CLAY STRUCTURE

Phyllosilicates (Sheet Silicates) of clay

The phyllosilicates, or sheet silicates, are an important group of minerals that includes the
micas, chlorite, serpentine, talc, and the clay minerals.  Because of the special importance of the
clay minerals as one of the primary products of chemical weathering and one of the more
abundant constituents of sedimentary rocks, they will be discussed in more detail in the next
lecture.

The basic structure of the phyllosilicates is based on

interconnected six member rings of SiO4-4 tetrahedra that
extend outward in infinite sheets.  Three out of the 4
oxygens from each tetrahedra are shared with other
tetrahedra.  This leads to a basic structural unit of Si2O5-2.

 Most phyllosilicates contain hydroxyl ion, OH-, with the OH

located at the center of the 6 membered rings, as shown here. 
Thus, the group becomes Si2O5(OH)-3.  When other cations are
bonded to the SiO4 sheets, they share the apical oxygens and
the (OH) ions which bond to the other cations in octahedral
coordination.  This forms a layer of cations, usually Fe+2, Mg+2,
or Al+3, that occur in octahedral coordination with the O and
OH ions of the tetrahedral layer.  As shown, here, the triangles
become the faces of the octahedral groups that can bind to the
tetrahedral layers.
The octahedral layers take on the
structure of either Brucite [Mg(OH)3], if
the cations are +2 ions like Mg+2 or Fe+2,
or Gibbsite [Al(OH)3], if the cations are
+3 like Al+3.  In the brucite structure, all
octahedral sites are occupied and all
anions are OH-1.  In the Gibbsite structure
every 3rd cation site is unoccupied and all
anions are OH-1.  
This gives rise to 2 groups of sheet silicates:

1. The trioctahedral sheet silicates where each O or OH ion is surrounded by 3 divalent

cations, like Mg+2 or Fe+2.

2. The dioctahedral sheet silicates where each O or OH ion is surrounded by 2 trivalent

cations, usually Al+3.
We can build the structures of the various sheet silicates by starting with the octahedral layers
similar to the structures of brucite or gibbsite, as shown below.
The trioctahedral phyllosilicates are based on the
structure where the octahedral layers are similar to
brucite, where Mg+2 occupies the cation position.

The dioctahedral phyllosilicates are based on the

structure where the octahedral layers are similar to
gibbsite, where Al+3 occupies the cation position.
The octahedral sheets in both cases are held together by weak Van der Waals bonds.
If we start with the brucite and
gibbsite structures shown
above, and replace 2 of the
OH ions with O, where the
Oxygens are now the apical
Oxygens of the tetrahedral
sheets, then we get the
structure of the serpentine
       
mineral, Lizardite, if the
octahedral layer is
trioctahedral, containing
Mg+2.  If the octahedral layer
is dioctahedral, containing
Al+3, the structure of the clay
mineral Kaolinite, is obtained.

This leads to a tetrahedral - octahedral (T-O) structure, where each T-O layer is bonded to the
top (or bottom) of another T-O layer by Van der Waals bonds.

If 2 more of the OH ions in the octahedral

layer are replaced by O, and these O
become the apical Oxygens for another
tetrahedral layer, the this builds the
trioctahedral phyllosilicate talc or the
dioctahedral pyrophyllite. This becomes a
T-O-T layer that can bond to other T-O-T
layers by weak Van der Waals bonds.

If an Al+3 is substituted for every 4th Si+4 in the tetrahedral layer, this causes an excess -1 charge
in each T-O-T layer.  To satisfy the charge, K+1 or Na+1 can be bonded between 2 T-O-T sheets
in 12-fold coordination.
For the trioctahedral sheet silicates this becomes Phlogopite (Mg-biotite), and for the
dioctahedral sheet silicates this becomes Muscovite.  This makes a T-O-T -  T-O-T layer that,
again can bind to another T-O-T - T-O-T layer by weak Van der Waals bonds.  It is along these
layers of weak bonding that the prominent {001} cleavage in the sheet silicates occurs.

Replacing 2 more Si+4 ions with Al+3 ions in the tetrahedral layer results in an excess -2 charge
on a T-O-T layer, which is satisfied by replacing the K+1 with Ca+2.  

This results in the trioctahedral sheet silicate - Clintonite and the dioctahedral sheet silicate -
Margarite.  

Because of the differences in charge balance between the trioctahedral and dioctahedral sheet
silicates, there is little solid solution between the two groups.  However, within the trioctahedral
sheet silicates there is complete substitution of Fe+2 for Mg+2 and limited substitution of
Mn+2into the octahedral sites.  Within the dioctahedral sheet silicates there is limited substitution
of Fe+3 for Al+3 in octahedral sites.  In addition, F- or Cl- can substitute for (OH)- in the hydroxyl
site.  As previously discussed, substitution of F -1 stabilizes the mineral to higher pressures and
temperatures.
Another group of phyllosilicates that is more of mixture of structural types is the chlorite
group.  Although chlorite is complex in that the amount of Al that can substitute Mg and Si is
variable, one way of looking at the chlorite structure is shown below. 
Here, the chlorite structure is depicted as
consisting of a brucite-like layer (with some
Al) sandwiched between tetrahedral layers
that are similar to phlogopite.

Another important sheet silicate structure is that of vermiculite. This is similar to the talc
structure, discussed above, with layers of water molecules occurring between each T-O-T
layer.  
Similarly, insertion of layers of water molecules between the T-O-T sheets of pyrophyllite
produces the structure of smectite clays.  The vermiculite and smectite groups are therefore
expanding type sheet silicates and as the water is incorporated into the structure the mineral
increases its volume.
Although we have shown that the octahedral layers fit perfectly between the tetrahedral layers,
this is an oversimplification.  If the tetrahedral layers were stacked perfectly so that apical
oxygens were to occur vertically aligned, then the structure would have hexagonal symmetry. 
But, because this is not the case, most of the phyllosilicates are monoclinic.
Serpentine Group

The serpentine group of minerals has the formula - Mg 3Si2O5(OH)4.  Three varieties of
serpentine are known.  Antigorite and Lizardite are usually massive and fine grained, while
Chrisotile is fibrous.  As discussed above, the imperfect fit of the octahedral layers and the
tetrahedral layers causes the crystal structure to have to bend.

In Antigorite the bending of the sheets is not

continuous, but occurs in sets, similar to
corrugations, as shown here.

In Chrisotile, the bending of the sheets is more

continuous, resulting in continuous tubes that give
the mineral it's fibrous habit.  The Chrisotile variety
is commonly referred to as asbestos.  

Occurrence - Serpentine is found as an alteration product of Mg-rich silicates like pyroxene and
olivine.  It results due to hydration.  For example:
 
2Mg2SiO4  + 3H2O  <=> Mg3Si2O5(OH)4  + Mg(OH)2
  Olivine                water                 Serpentine                      Brucite

Thus, serpentine is commonly found pseudomorphed after olivines and pyroxenes in altered
basic and ultrabasic igneous rocks, like altered peridotites, dunites, and sometimes basalts and
gabbros.  It is commonly associated with minerals like magnesite (MgCO 3), chromite, and
magnetite. If the rock is made up almost entirely of serpentine, it is called a serpentinite. 

Properties - Because the serpentines usually occur either as fine-grained aggregates or fibrous
crystals, optical properties are difficult to determine.  Most of the time, serpentine can be
distinguished by its characteristic pseudomorphing of other crystals like olivines and
pyroxenes.  In hand specimen it generally tends to have a dark green color with a greasy luster. 
In thin section it is clear to pale green to pale yellow, but does not show pleochroism, shows a
generally low relief compared to minerals like olivine and pyroxene with which it is associated,
and show very low order interference colors due to its low birefringence.
 
Talc

Talc has the chemical formula - Mg3Si4O10(OH)2.  It is probably best know for its low hardness. 
Although it has a micaceous structure, it is so easily deformed, that crystals are rarely seen.  

Occurrence - Like serpentine, talc requires an environment rich in Mg.  It is therefore found in
low grade metamorphic rocks that originated as ultrabasic to basic igneous rocks.  Rocks
composed almost entirely of talc have a greasy feel and are referred to as soapstone.

Properties -  Talc is most easily distinguished in hand specimen by its low hardness, greasy feel,
and association with other Mg-bearing minerals.  When crystals are present they show the
characteristic micaceous cleavage on {001}.  In thin section, talc is colorless, biaxial negative
with a 2V of 0 to 30o.  Like other sheet silicates, it shows the well developed {001} cleavage.
Maximum interference colors, consistent with a birefringence of 0.05 is 3o yellow.  Muscovite
has a higher birefringence and higher 2V, properties which easily distinguish the 2 minerals.
 
Mica Group

The micas can be divided into the dioctahedral micas and the trioctahedral micas, as discussed
above.  Muscovite, Paragonite, and  Margarite are the white micas, and represent the
dioctahedral group, and Biotite and Clintonite (Xanthophyllite) the black or brown mica,
represents the trioctahedral group.  Muscovite and Biotite are the most common micas, but  the
Lithium- rich, pink mica, Lepidolite, K(Li,Al) 2AlSi3O10(OH)2 is also common, being found
mostly in pegmatites.  

Muscovite

Muscovite, KAl3Si3O10(OH)2, and Paragonite, NaAl3Si3O10(OH)2, are two potential end

members of the solid solution series involving K and Na.  But, there is a large miscibility gap
between the two end members with Muscovite being between 65%  and 100% of K-rich end
member, and Paragonite showing compositions between about 80% and 100% of the Na-rich
end member.

Occurrence - Muscovite is common constituent of Al-rich medium grade metamorphic rocks

where is found in Al-rich schists and contributes to the schistose foliation found in these rocks. 
Muscovite is also found in siliceous, Al-rich plutonic igneous rocks (muscovite granites), but
has not been found as a constituent of volcanic rocks.  In these rocks it is commonly found in
association with alkali feldspar, quartz, and sometimes biotite, garnet, andalusite, sillimanite, or
kyanite.

Properties - Muscovite is easily identified in hand specimen by its white to sometimes light
brownish color and its perfect {001} cleavage.  In thin section, the {001} cleavage is easily seen
and it's high birefringence is exhibited by the large change in relief on rotation of the stage and
it's 2nd to 4th order interference colors.  It is clear and shows no pleochroism (which
distinguishes it from Biotite), and it is biaxial negative with a 2V between 28 and 50 o.  One of
the most diagnostic properties of the micas, including muscovite, is the mottled or birds-eye
extinction exhibited by these minerals.

 
Biotite

Biotite is a solid solution between the end members Phlogopite KMg 3AlSi3O10(OH)2 and Annite
KFe3AlSi3O10(OH)2, although pure Annite does not occur in nature.  In addition, small amounts
of Na, Rb, Cs, and Ba may substitute for K, and like in other minerals, F can substitute for OH
and increase the stability of Biotite to higher temperatures and pressures.

Occurrence -  Nearly pure phlogopite is found in hydrous ultrabasic rocks like kimberlite, and
is also found in metamorphosed dolomites.  Biotite, with more Fe-rich compositions is common
in dacitic, rhyolitic, and trachytic volcanic rocks, granitic plutonic rocks, and a wide variety of
metamorphic rocks.  In metamorphic rocks, biotite usually shows a preferred orientation with its
{001} forms parallel to the schistose foliation.  

Properties - In hand specimen, Biotite is brown to black and shows the perfect {001}
micaceous cleavage.  In thin section, it shows the perfect cleavage and mottled extinction
typical of all micas.  It's most characteristic property is its pleochroism, showing yellow to
brown to green colors.  Hornblende shows similar pleochroic colors, but is distinguished from
biotite by the differences in cleavage of the 2 minerals.  Biotite is biaxial negative with a low
2V of 0o to 25o.
Chlorite Group

As discussed above, the Chlorite group has a structure that consists of phlogopite T-O-T layers
sandwiching brucite-like octahedral layer.  There is substantial substitution of Mg for Fe, and Al
can substitute for (Mg, Fe) in both the octahedral sites, as well as for Si in the tetrahedral sites. 
Thus, chlorite can have a rather complicated formula - (Mg,Fe,Al)3(Si,Al)4O10(OH)6.  

Occurrence- Chlorite is a common mineral in low grade metamorphic rocks, where it occurs in

association with minerals like actinolite, epidote, and biotite.  It also forms as an alteration
product of pyroxenes, amphiboles, biotite, and garnet in igneous as well a metamorphic rocks.

Properties - In hand specimen, chlorite is recognized by its green color, micaceous habit and
cleavage, and association with other minerals like actinolite and epidote.  In thin section,
Chlorite shows low relief and low birefringence, with a characteristic midnight blue to black
anomalous interference color.  It shows some pleochroism in the range of green to pale yellow. 
It is easily distinguished from biotite by its lower relief and anomalous interference color. 

A soil particle may be a mineral or a rock fragment. A mineral is a chemical compound formed in nature
during a geological process, whereas a rock fragment has a combination of one or more minerals. Based on the
nature of atoms, minerals are classified as silicates, aluminates, oxides, carbonates and phosphates.

Out of these, silicate minerals are the most important as they influence the properties of clay soils. Different
arrangements of atoms in the silicate minerals give rise to different silicate structures.

Basic Structural Units

Soil minerals are formed from two basic structural units: tetrahedral and octahedral. Considering the valencies
of the atoms forming the units, it is clear that the units are not electrically neutral and as such do not exist as
single units.

The basic units combine to form sheets in which the oxygen or hydroxyl ions are shared among adjacent units.
Three types of sheets are thus formed, namely silica sheet, gibbsite sheet and brucite sheet.

Isomorphous substitution  is the replacement of the central atom of the tetrahedral or octahedral unit by
another atom during the formation of the sheets.

The sheets then combine to form various two-layer or three-layer sheet minerals. As the basic units of clay
minerals are sheet-like structures, the particle formed from stacking of the basic units is also plate-like. As a
result, the surface area per unit mass becomes very large.

Structure of Clay Minerals

A tetrahedral unit consists of a central silicon atom that is surrounded by four oxygen atoms located at
the corners of a tetrahedron. A combination of tetrahedrons forms a silica sheet.

An octahedral unit consists of a central ion, either aluminium or magnesium, that is surrounded by six
hydroxyl ions located at the corners of an octahedron. A combination of aluminium-hydroxyl octahedrons
forms a gibbsite sheet, whereas a combination of magnesium-hydroxyl octahedrons forms a brucite sheet.
Kaolinite and halloysite clay minerals are the most common.

TWO-LAYER SHEET MINERALS

Kaolinite Mineral

The basic kaolinite unit is a two-layer unit that is formed by stacking a gibbsite sheet on a silica
sheet. These basic units are then stacked one on top of the other to form a lattice of the mineral. The
units are held together by hydrogen bonds. The strong bonding does not permit water to enter the
lattice. Thus, kaolinite minerals are stable and do not expand under saturation.

Kaolinite is the most abundant constituent of residual clay deposits.

Halloysite Mineral 
The basic unit is also a two-layer sheet similar to that of kaolinite except for the presence of water
between the sheets.

THREE-LAYER SHEET MINERALS

Montmorillonite and illite clay minerals are the most common. A basic three-layer sheet unit is
formed by keeping one silica sheet each on the top and at the bottom of a gibbsite sheet. These
units are stacked to form a lattice as shown. 

Montmorillonite Mineral 

The bonding between the three-layer units is by van der Waals forces. This bonding is very weak
and water can enter easily. Thus, this mineral can imbibe a large quantity of water causing swelling.
During dry weather, there will be shrinkage.
Illite Mineral 

Illite consists of the basic montmorillonite units but are bonded by secondary valence
forces and potassium ions, as shown. There is about 20% replacement of aluminium with silicon in
the gibbsite sheet due to isomorphous substitution. This mineral is very stable and does not swell
or shrink.