Clay Minerals
Recall the formation of clay minerals:Chemical Weathering
Introduction
• In civil engineering, clay often means a soil
which contains some clay minerals as well as
other minerals constituents.
• Clay can refer to specific minerals such as
kaolinite or illite.
Clay minerals
• Chemically, clays are hydrous alumino-silicates
plus other metallic ions.
• Clays can be only seen with an electron
microscope
• Individual crystals look like tiny plates or flakes
• X-ray diffraction studies showed that these
flakes consist of many crystal sheets which
have a repeating atomic structure.
Fundamental crystal sheets
• Tetrahedral or silica sheet
• Octahedral or alumina sheet
• The particular way in which these sheets are
stacked, together with different bonding and
metallic ions in the crystal lattice, constitute
the different clay minerals.
Basic Structural Units
Clay minerals are made of two distinct
structural units.
hydroxyl or
oxygen oxygen
aluminium or
silicon magnesium
0.26 nm
0.29 nm
Silicon tetrahedron Al or Mg Octahedron
Tetrahedral sheet
• Tetrahedral or silica sheet is basically a
combination of silica tetrahedral units which
consists of four oxygen atoms at the corners,
surrounding a single silicon atom.
Silicon
Oxygen
Single silica tetrahedron
Tetrahedral sheet
• The oxygen atoms at the base of each tetrahedron are in one
plane.
• Oxygen atoms at the bases of each tetrahedron are combined
to form a sheet structure
Isometric view of tetrahedral Schematic representation
or silica sheet
Octahedral sheet
• Octahedral sheet is basically a combination of
octahedral units consisting of six oxygen or
hydroxyls enclosing an aluminum, magnesium,
iron or other atom.
Aluminum or magnesium
Oxygen or hydroxyl
Single aluminum (or magnesium) octahedron
Octahedral sheet
Isometric view of octahedral sheet
Schematic representation of octahedral or alumina (or magnesia) sheet
• Substitution of different cations in the
octahedral sheet is rather common and leads
to different clay minerals.
• Since the ions substituted are approximately
the same physical size such substitution is
called isomorphous substitution.
Example:
• If all the anions of the octahedral sheet are hydroxyls and
two-thirds of the cation positions are filled with aluminum,
then the mineral is called gibbsite.
• If magnesium is substituted for the aluminum in the sheet and
fills all the cation positions, then the mineral is called brucite.
• The variations in the basic sheet structures make up the
dozens of clay minerals which have been identified.
• All clay minerals consist of the two basic
sheets which are stacked together in certain
unique ways and with certain cations present
in the octahedral and tetrahedral sheets.
• For engineering purposes, it sufficient to
describe only few clay minerals.
Kaolinite
• Kaolinite consists basically repeating layers of
one tetrahedral (silica) sheet and one
octahedral (alumina or gibbsite) sheet.
• Because of the stacking of one layer of each of
the two basic sheets, kaolinite is called as 1:1
clay mineral.
• Kaolinite is the primary constituent in china
clay; used in paper, paint and pharamaceutical
industries.
Schematic diagram of the structure of kaolinite
Ionic bond
Hydrogen bond
• The basic layers(one set Al and Si) are stacked and
held together by hydrogen bonds between the
hydroxyls of the octahedral sheet and the oxygen of
the tetrahedral sheet.
• Since the hydrogen bond is very strong, it prevents
hydration and allows the layers to stack up to make a
rather large crystal.
• Typical crystal of kaolin can be 70 to 100 layers thick.
Kaolinite
Halloysite
• Halloysite is another 1:1 mineral related to
kaolinite.
• It differs from kaolinite in that when it was formed
it somehow became hydrated between the layers,
causing a distortion or random stacking in the
crystal lattice so that it is tubular in shape.
• The water can easily be driven out from between
the layers by heating or even air drying and the
process is irreversible.
Halloysite
Montmorillonite
• Montmorillonite is sometimes called as
smectite.
• It is an important mineral composed of two
silica sheets and one alumina (gibbsite) sheet.
• Thus it is called as 2:1 mineral.
• The octahedryal sheet is between two silica
sheets with tips of the tetrahedrons combining
with the hydroxyls of the octahedral sheet to
form a single layer.
Schematic diagram of the structure of montmorillonite
• The thickness of each 2:1 layer is about 0.96 nm
• Because the bonding by van der Waals’ forces
between the tops of the silica sheets is weak
and there is a net negative charge deficiency in
the octahedral sheet, water and exchangeable
ions can enter and separate the layers.
• Thus montmorillonite crystals can be very small
but at the same time they have very strong
attraction for water.
• Soils containing montmorillonite are very
susceptible to swelling as they change water
content, and the swelling pressures developed
can easily damage light structures and
highway pavements.
Montmorillonite applications:
• Drilling mud
• Industrial and pharmaceutical applications
Montmorillonite
Illite
• It also has 2:1 structure similar to montmorillonite, but
interlayers are bonded together with a potassium atom.
• In addition, there is some isomorphous substitution of
aluminium for silicon in the silica sheet.
Schematic diagram of the structure of illite
Illite
Identification of clay minerals
X-ray diffraction technique
• Materials with regular or repeating patterns of
crystal structure will diffract X-rays.
• Different minerals with different crystalline
structures will have different X-ray diffraction
patterns.
• Patterns of common minerals are published
• Detailed quantitative analysis is impossible – about
all that one can tell is which minerals are present
and roughly how much of each.
X-Ray Diffraction
2500
I (VS)
[3.3]
2000
1500
Intensity
V
K
Chl K [3.5]
1000 [4.1] M
[7] [4.3]
V [2.5]
[9.2]
500
0
0 5 10 15 20 25 30 35 40
2 theta
V = Vermiculite; Chl = Chlorite; K = Kaolinite; I(VS) = Illite
(Very Strong); M = Montmorillonite; [ ] is the d spacing in A 0
(From Fang & Bloss, 1966)
Identification clay minerals by Atterberg limits
Location of common clay minerals on Casagrande’s plasticity
chart (develped from Casagrande, 1948 and Mitchell 1976)
Clay Fabric
edge-to-face contact
face-to-face contact
Flocculated Dispersed
Dispersed structure
Flocculated
