Structure of Clay and its

interaction with Water

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Resource material: Various lecture notes, book chapters, and journals
 Building Blocks of Clay
• Silica Tetrahedron-four sides, four oxygen
molecules and one silica (Si+4)
• Aluminum Octahedron-eight sides, six oxygen
molecules and one Al+3
• These are bound together by shared oxygen
molecules into different layers

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 Silicate structure:The
SiO4 Tetrahedron

❑ Each silicon atom bonds strongly

with 4 oxygen atoms to give SiO4
tetrahedron.
❑ This stable SiO4 tetrahedron is the
basic building block of all silicates,
including pure silica.

❑ Treated as a negatively charged entity; each SiO4 unit

carries with it a net 4 negative charge (SiO44-).

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 The SiO4 Tetrahedron
❑ Silicates are not considered to be ionic, due to strong
covalent character of Si-O bond
❑ Bonds are directional and relatively strong.

Various silicate structures form due to the ways in which

SiO4 units can be linked together to form 1-, 2-, and 3-D
arrangements.

❑ The SiO4 units link to each other either directly by

the bridging oxygen (BO), or via a metal ion (M) link.

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 Simple Silicate Structures

❑ When silica combines with a metal oxide such

that the ratio MO/SiO2 ≥ 2

⚫ example: Olivine Mg2SiO4 MgO SiO2

⚫ the resultant silicates are made up of

separated SiO4 tetrahedron (island silicates
or, in polymer terms, monomers) ),
ionically linked by MO molecules.
(BO = 0, NBO = 4)
⚫ this group of silicates is called
orthosilicates AX(SiO4)

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 Silicate Structures

❑ When ratio MO/SiO2 < 2

⚫ two tetrahedra are shared by one bridging oxygen atom

(BO = 1, NBO = 3)
⚫ the resulted ion Si2O76- is known as silica dimer.
⚫ example: Akermanite (Ca2MgSi2O7), where two Ca2+
and one Mg2+ ions are bonded to each Si2O76- unit.
2CaO. MgO.2SiO2
This is the first step of the so called “polymerisation” of SiO4 monomer to give
chain, sheet and network silicates.

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 Silicate Structures

Chain/Ring Silicates
❑ With decreasing MO, degree of polymerisation increases.
❑ Chains of linked tetrahedra forms (-Si-O-Si-O-Si-).

❑ For single chain, O/Si = 3 (BO = 2, NBO = 2)

❑ For double chain, O/Si = 2.75 (BO = 2.5, NBO = 1.5)

❑ The NBO bonds between chains, joined by MO;

these bonds are weaker than Si-O bond.
❑ Thus, chain silicates are fibrous in nature.
❑ Example: single chain - Enstatite (MgSiO3)

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Fibrous and asbestos like minerals

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 Silicate Structures
Sheet/Layered Silicates
❑ O/Si = 2.5; BO = 3, NBO = 1
❑ the two bridging oxygen form 2-D sheets by joining repeating
units of (Si2O5)2-
❑ the unbonded oxygen projected outwards of the sheet and
combined with positively charged M ions.
❑ the sheet becomes polarised; can be hydroplastic.
❑ example: kaolinite clay Al2(Si2O5)(OH)2
talc Mg3(Si2O5)2(OH)2

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Silicate Structures

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 Quartz
Corundum structure

Silica sheet structure 11

Gibbsite sheet structure
 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 Aluminium Octahedron

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PHYLLOSILICATES Repeat formula: (Si2O5)2-n

Basic tetrahedral unit. The Si - O combination has a radius ratio of 0.30, which means
that the silicon ion fits nicely into a tetrahedral polyhedron.

Silicon ion shares its charge equally between the four oxygen ions, leaving each
oxygen with an excess charge of negative one.

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PHYLLOSILICATES

If each of the four oxygen ions bond with two silicon ions the result is a QUARTZ crystal.

In the phyllosilicates only one plane of oxygen ions bond with two silicon ions. This
bonding is extended in two directions to form a sheet of silicon tetrahedrons. This
sheet of tetrahedral units with unbalanced charges on the apical O ions.

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PHYLLO (layer, sheet) SILICATES
Repeat formula: (Si2O5)2-n

The result is the creation of an infinite, 2-dimensional sheet of tetrahedra.

The closest packing arrangement for spheres in two dimensions is a plane having
hexagonal symmetry. If we examine any one sphere in the hexagonal closest
packing arrangement, we can see that there are 6 interstitial spaces or holes
contained within each hexagonal ring.

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The basic structure of clay minerals can be obtained though the stacking of two
sheets: tetrahedral sheets and octahedral sheets sometime separated by an interlayer.
Different clay minerals are formed by: (1) different combination of these two units and
the interlayer and (2) changes in the composition of the sheets
The tetrahedral sheet
The basic unit of this layer is a tetrahedron, which contains normally one Si4+ in the
centre with four O2- at the corners. The tetrahedra are linked to neighboring
tetrahedra by sharing three oxygen atoms each to form a hexagonal mesh pattern. All
the unshared corners with the apical oxygen atoms point in the same direction to form
part of the adjacent octahedral sheet

oxygen
tetrahedr
silicon on

0.26 nm

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The octahedral sheet
The unit is an octahedron, contains mainly Al3+ or Mg2+ surrounded by six oxygen
atoms or hydroxyl groups. When the cations are trivalent, the sheet contains two
cations per half unit cell and one vacancy, and is known as a dioctahedral structure.
When the cations are divalent, the sheet contains three cations per half unit cell and
no vacancy, and is known as a trioctahedral structure. Octahedral sheets can contain
other cations including Li+ , Fe2+ , and Fe3+

hydroxyl or
oxygen

aluminium or
magnesium

0.29 nm

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The octahedral sheet
Aluminum shares +0.5 of its charge with each of the surrounding oxygen ions,
leaving each oxygen ion with a negative 1.5 charge.

In this case aluminum is slightly less electropositive than is silicon and is able to
approach close enough that corner oxygen ions can be shared. In a matrix of these
octahedral units each oxygen will be bonded to two aluminum ions, leaving it with
a remaining -1 charge.

The charge can be satisfied by attaching a proton (hydrogen ion) and when this
type of structure is continued in three dimensions we have the mineral GIBBSITE

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Clay Structure

Remember we left a sheet of octahedral units with apical oxygen ions still having an
unbalanced charge?
The two sheets can be brought together with the apical oxygen ions of the tetrahedral layer
also being in the octahedral layer. As a result, the charge on these oxygen ions is balanced
by bonding to one silicon ion and two aluminum ions.

Al
O
Ex. Kaolinite
Si
1:1 clay
H nonexpandable

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 PHYLLOSILICATES

The Si-O tetrahedral linkage represents the strongest bonds within the
silicate structures and, therefore, tends to dominate other bonding
linkages with respect to stability and general properties of the silicate
minerals.

How many types of Phyllosilicates exist?

How do they differ?

It is the combination of various tetrahedral and octahedral

sheets which distinguishes the individual members of the
phyllosilicate minerals and also the presence of various
elements in the structures.

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•The fundamental units of tetrahedral sheets and octahedral sheets can combine with
the hydroxyl group of the tetrahedral layer contributing to the octahedral layer.

•Different combinations of these units and chemical modification of the basic

structure give rise to the range of clay minerals with different properties.

Structure

Tetrahedron and octahedral Layers

units 21
 Tetrahedral & Octahedral Sheets
For simplicity, let’s represent silica tetrahedral sheet by:

Si

and alumina octahedral sheet by:

Al

Different combinations of tetrahedral and octahedral

sheets form different clay minerals:
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 Clay Mineral Classification
• 1:1 Clay Minerals
• 2:1 Clay Minerals
• Mixed Mineralogy

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 1:1 Clay Minerals
• Like an open face sandwich
– One silica tetrahedron (bread)
– One aluminum octahedron (filling)
• The most common 1:1 minerals is Kaolinite

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 1:1 Clay Structure
(Kaolinite)

Al
Al
Si
Si
Typically
Typically
70-100 Al
Al
70-100 0.72 nm
layers
layers Si
Si
Al
Al
joined by
joined by strong
strong H-bond
H-bond Si
no
no easy
easy separation
separation Si
Al joined by oxygen
sharing
Si
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1:1 Clay Minerals
CEC ~ 7 meq/100 g
non-expanding

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 1:1 Minerals-Kaolinite
Basal spacing is 7.2 Å

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~ 4m, Thickness: 0.05~2 m
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17 m
 2:1 Clay Minerals
• Like a sandwich with two slices of bread
– Two silica tetrahedrons (bread)
– One aluminum octahedron (filling)
• The 2:1 clays can be broken into 2 groups
– Expansive
– Non expansive

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 2:1 Clay Mineral
Montmorillonite (expanding)
➢ also called smectite; expands on contact with water
Si

Al

Si

Si

Al 0.96 nm
easily separated Si
by water

joined by weak Si
van der Waal’s bond Al

Si 29
 2:1 Minerals-Montmorillonite
•Si8Al4O20(OH)4·nH2O (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.
•n·H2O and cations exist between unit
n·H2O+cations layers, and the basal spacing is from
9.6 Å 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
30
5 m (Holtz and Kovacs, 1981) Å~1/100 width
2:1 Clay Minerals (expanding)
CEC: 100 – 200 meq/100 g (vermiculite)
70 – 120 meq/100 g (smectite)

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 2:1 Clay Mineral
Illite (non-expanding)
Si

Al

Si
joined by K+ ions

Si
fit into the hexagonal 0.96 nm
Al
holes in Si-sheet
Si

Si

Al
Si

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 2:1 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 Å in the
presence of polar liquids (no interlayer
swelling).
Trovey, 1971 ( from
7.5 m Mitchell, 1993) •Width: 0.1~ several m, Thickness: ~ 30 Å 33
2:1 Clay Minerals
CEC ~ 40 meq/100 g
non-expanding

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Kaolinite

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Smectite (montmorillonite)

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Illite

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Chlorite
Vermiculite

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40
 Properties
• Surface Area
• Cation Exchange Capacity
• Expansion

These properties are correlated to

Water - Clay interaction

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 Definition (Surface Area)
Specific surface = surface / volume
Specific surface = surface / mass Preferred
Surface related force Surface related forces: van der
Gravational force Waals forces, capillary forces, etc.

Example:
111 cm cube,  = 2.65g / cm3
6 1cm2 −4
Ss = = 2.3  10  m 2
/g Ss is inversely
1cm  2.65 g / cm
3 3

proportional to
111m cube,  = 2.65g / cm3 the particle size
6 1m 2
Ss = = 2. 3  m 2
/g
1m  2.65 g / cm
3 3

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 Typical Values
700-840 m2/gm (including the interlayer surface)
Montmorillonite

Interlayer surface

Illite
65-100 m2/gm

Kaolinite

10-20 m2/gm

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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

1 mm cube
10 mm cube

spec. surface = 222.2 mm2/g spec. surface = 2222.2 mm2/g

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Interaction of Water and Clay
Minerals

45
46
47
 Origins of Charge Deficiencies
1. Imperfections in the crystal lattice -
Isomorphous substitution.
• The cations in the octahedral or tetrahedral sheet can be replaced by
different kinds of cations without change in crystal structure (similar
physical size of cations).
For example,
Al3+ in place of Si4+ (Tetrahedral sheet)
Mg2+ instead of Al3+(Octahedral sheet)
unbalanced charges (charge deficiencies)

• This is the main source of charge deficiencies for montmorillonite.

• Only minor isomorphous substitution takes place in kaolinite.

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Origins of Charge Deficiencies (Cont.)
2. Imperfections in the crystal lattice -
The broken edge

The broken edge can be positively

or negatively charged.

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 Origins of Charge Deficiencies (Cont.)
3. Proton equilibria (pH-dependent charges)
M − OH + H +  M − OH 2+ (Pr tonation)
M − OH + OH −  M − O − + H 2O ( Deprotonation)

H
M O Kaolinite particles are positively
H+ charged on their edges when in a
low pH environment, but negatively
M O H
M: metal charged in a high pH (basic)
environment.
M O-

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 “Charged” Clay Particles
- or + • External or interlayer surfaces are
negatively charged in general.
• The edges can be positively or
negatively charged.
• Different cations balance charge
deficiencies.

Cation

- or +
Kaolinite and negative gold sol Dry condition
(van Olphen, 1991)
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 Clay-Water Interaction
1. Hydrogen bond
Kaolinite

H
O O
H H

Clay Surfaces
Adsorbed layers Free water
3 monolayers Bulk water

Oxygen Hydroxyl
O OH
The water molecule “locked” in the
adsorbed layers has different properties
compared to that of the bulk water due to
the strong attraction from the surface.
H
O 52
H
 (c)2001 Brooks/Cole, a division of Thomson Learning, Inc. Thomson Learning ™ is a trademark used herein under license.

double layer
Figure 2.12 Attraction of

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dipolar molecules in diffuse
 Polar Water Molecules
Structure Polar molecule O(-)

H(+) H(+)
Hydrogen bond Salts in aqueous solution

hydration
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 Clay-Water Interaction (Cont.)
Na+ crystal radius: 0.095 nm
2. Ion hydration
radius of hydrated ion: 0.358 nm

cation

Clay
layers

The cations are fully hydrated,

Dry condition The water molecules which results in repulsive forces
(Interlayer) wedge into the interlayer and expanding clay layers
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after adding water (hydration energy).
 Clay-Water Interaction (Cont.)

Relative sizes of adsorbed water layers on sodium montmorillonite and

sodium kaolinite

Holtz and Kovacs, 1981

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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
+ +
+ + _
+ _ _
_ _ negatively charged faces
+ _ _ _ _
_ _
+ _ _
_ _ _ _ _ _
_ _ _ _

Clay Particle with Net negative Charge 57

 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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 Cation Concentration in Water
➢ cation concentration drops with distance from clay particle
clay particle
+ +

+ + 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

adsorbed water
- -
- -
- -
- -
- -
- -
- -

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Clay Particle in Water

adsorbed water

- - 1nm
- -
- - 50 nm
- - free water
- -
- -
- -
double layer
water

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 Terminology
Face (F)
Edge (E)
Clay Particle
• Dispersed: No face-to-face association of clay particles
• Aggregated: Face-to-face association (FF) of several clay particles.

• Flocculated: Edge-to-Edge (EE) or edge-to-face (EF) association

• Deflocculated: No association between aggregates

van Olphen, 1991 (from Mitchell, 1993)

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 Particle Associations

Dispersed and deflocculated Aggregated but deflocculated

Edge-to-face flocculated Edge-to-edge flocculated but

but dispersed dispersed

Edge-to-face flocculated Edge-to-edge flocculated Edge-to-face and edge to

and aggregated and aggregated edge flocculated and
aggregated

van Olphen, 1991

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 Summary of Particle Associations
Flocculated fabric Dispersed fabric
Edge-to-face (EF): positively
charged edges and negatively
charged surfaces (more common)
Edge-to-edge (EE)
The net interparticle force
Aggregated fabric between surfaces is repulsive

Face-to-Face (FF) Shifted

Face-to-Face (FF)

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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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 Non-expansive 2:1 Clays
• the sheets or layers are held together strongly
• neither water nor a change in the interlayer
cations causes them to swell
• Illites are one group of non-expandable clays

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2:1 Clay Minerals
CEC ~ 40 meq/100 g
non-expanding

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 Expansive 2:1 Clays
• Bound together by very weak hydrogen
bounds (easily broken)
• Will swell upon wetting
• Smectites (montmorillonite) are one group of
expandable clays

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2:1 Clay Minerals (expanding)
CEC: 100 – 200 meq/100 g (vermiculite)
70 – 120 meq/100 g (smectite)

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Why water causes the mineral to expand
• Water is dipolar- which simply means it can be
attracted to a net negative charge or a net
positive charge
• Water carries many different ions in soil
solution
• Water has a physical size

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 Selected Properties
Specific
Interlayer CEC
Swelling Surface
Clay mineral Type condition/ meq/100
potential Area
Bonding gm
m/g
lack of interlayer
1 : 1 (non- almost
Kaolinite surface, strong 3 - 15 5 - 20
expanding) none
bonding
2:1 very weak bonding,
Montmorillonite 80 - 150 high 700 - 800
(expanding) great expansion
2:1 weak bonding,
Vermiculite 100 -150 high 500 - 700
(expanding) great expansion
2 : 1 (non- partial loss of K,
Hydrous Mica 10 - 40 low 50 - 200
expanding) strong bonding
moderate to strong
2 : 1 : 1 (non-
Chlorite bonding, non- 10 - 40 none
expanding)
expanding

Allophane - - 10 - 50 -
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 Formation
• Parent material
• Weathering

73
 Weathering Pathways
Noncrystaline
Olivine hydrous oxides of Si, Goethite
Pyroxene Al, Fe and Ti Hematite
Amphibole Gibbsite
Chlorite
+ Na
+H + OH
Biotite Trioctahedral + Na
Vermiculite Smectite
+ Na
Muscovite Dioctahedral
Illite +K - Si
+ Si

Feldspar Noncrystaline - Si Kaolinite

aliminosilicates - Si
Halloysite
+ Al
Quartz Silicic Acid Chalcedony
Opal
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 Clay Minerals
• Layered silicates
• Properties relate to surface area and charge
• Weathering is predictable
• Parent material of primary importance
• Drainage also may relate to clay mineralogy

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