Clay Minerals

1
 Origin of Clay Minerals
The contact of rocks and water produces clays, either at or near the surface
of the earth (from Velde, 1995).
Rock +Water Clay
For example,
The CO2 gas can dissolve in water and form carbonic acid, which will become
hydrogen ions H+ and bicarbonate ions, and make water slightly acidic.
CO2+H2O H2CO3 H+ +HCO3-
The acidic water will react with the rock surfaces and tend to dissolve the K
ion and silica from the feldspar. Finally, the feldspar is transformed into
kaolinite.
Feldspar + hydrogen ions+water clay (kaolinite) + cations, dissolved silica
2KAlSi3O8+2H+ +H2O Al2Si2O5(OH)4 + 2K+ +4SiO2
Note that the hydrogen ion displaces the cations.

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 Origin of Clay Minerals (Cont.)
The alternation of feldspar into kaolinite is very common in
the decomposed granite.

The clay minerals are common in the filling materials of joints

and faults (fault gouge, seam) in the rock mass.
Weak plane!

3
 Basic Unit-Silica Tetrahedra
(Si2O10)-4
1 Si
4O Replace four
Oxygen with
hydroxyls or
combine with
positive union

Tetrahedron

Hexagonal Plural: Tetrahedra

hole

(Holtz and Kovacs, 1981) 4

 Basic Unit-Octahedral Sheet
1 Cation
6 O or OH

Gibbsite sheet: Al3+

Al2(OH)6, 2/3 cationic spaces are filled
Different
One OH is surrounded by 2 Al: cations
Dioctahedral sheet

Brucite sheet: Mg2+

Mg3(OH)6, all cationic spaces
are filled
One OH is surrounded by 3 Mg:
Trioctahedral sheet

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(Holtz and Kovacs, 1981)
Basic Unit-Summary

Mitchell, 1993

6
 Synthesis

Mitchell, 1993

Noncrystalli
ne clay -
allophane
7
 Minerals-Kaolinite
Basal spacing is 7.2

layer

Si4Al4O10(OH)8. Platy shape

The bonding between layers are van der
Waals forces and hydrogen bonds
(strong bonding).
There is no interlayer swelling
Trovey, 1971 ( from
Mitchell, 1993)
Width: 0.1~ 4m, Thickness: 0.05~2 m
8
17 m
 Minerals-Halloysite
Si4Al4O10(OH)84H2O
A single layer of water between unit
layers.
The basal spacing is 10.1 for hydrated
halloysite and 7.2 for dehydrated
halloysite.
If the temperature is over 50 C or the
relative humidity is lower than 50%, the
hydrated halloysite will lose its interlayer
water (Irfan, 1966). Note that this process is
irreversible and will affect the results of
soil classifications (GSD and Atterberg
limits) and compaction tests.
There is no interlayer swelling.
Trovey, 1971 ( from
Mitchell, 1993)
Tubular shape while it is hydrated.
2 m
9
 Minerals-Montmorillonite
Si8Al4O20(OH)4nH2O (Theoretical
unsubstituted). Film-like shape.
There is extensive isomorphous
substitution for silicon and aluminum
by other cations, which results in
charge deficiencies of clay particles.
nH2O and cations exist between unit
nH2O+cations layers, and the basal spacing is from
9.6 to (after swelling).
The interlayer bonding is by van der
Waals forces and by cations which
balance charge deficiencies (weak
bonding).
There exists interlayer swelling,
which is very important to
engineering practice (expansive
clay).
Width: 1 or 2 m, Thickness: 10
10
5 m (Holtz and Kovacs, 1981) ~1/100 width
 Minerals-Illite (mica-like minerals)
Si8(Al,Mg, Fe)4~6O20(OH)4(K,H2O)2. Flaky shape.
The basic structure is very similar to the mica,
so it is sometimes referred to as hydrous mica.
Illite is the chief constituent in many shales.
potassium K
Some of the Si4+ in the tetrahedral sheet are
replaced by the Al3+, and some of the Al3+ in
the octahedral sheet are substituted by the
Mg2+ or Fe3+. Those are the origins of charge
deficiencies.
The charge deficiency is balanced by the
potassium ion between layers. Note that the
potassium atom can exactly fit into the
hexagonal hole in the tetrahedral sheet and
form a strong interlayer bonding.
The basal spacing is fixed at 10 in the
presence of polar liquids (no interlayer
swelling).

Trovey, 1971 ( from

Width: 0.1~ several m, Thickness: ~ 30
11
7.5 m Mitchell, 1993)
 Minerals-Vermiculite (micalike minerals)
The octahedral sheet is brucite.
The basal spacing is from 10 to 14
.
It contains exchangeable cations
such as Ca2+ and Mg2+ and two
layers of water within interlayers.
It can be an excellent insulation
material after dehydrated.

Illite Vermiculite

Mitchell, 1993

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 Minerals-Chlorite

The basal spacing is fixed at 14 .

Gibbsite or
brucite

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Chain Structure Clay Minerals
Attapulgite They have lathlike or threadlike
morphologies.
The particle diameters are from 50
to 100 and the length is up to 4 to
5 m.
Attapulgite is useful as a drilling mud
in saline environment due to its high
stability.

4.7 m
Trovey, 1971 ( from Mitchell, 1993) 14
 Mixed Layer Clays
Different types of clay minerals have similar structures (tetrahedral and
octahedral sheets) so that interstratification of layers of different clay
minerals can be observed.

In general, the mixed layer clays are composed of interstratification of

expanded water-bearing layers and non-water-bearing layers.
Montmorillonite-illite is most common, and chlorite-vermiculite and
chlorite-montmorillonite are often found.
(Mitchell, 1993)

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 Noncrystalline Clay Materials
Allophane
Allophane is X-ray amorphous and has no
definite composition or shape. It is composed of
hollow, irregular spherical particles with
diameters of 3.5 to 5.0 nm.

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Identification of Clay Minerals

17
 X-ray diffraction

Mitchell, 1993

The distance of atomic planes d can be determined based on the Braggs

equation.
BC+CD = n, n = 2dsin, d = n/2 sin
where n is an integer and is the wavelength.
Different clays minerals have various basal spacing (atomic planes). For
example, the basing spacing of kaolinite is 7.2 .

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 Differential Thermal Analysis (DTA)
For example:
Quartz changes from the to form at 573 C
and an endothermic peak can be observed.
T
Temperature (100 C)
Differential thermal analysis (DTA)
consists of simultaneously heating
a test sample and a thermally inert
substance at constant rate (usually
about 10 C/min) to over 1000 C
and continuously measuring
differences in temperature and the
inert material T.
Endothermic (take up heat) or
exothermic (liberate heat)
reactions can take place at
different heating temperatures.
The mineral types can be
characterized based on those
signatures shown in the left figure.
(from Mitchell, 1993)
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 DTA (Cont.)
If the sample is thermally inert, If the phase transition of the
sample occurs,

T T

Crystallize

Melt

Time t
Endothermic reactions take
up heat from surroundings
and therefore the
temperature T decreases.
Time t
Exothermic reactions liberate
heat to surroundings and
therefore the temperature T
increases.

T= the temperature of the sample the temperature of the thermally inert 20

substance.
 Other Methods
1.Electron microscopy
2.Specific surface (Ss)
3.Cation exchange capacity (cec)
4.Plasticity chart

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 Other Methods (Cont.)
5. Potassium determination
Well-organized 10 illite layers contain 9% ~ 10 % K2O.

6. Thermogravimetric analysis
It is based on changes in weight caused by loss of
water or CO2 or gain in oxygen.

Sometimes, you cannot identify clay minerals only

based on one method.
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