Mud chemistry, Clay

mineralogy and the colloid

chemistry of Drilling Fluids
By:
Vignesh Shenoy
Introduction
• Drill cuttings from argillaceous formations become incorporated in any drilling fluid, and can profoundly
change its properties.
• The stability of the borehole depends to a large extent on interactions between the drilling fluid and exposed
shale formations.
• The development of “inhibitive” aqueous drilling fluids was initiated to control clay hydration and swelling.
• In nonaqueous fluids, the introduction of water-wet solids can upset the properties of the fluid.
• Interactions between the mud filtrate, whether water or oil, and the clays present in producing horizons may
restrict productivity of the well.
• All of these point out the need for the drilling fluids technologist to have knowledge of clay mineralogy.
CHARACTERISTICS OF COLLOIDAL
SYSTEMS
• Colloids are not, as is sometimes supposed, a specific kind of matter. They are particles whose size falls
roughly between that of the smallest particles that can be seen with an optical microscope and that of true
molecules, but they may be of any substance.
• The interactions between two phases of matter are an essential part of colloidal behavior. Colloidal systems
may consist of solids dispersed in liquids (e.g., clay suspensions, polymers), liquid droplets dispersed in
liquids (e.g., emulsions), or solids dispersed in gases (e.g., smoke).
• One characteristic of aqueous colloidal systems is that the particles are so small that they are kept in
suspension indefinitely by bombardment of water molecules, a phenomenon known as the Brownian
movement.
• The erratic movements of the particles can be seen by light reflected off them when they are viewed against
a dark background in the ultramicroscope.
CHARACTERISTICS OF COLLOIDAL
SYSTEMS
• Another characteristic of clay colloidal systems is that 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, i.e., they have similar molecules on one side and
dissimilar molecules on the other, whereas molecules in the interior of a
phase have similar molecules on all sides.
• Therefore, 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, which is
explained later.
 CHARACTERISTICS OF COLLOIDAL
SYSTEMS

2 mm
1 mm
A = 6(sides)* A = 8(no. of cubes)*
4(Area of each side) 6(sides)*
= 24 mm2 1(Area of each side)
= 48 mm2
The Suggested Particle Size Classification
Published in the API Recommended Practice
13C 2009
CHARACTERISTICS OF COLLOIDAL
SYSTEMS
• A large proportion of the solids in drilling muds falls in the silt size range.
• These particles are derived either from natural silts picked up from the formation, from larger particles
manufactured by the action of the bit, or from barite added to raise the density.
• Particles in this size fraction are commonly called the inert solids, but the term is relative, and when present
in high enough concentrations, inert solids exercise a considerable influence on the viscous properties of a
mud.
• Even NADFs can experience erratic viscous properties from inert solids if they are allowed to build up.
• Colloids, on the other hand, usually constitute a small proportion of the total solids, but exercise a relatively
high influence on mud properties because of their high degree of activity. They may be divided into two
classes:
• clay minerals, and
• organic colloids, such as starches, the carboxycelluloses, biopolymers, and the polyacrylamide
derivatives. These substances have macromolecules, or are long-chain polymers, whose size gives them
colloidal properties.
CLAY MINERALOGY
• Ordinary chemical analysis plays only a minor part in identifying and classifying
clay minerals.
• Clay minerals are of a crystalline nature, and the atomic structure of their
crystals is the prime factor that determines their properties.
• Identification and classification is carried out mainly by analysis of X-ray
diffraction patterns, adsorption spectra, and differential thermal analysis.
• Most clays have a mica-type structure.
• Their flakes are composed of tiny crystal platelets, normally stacked together
face-to-face. A single platelet is called a unit layer, and consists of:
• An octahedral sheet
• One or two sheets of silica tetrahedra
CLAY MINERALOGY
• Octahedral sheet:
• An octahedral sheet, made up of either aluminum or
magnesium atoms in octahedral coordination with
oxygen atoms as shown.
• If the metal atoms are aluminum, the structure is the
same as the mineral gibbsite, Al2(OH)6.
• In this case, only two out of three possible sites in the
structure can be filled with the metal atom, so the
sheet is termed dioctahedral.
• If, on the other hand, the metal atoms are
magnesium, the structure is that of brucite, Octahedral sheet; structure shown is that
Mg3(OH)6. of brucite.
• In this case all three sites are filled with the metal
atom, and the structure is termed trioctahedral.
CLAY MINERALOGY
• Sheets of Silica Tetrahedron:
• One or two sheets of silica tetrahedra, each silicon atom being
coordinated with four oxygen atoms, as shown.
• The base of the tetrahedral form a hexagonal network of oxygen atoms
of indefinite areal extent.
• The sheets are tied together by sharing common oxygen atoms.
• When there are two tetrahedral sheets, the octahedral sheet is
sandwiched between them, as shown.
• The tetrahedra face inwards and share the oxygen atom at their apexes
with the octahedral sheet, which displaces two out of three of the
hydroxyls originally present.
• This structure is known as the Hoffmann structure (Hofmann et al.,
1933), the dimensions of which are shown.

Atom arrangement in the unit cell of a three-

layer mineral (schematic).
Bonding between one octahedral sheet and two
tetrahedral sheets through shared
oxygen atoms.
The Smectites
• As mentioned earlier, pyrophyllite and talc are the
prototype minerals for the smectite group.
• In their crystal lattice, the tetrahedral sheet of one layer
is adjacent to the tetrahedral sheet of the next, so that
oxygen atoms are opposite oxygen atoms.
• Consequently, bonding between the layers is weak and
cleavage is easy (Grim, 1953, p. 16).
• Partly because of the weak bonding, and partly because
of high repulsive potentials on the surface of the layers
arising from isomorphous substitutions, water can enter
between the layers, thereby causing an increase in the c-
spacing. Diagrammatic representation of a three-layer
expanding clay lattice.
The Smectites
• Thus, smectites have an expanding lattice, which greatly
increases their colloidal activity, because it has the effect
of increasing their specific surface many times over.
• All the layer surfaces, instead of just the exterior surfaces,
are now available for hydration and cation exchange, as
shown.
• Members of the smectite group are differentiated on the
basis of the prototype mineral, the relative amounts of
substitutions in the octahedral or tetrahedral layer, and on
the species of atoms substituted.

Diagrammatic representation of a three-layer

expanding clay lattice.
The Smectites
The Smectites
• Montmorillonite is by far the best known member of the
smectite group, and has been extensively studied because
of its common occurrence and economic importance.
• It is the principal constituent of Wyoming bentonite and of
many other clays added to drilling fluids.
• It is the active component in the younger argillaceous
formations that cause problems of swelling and heaving
when drilled.
• Like other smectites, montmorillonite swells greatly
because of its expanding lattice.

Electron micrograph of
montmorillonite. Magnification
387,500.
Illites
• Illites are hydrous micas, the prototypes for which are muscovite (dioctahedral mica) and biotite
(trioctahedral mica).
• They are three-layer clays, with a structure similar to montmorillonite, except that the substitutions
arepredominately aluminum for silicon in the tetrahedral sheet.
• In many cases, as much as one silicon in four may be so replaced.
• Substitutions may also take place in the octahedral sheet, typically magnesium and iron for aluminum.
• The average charge deficiency is higher than that of montmorillonite (0.69 vs 0.41) (Weaver and Pollard,
1973, p. 63), and the balancing cation is always potassium.
• Illites differ sharply from montmorillonite in that they do not have an expanding lattice and in that no water
can penetrate between the layers.
Illites
• The strong interlayer bonding is probably because of the higher layer charge, because the site of the charge
is nearer the surface in the tetrahedral sheet, and because the size of the potassium ion is such that it just
fits into the holes in the oxygen network and forms secondary valance links between adjacent layers.
• Thus, the potassium normally is fixed, and cannot be exchanged.
• Ion exchange can, however, take place at the exterior surfaces of each aggregate.
• Since hydration is also confined to the exterior surfaces, the increase in volume is much less than that caused
by the hydration of montmorillonite.
• Illites disperse in water to particles having an equivalent spherical radius of about 0.15 μm, widths of about
0.7 μm, and thickness of about 720 A ° .
• Some illites occur in degraded form, brought about by leaching of potassium from between the layers.
• This alteration permits some interlayer hydration and lattice expansion, but never to the degree attained by
montmorillonite.
Kaolinite
• Kaolinite is a two-layer clay with a structure similar to that shown.
• One tetrahedral sheet is tied to one octahedral in the usual
manner, so that the octahedral hydroxyls on the face of one layer
are juxtaposed to tetrahedral oxygens on the face of the next
layer.
• In consequence, there is strong hydrogen bonding between the
layers, which prevent lattice expansion.
• There is little, if any, isomorphous substitutions, and very few, if
any, cations are adsorbed on the basal surfaces.
• Not surprisingly, therefore, most kaolinites occur in large, well-
ordered crystals that do not readily disperse to smaller units in
Atom arrangement in the unit cell of a two-layer
water.
mineral (schematic).
• The width of the crystals ranges from 0.3 to 4 μm and a thickness
from 0.05 to 2 μm. Dickite and nacrite are two other members of
the kaolinite group.
• They differ from kaolinite in their stacking sequences.
Chlorites
• Chlorites are a group of clay minerals whose characteristic structure consists of a layer of brucite alternating
with a three-sheet pyrophyllite-type layer, as shown.
• There is some substitution of Al+3 for Mg+2 in the brucite layer, giving it a positive charge which is balanced by
a negative charge on the three-sheet layer, so that the net charge is very low.
• The negative charge is derived from the substitution of Al13 for Si14 in the tetrahedral sheet. The general
formula is:
2[(Si,Al)4(Mg,Fe)3O10(OH)2] + (Mg,Al)6(OH)12

Diagrammatic representation of chlorite.

Chlorites
• The members of the chlorite group differ in the amount and species of atoms substituted in the two layers,
and in the orientation and stacking of the layers.
• Normally, there is no interlayer water, but in certain degraded chlorites, part of the brucite layer has been
removed, which permits some degree of interlayer hydration and lattice expansion.
• Chlorites occur both in macroscopic and in microscopic crystals.
• In the latter case, they always occur in mixtures with other minerals, which makes determination of their
particle size and shape very difficult.
• The c-spacing, as determined from macroscopic crystals, is 14 A ° , reflecting the presence of the brucite
layer.

Diagrammatic representation of chlorite.

Mixed-Layer Clays
• Layers of different clay minerals are sometimes found stacked in the same lattice.
• Interstratified layers of illite and montmorillonite, and of chlorite and vermiculite, are the most common
combinations.
• Generally, the layer sequence is random, but sometimes the same sequence is repeated regularly.
• Usually, mixed-layer clays disperse in water to smaller units more easily than do single mineral lattices,
particularly when one component is of the expanding type.
Attapulgite
• Attapulgite particles are completely different in structure and shape from
the mica-type minerals discussed so far.
• They consist of bundles of laths, which separate to individual laths when
mixed vigorously with water (see Fig. 4.10).
• The structure of these laths has been described by Bradley (1940).
• There are very few atomic substitutions in the structure, so the surface
charge on the particles is low.
• Also, their specific surface is low. Consequently, the rheological
properties of attapulgite suspensions are dependent on mechanical
interference between the long laths, rather than on electrostatic
interparticle forces.
• For this reason, attapulgite makes an excellent suspending agent in salt Electron micrograph of attapulgite clay
water. showing open mesh structure magnified
45,000 times.
Attapulgite
• Sepiolite is an analagous clay mineral, with different substitutions in the
structure, and wider laths than attapulgite. Sepiolite-based muds are
recommended for use in deep, hot wells because their rheological
properties are not affected by high temperatures (Carney and Meyer,
1976).

Electron micrograph of attapulgite clay

showing open mesh structure magnified
45,000 times.