs is known as the flocculation
value.
• The flocculation value of clays may be readily
determined by adding increasing amounts of
electrolyte to a series of dilute suspensions.

Schematic representation of
flocculated clay platelets (assuming
negative edge potential)
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Flocculation and Deflocculation
• The flocculation value depends on
• The species of clay mineral,
• The exchange cations
• kind of salt added
• The higher the valence of the cations (either on the clay or in the salt) the lower
the flocculation value
• Sodium montmorillonite is flocculated by about 15 meq/l of sodium chloride, and
• Calcium montmorillonite by about 0.2 meq/l of calcium chloride.

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Flocculation and Deflocculation
• When the cation of the salt is different from the cation on the clay, then base
exchange occurs, but the flocculation value is always much lower whenever
polyvalent cations are involved.
• For instance, the flocculation value of sodium montmorillonite by calcium chloride
is about 5 meq/l, and of calcium montmorillonite by sodium chloride about 1.5
meq/l.
• There is a slight difference in the flocculating power of monovalent salts, as
follows:
Cs>Rb>NH4>K>Na>Li.
This series is known as the Hoffmeister series, or as the lyotropic series.

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Flocculation and Deflocculation
• If the concentration of clay in a suspension is high enough, flocculation will cause
the formation of a continuous gel structure instead of individual flocs.
• The gels commonly observed in aqueous drilling fluids are the result of
flocculation by soluble salts, which are always present in sufficient concentrations
to cause at least a mild degree of flocculation.
• Gel structures build up slowly with time, as the particles orient themselves into
positions of minimum free energy under the influence of Brownian motion of the
water molecules
• Flocculation may be prevented, or reversed, by the addition of the sodium salts of
certain complex anions, notably polyphosphates, tannates, and lignosulfonates
• Example: if about 0.5% of sodium hexameta-phosphate is added to a dilute
suspension of sodium montmorillonite, the flocculation value is raised from 15
meq/l to about 400 meq/l of sodium chloride
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Aggregation and Dispersion
• The term flocculation is limited to the loose association of clay platelets which
forms flocs or gel structures

• The term aggregation, referes to the collapse of the diffuse double layers and the
formation of aggregates of parallel platelets spaced 20 A or less, apart.

• Flocculation causes an increase in gel strength, whereas aggregation causes a

decrease because it reduces
(1) the number of units available to build gel structures and

(2) the surface area available for particle interaction

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 Aggregation and Dispersion
• The term dispersion is commonly used to
describe the subdivision of particle aggregates
in a suspension, usually by mechanical means

• The subdivision of clay platelet stacks, which is

usually the result of electro-chemical effects,
and thus to distinguish between the
dispersion-aggregation process and the
deflocculation flocculation process.

Schematic representation of the flocculation-deflocculation

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mechanism and the aggregation-dispersion mechanism.
Aggregation and Dispersion
• The onset of flocculation is shown in
Figure by the rise in gel strengths from 10
meq/l or greater.

• The gel strength continues to rise

with concentration of sodium chloride up
to 400 meq/l, but the particles reach
equilibrium positions slowly, as indicated
by the difference between the initial and
ten-minute gel strengths.

Flocculation and aggregation of sodium bentonite

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by
sodium chloride
Aggregation and Dispersion
• The addition of polyvalent salts to
sodium bentonite suspensions show
flocculation at first, and then
aggregation as the concentration
increases

• Many clays encountered in drilling are

predominately calcium and magnesium
clays, and hence are aggregated

Flocculation and aggregation of sodium bentonite by calcium

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chloride
 Aggregation and Dispersion

Floccuiation and aggregation of sodium bentonite by

aluminium chloride. 60
Aggregation and Dispersion
• When treated with thinner, both deflocculation and dispersion occur
simultaneously—deflocculation because of the action of the anion, and
dispersion because of the conversion of the clay to the sodium form

• Dispersion is undesirable because it increases the plastic viscosity

• Dispersion may be avoided by the simultaneous addition of a polyvalent

salt or hydroxide with the thinner

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Mechanism of Gelation
Various linkages and plate orientations proposed to account for gel structure
may be summarized as follows:
1. Cross-linking between parallel plates, through positive edge to negative
surface linkages, to form a house of cards structure.
2. Edge-to-edge association, to form intersecting ribbons.
 The basis for this theory is, briefly, that because of the relatively high repulsive
potential between the basal surfaces, the preferred platelet orientation will be
parallel with edge-to-edge association.
3. Parallel association of plates, held together by the quasi-crystalline water
between them

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Mechanism of Gelation
• When the edges are positive, the platelets will
flex toward a negative basal surface, as shown
in Figure

• When the edges are negative, the stronger

basal repulsive potential will cause the
platelets to align parallel, when not prevented
from doing so by mechanical interference.

• Addition of a thinner reverses positive

edge potentials, and increases the repulsive
forces between the edges Schematic representation of edge-to-face bonds.
63
Polymers
• Organic colloids composed of unit cells
(monomers) such as the cellulose cell
shown in Figure
• Linked together either in straight or
branched chains to form macromolecules
• Polymer configuration when it mixed with
water depends on its degree of
polymerization (D.P) and its degree of
substitution (D.S)
• D.P refers to number of times the ring
structure is repeated,
• D.S refers to number of substitutions
occurring on a single repeating ring
structure
64
Polymers Use
• To give desired properties which cannot be obtained
with colloidal clays.
• Example: Starch (filtration control in salt water mud)

• Starch is stable in salt water, whereas clays are not

• Synthetic polymers are often made by modifying

natural polymers.
• Example: Carboxymethylcellulose (CMC) is made by
reacting cellulose with chloracetic acid and NaOH,
substituting CH3COO~ Na+ for H, as shown in Figure

65
• Polymer applications and functions in drilling fluids depend on its molecular
weight distribution and ionicity
• Polymer stability in solution depends on salt concentrating, pH, calcium presence,
and degradation.
• Drilling fluids viscosity and filtration are controlled by polymer molecular weight;
• The negative charged anionic polymer functions as deflocculant, fluid loss
controller and shale stabilizers.
• Polymer ability to hydrate in water nor to perform its functions can be hampered
if the salinity of water.

66
Polymers Use
Important function of carboxyl group
1. It imparts water solubility (strictly speaking, water dispersibility) to the
otherwise insoluble cellulose polymer
2. Dissociation of Na creates negative sites along the chain, Mutual repulsion
between the charges causes the randomly coiled chains to stretch linearly,
thereby increasing the viscosity

 Soluble salts, especially polyvalent salts, repress dissociation, allowing the

chains to coil.
 Polymers that carry electrostatic charges are termed polyelectrolytes. Because
its charges are negative, CMC is an anionic polyelectrolyte.

67
Polymers Use
• Degree of polymerization (DP): The number of monomers in a macromolecule
• Polymers are synthesized by varying By varying the DP and the DS.
• A high DP results in a high viscosity.
• A high DS also gives a high viscosity (a phenomenon known as the
electroviscous effect) and increases the resistance to soluble salts.

68
Polymers Examples
• CMC is used as a viscosifier and as a filtration control agent.
• Three grades covering a range of viscosity are available, and there is a
proprietary product called polyanionic cellulose for use in salt-water muds.
• It is made by converting some of the amides on a polyacrylamlde chain to
carboxylates, a process called hydrolysis.
• 70% hydrolyzed copolymer is used for filtration control;
• 30% one for preserving hole stability

69
Polymers Use
• The most likely explanation of the shale stabilizing action of the 30% hydrolyzed
copolymer is that it coats the shale surfaces exposed on the sides of the hole, thereby
inhibiting disintegration. Similarly, it coats and protects shale drill cuttings—a process
known as encapsulation.

• The coating is believed to result from the attraction between the negative sites on the
polymer chain and the posilive sites on the edges of the clay platelets. The reason the
30% hydrolyzed copolymer is the most effective for shale preservation is probably that
the charged sites on the chain match the spacing of the clay platelets.

70
Mechanism of water clarification
• The copolymer does not by itself cause flocculation; at least enough salt must be
present to initiate flocculation, and then the polymer chains will bind the
flocculated particles together.
• This point may be demonstrated by changing the order in which salt and
the copolymer are added to a suspension of clay in fresh water (see Figure
4-30A).
• If the copolymer is added first, the chains are adsorbed around the edges
of individual platelets, and are therefore not available for linking between
platelets when the salt is subsequently added.
• Consequently, the platelets separate if the salt concentration is diluted below the
flocculation value.
• On the other hand, if the salt is added first, then the chains can link between
adjacent platelets and hold the floes together when the suspension is diluted.

71
 72
Effect of order of addition of salt and polymer
Platelets repel each other when the edges are
saturated with polyelectrolyte 73
• Another acrylic copolymer, vinyl acetate-maleic acid, is used as a
bentonite extender to increase the yield of commercial bentonite
• Between 0.1% and 2 % of the copolymer is added to the bentonite
• When the bentonite is dispersed in fresh water, the copolymer chains
form links between the dispersed platelets, increasing the viscosity
and yield point.

74
• Nonionic polymers have no dissociable inorganic radical, and
therefore carry no electrostatic charge
• Greater stability in high salinity fluids
• Example: Starch is nonionic, and is used for filtration control in salt
water muds.
• It has the advantage of being inexpensive,
• Disadvantage of being biodegradable, and a biocide must be used
with it.

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• Other nonionic polymers include hydroxyethylcellulose (HEC) and guargum
• Like CMC, HEC is made from cellulose, but its functional group is an ethylene
oxide chain, (CH2-O-CH2)n- HEC
• Advantages: it is stable in polyvalent brines, and it is almost completely soluble in
acid.
• It is used as completion and workover fluids.
• Guar gum is also used in workover fluids, but is degraded by enzymes instead of
acid.
• The colloidal activity of natural gums is reduced by high concentrations of
monovalent salts, and eliminated in polyvalent brines. However, gums that have
been reacted with ethylene oxide or propylene oxide (see Figure 4-31) are stable
even in saturated polyvalent brines.

76
Disadvantage of organics polymer
• Thermal decomposition
• Bacterial degradation

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Problem 1

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79
Solution

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