Lecture 13

Clay Mineralogy
Dr. K. Vijaya Kumar School of Earth Sciences SRTM University, Nanded 431 606 Maharashtra, INDIA (E-mail: vijay_kumar92@hotmail.com)

Outline
Building blocks Classification Properties Formation

Elements of Earth
8-35 km crust % by weight in crust O Si Al Fe Ca Na K Mg other = 49.2 = 25.7 = 7.5 = 4.7 = 3.4 = 2.6 = 2.4 = 1.9 = 2.6

82.4%

12500 km dia
Geotechnical engineers are interested mainly in the top 100 metres of the earth crust. As you can see from the table, 82% of the elements are oxygen, silicon and aluminium.

What is Clay ?
The term clay is used in a number of ways. It can refer to: A member of a large group of fine-grained platy minerals related to micas. It can refer to a mixture of minerals with claysize particles, i.e. <1/256 mm; smaller than the wavelength of light)--These are generally dominated by clay minerals.

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

Tetrahedron and Octahedron

All clay minerals are made of two distinct building blocks: tetrahedrons and octahedrons. The tetrahedron on the left has oxygen atoms at the corners, and there is a silicon in the centre. Octahedron has six oxygen or hydroxyl atoms in the corners, and an aluminium or magnesium ion at the centre.

Clay Mineralogy: Why is it important?

The minerals in the clay-sized fraction of the soil affects the degree to which soils shrink (when dry) and swell (when wetted). As a clay soil swells the amount and size of pore space decreases and affects the ability to move water (effluent) through the soil.

Expansive clay in thin section

Bright colors due to the clay being oriented. Orientation due to stress (shrink-swell) Porosity limited

4 mm

Nonexpansive clay in thin section

Less oriented clay Voids outlines with clay skins

4 mm

Mixed clay in thin section

Less oriented clay Thin argillans High iron content

4 mm

Clay Minerals
Layer(s) of linked Si tetrahedra Layer(s) of Al octahedra

Sheets of Tetrahedron and Octahedron

Definitions
Plane-plane of atoms, individual row in the composition and structure of the clay mineral Sheet-combination of planes Layer- combination of sheets i.e.. 1:1

Clay Mineral Classification

1:1 Clay Minerals 2:1 Clay Minerals Mixed Mineralogy

Clay Structure

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

1:1 Clay Mineral

1:1 Clay Minerals

non-expanding

Kaolinite
Al Typically 70100 layers Si Al Si joined by strong H-bond no easy separation Al Si Al Si Kaolinite is used for making paper, paint and in pharmaceutical industry. A nanometer is 10-9 metres. joined by oxygen sharing

0.72 nm

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

2:1 Clay Mineral

2:1 Clay Minerals

non-expanding

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

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

2:1 Clay Minerals (expanding)

Clay soil structure

Dispersed structure

Card house structure (Flocculated)

Flocculated clay
Thin adsorbed water layer Negative faces bond with positive edges Card house structure Rigid configuration Apparent larger particles Better engineering properties

Dispersed structure
Thick adsorbed water layer Negative faces repel. Clay plate stack parallel to each other Large variation in water content (high PI) Large shrink / swell capacity Poor engineering properties

Interchangeability
Dispersed structure may be changed to flocculated by adding Ca++.
For Portland cement or hydrated lime (Soil stabilisation)

Alteration of the ground water electrolyte condition can change the flocculation / dispersion potential of a soil.

Properties of Clay Minerals

Surface Area Cation Exchange Capacity Expansion

Surface Area
surface smaller

area per unit mass (m2/g) the grain, higher the specific

surface

10 mm cube spec. surface = 222.2 mm2/g

1 mm cube spec. surface = 2222.2 mm2/g

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

Surface Area
Smectite group minerals have higher CEC Smectite group minerals have a higher surface area Isomorphic substitutions plays a role in the above and in the expansive nature of this group

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+ The negatively charged clay particles can attract cations from the water. These cations can be freely exchanged with other cations present in the water. For example Al3+ can replace Ca2+ and Ca2+ can replace Mg2+.

Selected Properties of Clay Minerals

Clay mineral Type Interlayer condition/ Bonding lack of interlayer surface, strong bonding

CEC cmol/kg

Specific Swelling Surface potential Area m/g almost none high 5 - 20

Kaolinite

1 : 1 (nonexpanding) 2:1 (expanding) 2:1 (expanding)

3 - 15

Montmorillonite Vermiculite Hydrous Mica

very weak bonding, 80 - 150 great expansion

700 - 800 500 - 700 50 - 200

weak bonding, 100 -150 high great expansion 10 - 40 low

2 : 1 (nonpartial loss of K, expanding) strong bonding 2 : 1 : 1 (nonexpanding) moderate to strong bonding, nonexpanding

Chlorite

10 - 40

none

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

Expansion of Clays
Ion hydration
cation Na+ crystal radius: 0.095 nm radius of hydrated ion: 0.358 nm

Clay layers

Dry condition (Interlayer)

The water molecules wedge into the interlayer after adding water

The cations are fully hydrated, which results in repulsive forces and expanding clay layers (hydration energy).

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+ +HCO3The 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.

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!

Synthesis of Clay Minerals

(after Mitchell (1993)

39

Controlling Factors
Weathering regimes Parent material

Typical Weathering Sequence

Poorly drained conditions (slow water movement)
H4SiO40 dissolves from primary minerals Accumulates in soil Favors 2:1 clay formation (smectite)

Well drained conditions (high rainfall)

H4SiO40 leaches through profile Bases leach through profile (more acid) Favors: 2:1 illite/vermiculite to 1:1 kaolinite to gibbsite

Jackson-Sherman Weathering Stages

Minerals in clay fraction Olivine/pyroxene/amphibole Fe(II) micas Feldspars Quartz Illite Vermiculite, chlorite Smectite Soil Chemical and Physical Properties Early stage Low water and OM, limited leaching Reducing environment Limited time for weathering Retention of Na, Ca, Mg, Fe(II) and silica Ineffective leaching Igneous rocks rich in Ca, MG, Fe(II) Silicates easily hydrolyzed Transport of Silica into weathering zone Advanced Stage Kaolinite Gibbsite Fe-oxides Ti-oxides Removal of Na, K, Ca, Mg, Fe(II), Silica Effective leaching Oxidation of Fe(II) Acidification Dispersion of Silica Al-hydroxy polymers

Intermediate Stage

Weathering Pathways
Olivine Pyroxene Amphibole

Noncrystaline hydrous oxides of Si, Al, Fe and Ti

Chlorite
+H + OH + Na + Na

Goethite Hematite Gibbsite

Biotite

Trioctahedral Vermiculite

Smectite
+ Na +K + Si - Si - Si

Muscovite

Dioctahedral Illite
Noncrystaline aliminosilicates
+ Al

Feldspar

- Si

Kaolinite

Halloysite
Chalcedony Opal

Quartz

Silicic Acid

Parent Material
The 1:1 minerals are usually weathered from acidic or felsic parent materials The expanding 2:1 minerals are usually weathered from basic or mafic parent material Parent material plays the biggest part of whether the soil will be expansive

In summary.

Clay minerals are layered hydrous alumina silicates formed by surface processes Clay minerals are important for their expansive and cation exchange capabilities Clay minerals classified based on the SilicaOxygen tetrahedra and Alumina-Oxygen octahedra arrangement Parent material is of primary importance in the formation of a particular variety of clay Drainage also may relate to clay mineralogy