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Basic Structural Units

Clay minerals are made of two distinct structural units.
oxygen hydroxyl or oxygen aluminium or magnesium

silicon

0.26 nm

0.29 nm

Silicon tetrahedron
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Aluminium Octahedron
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Tetrahedral Sheet
Several tetrahedrons joined together form a tetrahedral sheet.

tetrahedron hexagonal hole

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Tetrahedral & Octahedral Sheets

For simplicity, lets represent silica tetrahedral sheet by:
Si

and alumina octahedral sheet by:

Al

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Different Clay Minerals

Different combinations of tetrahedral and octahedral sheets form different clay minerals:
1:1 Clay Mineral (e.g., kaolinite, halloysite):

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Different Clay Minerals

Different combinations of tetrahedral and octahedral sheets form different clay minerals:
2:1 Clay Mineral (e.g., montmorillonite, illite)

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Kaolinite

Typically 70-100 layers

Al Si Al Si Al Si Al Si
0.72 nm

joined by strong H-bond no easy separation

joined by oxygen sharing

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Kaolinite
used in paints, paper and in pottery and

pharmaceutical industries
(OH)8Al4Si4O10

Halloysite
kaolinite family; hydrated and tubular structure (OH)8Al4Si4O10.4H2O

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Montmorillonite
also called smectite; expands on contact with water Si Al Si Si Al Si Si Al

easily separated by water

0.96 nm

joined by weak van der Waals bond

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Si

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Montmorillonite
A highly reactive (expansive) clay (OH)4Al4Si8O20.nH2O swells on contact with water

Bentonite

high affinity to water

montmorillonite family used as drilling mud, in slurry trench walls,

stopping leaks
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Illite
Si

joined by K+ ions
fit into the hexagonal holes in Si-sheet

Al Si
Si Al Si
0.96 nm

Si Al Si
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Others
Chlorite
A 2:1:1 (???) mineral. Si Al Al or Mg

Vermiculite
montmorillonite family; 2 interlayers of water

Attapulgite
chain structure (no sheets); needle-like appearance
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A Clay Particle

Plate-like or Flaky Shape

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Clay Fabric
edge-to-face contact face-to-face contact

Flocculated
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Dispersed
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Clay Fabric
Electrochemical environment (i.e., pH, acidity, temperature, cations present in the water) during the time of sedimentation influence clay fabric significantly. Clay particles tend to align perpendicular to the load applied on them.

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Scanning Electron Microscope

common technique to see clay particles qualitative

plate-like structure

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Others
X-Ray Diffraction (XRD)
to identify the molecular structure and minerals present

Differential Thermal Analysis (DTA)

to identify the minerals present

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Casagrandes PI-LL Chart

60 50

U-line

montmorillonite

Plasticity Index

illite kaolinite halloysite

A-line

40 30 20 10 0 0 10 20 30 40

chlorite
50 60 70 80 90 100

Liquid Limit

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Specific Surface
surface area per unit mass (m2/g)
smaller the grain, higher the specific surface

e.g., soil grain with specific gravity of 2.7

10 mm cube spec. surface = 222.2 mm2/g

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1 mm cube
spec. surface = 2222.2 mm2/g
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Isomorphous Substitution
substitution of Si4+ and Al3+ by other lower valence

(e.g., Mg2+) cations

results in charge imbalance (net negative) positively charged edges + + + + _ _ _ _ +_ + _ _ _ __ + _ _ _ _ _ _ _ _ _ _ _ _ _
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negatively charged faces

Clay Particle with Net negative Charge

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Cation Exchange Capacity (c.e.c)

known as exchangeable cations
capacity to attract cations from the water (i.e., measure of the net negative charge of the clay particle) measured in meq/100g (net negative charge per 100 g of clay) milliequivalents The replacement power is greater for higher valence and larger cations. Al3+ > Ca2+ > Mg2+ >> NH4+ > K+ > H+ > Na+ > Li+
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A Comparison
Mineral
Kaolinite Illite Montmorillonite Chlorite

Specific surface (m2/g) 10-20

80-100 800 80

C.E.C (meq/100g) 3-10

20-30 80-120 20-30

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Cation Concentration in Water

cation concentration drops with distance from clay particle clay particle + + ++ + ++ + + + + + + + + + + + ++ + + + + + + + + + + + + + ++ + +
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+
+ + +

- + cations + - ++ + + + + + + + + + + -+ + + + - + + + + ++ -+ + + + + + + -+ + +
double layer

+
+ + + free water
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Adsorbed Water
A thin layer of water tightly held to particle; like a skin 1-4 molecules of water (1 nm) thick more viscous than free water SIVA

adsorbed water

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Clay Particle in Water

adsorbed water

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1nm 50 nm - double layer - water

free water

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Summary - Clays
Clay particles are like plates or needles. They are

negatively charged.
Clays are plastic; Silts, sands and gravels are non-plastic. Clays exhibit high dry strength and slow dilatancy.

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Summary - Montmorillonite
Montmorillonites have very high specific surface,

cation exchange capacity, and affinity to water. They form reactive clays.
Montmorillonites have very high liquid limit (100+),

plasticity index and activity (1-7).

Bentonite (a form of Montmorillonite) is frequently used as drilling mud.
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