Unit 11 Chapter 1 - Clay Minerals

When we studied soil texture we learned that one of the soil separates was called clay. Now
we learn more about this important mineral component of the soil.
Clay minerals are the most important chemical weathering product of the soil. They are
formed by the alteration of existing minerals or by synthesis from elements when minerals
weather to their elemental form. It is not possible to make clays by grinding up silt or sand
particles. Clay has many uses today including, pottery, ceramics, linings for landfills,
computer chips, cosmetics, and pharmaceuticals.
Clay minerals are important in soils because of the negative charge they contribute for
cation exchange. Understanding about soil clays is also important because of their shrink
and swell potential upon wetting and drying. When soils are unsuitable for building because
of a high shrink/swell potential this is because of the amount and type of clay present. Our
study of clay minerals will involve looking at their structure and why this contributes to
their properties.
Clay minerals are part of the larger class of silicate minerals: the phyllosilicates. Included in
the phyllosilicate family are the larger true micas which include the familiar minerals
muscovite and biotite. Much of what we know about clay minerals is from the macroscopic
(i.e., single crystal) study of the true micas.
Silicate Clay Minerals are called aluminosilicates and they have a definite crystalline
structure. Clay minerals are very small in size (by definition are less than 0.002 mm in size)
and only seen with aid of
electron microscope.

Building Blocks for Clay

Minerals
Clay minerals are composed
of two basic building blocks.
1) Silicon - Oxygen
Tetrahedron (Si2O5-2)
2)Aluminum Octahedral (Gibsite Sheet) Al(OH)6-3
Tetrahedral sheets are composed of individual tetrahedrons which share every three out of
four oxygens. They are arranged in a hexagonal pattern with the basal oxygens linked and
the apical oxygens pointing up/down.
Octahedral sheets are composed of individual octahedrons that share
edges composed of oxygen and hydroxyl anion groups with Al, Mg,
Fe3+ and Fe2+ typically serving as the coordinating cation. These
octahedrons too, are arranged in a hexagonal pattern and called a
gibsite sheet.

Kaolinite - a 1:1 Clay Mineral

Kaolinite occurs when the Si-tetrahedral and gibsite sheet are
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.
The structure illustrated is about 0.7 nm thick (from the bottom oxygen to the
top oxygen) and extends 10 nm and more in the other two directions. This 3D structure is called a micelle.
Kaolinite is named for the ancient Chinese locality "Kauling," meaning high
ridge. You can hear the pronunciation at Kaolinite Information
The kaolinite mineral is actually made up of many micelles piled one atop the
other. Since the surface on one micelle contains hydrogen ions and the other surface only
oxygen ions there is a tendency for hydrogen bonds to form between micelles. While
individual hydrogen bonds are very low energy, the bonding energy is additive and the sum
of the many hydrogen bonds between micelles results in the micelles being very strongly
bonded together and nearly impossible to separate. This bonding of the layers together
results in kaolinite being a nonexpanding clay mineral. Since each micelle is constructed of
a layer of silicon tetrahedral units and a layer of octahedral units, kaolinite is called a 1:1
clay mineral.
Most soils of the world contain kaolinite in the clay size fraction (<2m). In highly
weathered soils, such as those of Southeastern U.S. and tropical regions of Africa, Asia, and
S. America, kaolinite is usually the dominant clay mineral because of its relative resistance
to chemical weathering. Since kaolinite only has negative sites at the edge of the mineral
that are not satisfied, the CEC is low, 3 - 15 meq/100g. This makes the soil easy to acidify
because the ability to hold on the basic cations is low.
Uses of Kaolinite
China clay is one of the purest of the clays and is composed chiefly of kaolinite. It forms
usually when granite is changed by hydrothermal metamorphism. Usage of the terms china
clay and kaolin is not well defined; sometimes they are used synonymously for a group of
similar clays, and sometimes kaolin refers to those obtained in the United States and china
clay to those that are imported.
China clays have long been used in the ceramic industry, especially in fine porcelains,
because they can be easily molded, have a fine texture, and are white when fired. France's
clays are made into the famous Svres and Limoges potteries. These clays are also used as a
filler in making paper. Kaolinite is the basic raw material for ceramics, and large quantities
are also used in the manufacture of coated paper. In the United States, deposits are found
primarily in Georgia, North Carolina, and Pennsylvania; china clay is also mined in
England (Cornwall) and France.
For a look at Minnesota Kaolin mines go to Minnesota Kaolin Mines

2:1 clay minerals

The basic structure of 2:1 clay minerals is two silicon tetrahedral layers and one aluminum
octahedral layer. This layer is weakly held to another 2:1 layer to make the 2:1 family of
clay minerals. An interlayer or the space between the sheets becomes an important

difference between 2:1 and 1:1 clay minerals. Smectite and Vermiculite are two kinds of 2:1
clay minerals.
Smectite Clay Mineral
The term "smectite" is used to describe a family of expansible
2:1 phyllosilicate clay minerals having permanent layer charge
because of the isomorphous substitution in either the
octahedral sheet (typically from the substitution of low charge
species such as Mg2+, Fe2+, or Mn2+ for Al3+) or the
tetrahedral sheet (where Al3+ or occasionally Fe3+ substitutes
for Si4+). It is common for smectites to have both tetrahedral
charge and octahedral charge.
These isomorphous substitutions lead to net negative charges on the clay structure which
must be satisfied by the presence of charge-balancing cations somewhere else in the
structure. The interlayer is hydrated, which allows cations to move freely in and out of the
structure. Because the interlayer is open and hydrated, cations may be present within the
interlayer to balance negative charges on the sheets themselves. These cations between the
layers are part of the cation exchange capacity of the soil. Smectites will have a CEC of
around 80 to 150 meq/100 g
Swelling Properties of smectite The interlayer in smectites is not only hydrated, but it is
also expansible; that is, the separation between individual smectite sheets varies depending
on: 1) the type of interlayer cations present (monovalent cations like Na+ cause more
expansion than do divalent cations like Ca2+), 2) the concentration of ions in the
surrounding solution, and 3) the amount of water present in the soil.
Because the interlayer is expansible, smectites are often referred to as "swelling clays".
Soils having high concentrations of smectites can undergo as much as a 30% volume
change due to wetting and drying or these soils have a high shrink/swell potential. These
dramatic changes in soil volume are responsible for the properties of soils in the Vertisol
order, which form deep cracks upon drying. Most soils in Minnesota will have smectite as
the dominant clay mineral.
Mining of smectite (bentonite) Early Americans found bentonite vital to their lives.
Pioneers found moistened bentonite to be an ideal lubricant for squeaky wagon wheels. The
mixture was also used as a sealant for log cabin roofing. The Indians found bentonite useful
as a soap. Small amounts of Wyoming bentonite were first commercially mined and
developed in the Rock River area during the 1880s. Newer, more substantial deposits were
discovered in other parts of Wyoming during the 1920s and the first processing plant in
Wyoming was built during this period. since that time many other processing plants have
been built for the purpose of processing Wyoming sodium bentonite.(source: Black Hills
Bentonite, LLC)

Wyoming bentonite (see Black Hills Bentonite) is composed essentially of smectite clay.
Wyoming bentonite is capable of absorbing 7 to 10 times its own weight in water, and
swelling up to 18 times its dry volume.
During the cretaceous age, volcanoes in the Yellowstone area of Wyoming were subject to
long periods of eruptions. Ash falling from these eruptions dropped into seas which covered
much of Wyoming, forming a sediment as much as 50 feet deep. These sediments were
slowly altered into the clay we know today as bentonite. In these deposits are contained
70% of the world's known supply of western or sodium type bentonite.

Bentonite is mined by surface "open pit" methods.

Various types of heavy equipment including bull
dozers and rubber-tired scrapers are used to remove
the shale rock overlying the bentonite. Topsoil, as
well as the underlying material, is carefully removed
and stockpiled. These "overburden" materials as they
are called will be placed back and reseeded once the
bentonite has been removed.
The bentonite which is exposed during this process
can be as little as 1 1/2 feet or as much as 10 feet
thick. This is the material which is mined and
processed. Many bentonite manufactures prefer to
"field dry" the exposed bentonite prior to hauling it to
the processing plants. This is accomplished by
plowing and discing while taking advantage of the low humidity and sunny days to dry the
bentonite prior to its removal. The moisture level prior to "field drying" can exceed 30%.
This process will normally extract 15 to 20% of the moisture from the clay prior to

hauling.?

Uses of Bentonite (Smectite)

Drilling mud, or drilling gel, has bentonite as a major component. Drilling mud is crucial
in the extraction of drill cuttings during the drilling process. Bentonite, when mixed with
water, forms a fluid (or slurry) that is pumped through the drill stem, and out through the
drill bit. The bentonite extracts the drill cuttings from around the bit, which are then floated
to the surface.
Taconite, a low grade iron ore, has been developed as an economic source for iron. During
processing, the taconite is ground into a very fine powder. The ground taconite is then
mixed with small amounts of bentonite which serves as a binder to the taconite. This
mixture is processed into balls or pellets. The process is finished when these pellets are
sintered in rotary kilns that give the pellets a hard surface.
The metal casting industry needs bentonite as an economical bonding material in the
molding processes associated with the metal casting industry. Bentonite, when mixed with
foundry molding sands, forms a pliable bond with the sand granules. Impressions are
formed into the face of the bentonite/sand mixtures. Molten metal is pored into the
impressions at temperatures exceeding 2,800 F. The unique bonding characteristics of
bentonite insures the durability of the mold during these high temperatures. Once the
process is complete, the bentonite/sand mold can then be broken away from the casting face
and reused.
In recent years, bentonite has become a major component in the manufacturing of cat litter.
Because of the unique water absorption, swelling, and odor controlling characteristics of
bentonite, it is ideal for use in "clumping" types of cat litters. Clumping cat litter has
become widely accepted as an economical alternative to conventional non-clumping type

cat litters. Because bentonite forms clumps when wet, the clumps can easily be removed
and disposed of. The remainder of the unused material stays intact and can continue to be
used. clumping cat box litters will last longer with less frequency
of changing.
For many years bentonite has been used as a binder in the feed
pelletizing industry. Small amounts of bentonite can be added to
feed products to insure tougher, more durable pellets. Bentonite has
also proved helpful in sealing freshwater ponds, irrigation ditches,
reservoirs, sewage and industrial water lagoons, and in grouting permeable ground. In
addition, it has been used in detergents, fungicides, sprays, cleansers, polishes, ceramic,
paper, used as a base for cosmetics and medicines, and applications where its unique
bonding, suspending or gellant properties are required.
Vermiculite Clay Mineral.
Vermiculite is a high-charge 2:1 phyllosilicate clay mineral. It is generally regarded as a
weathering product of micas. The charge in vermiculites may be both tetrahedral and
octahedral in nature, but most vermiculites have mainly tetrahedral charge due to the
substitution of Al3+ for Si4+. Typically, between 0.6 to 0.9 out of 4 Si are replaced by Al.
This negative charge must be balanced by the presence of positively-charged sites
somewhere else in the mineral structure. Generally vermiculite is like smectite except for
more tetrahedral charge, which results in vermiculite having a CEC of 150 meq/100g.
Therefore, to achieve charge-balance the presence of exchangeable cations in the interlayer
is necessary.
Like smectite, Vermiculite is also hydrated and somewhat expansible though less so than
smectite because of its relatively high charge. Soils rich in vermiculite do not display the
high shrink-swell characteristics of highly smectitic soils. In some soils the interlayer of
vermiculite is filled with potassium ions which act as a bridge holding the layers rigidly
together. This mineral is called Illite or Hydrous Mica.
Exfoliation of Vermiculite
Vermiculite possesses the special property of expanding to between six and twenty times its
original volume when heated to approximately 1,000 degrees Celsius. This process, called
exfoliation, liberates bound water from between the mica-like layers of the mineral and
literally expands the layers apart at right angles to the cleavage plane.
The resulting exfoliated Vermiculite has a characteristic concertina (worm like) shape (the
name vermiculite is derived from the Latin 'vermiculare' - to breed worms). This
characteristic of exfoliation, the basis for commercial use of the mineral, is the result of the
mechanical separation of the layers by the rapid conversion of contained water to steam.
The increase in bulk volume of commercial grades is 8 to 12 times, but individual flakes
may exfoliate as many as 30 times.
The bulk density of crude vermiculite or vermiculite concentrate is in the range of 40-70
lb/ft and exfoliated or expanded vermiculite is in the range of 4-10 lb/ft.
Vermiculite is used to loosen and aerate soil mixes. Mixed with soil, it improves water
retention and fertilizer release, making it ideal for starting seeds. Also used as a medium for
winter storage of bulbs and flower tubers.

Vermiculite has been used in various industries for over 80 years.

Exfoliated vermiculite has a high insulation value, is lightweight and will
absorb and hold a wide range of liquids. These granules are noncombustible, and are insoluble in water and all organic solvents.
Expanded vermiculite is easily poured, is light, clean, highly absorbent
and provides baffle against impact shock when used for packaging.
Exfoliated vermiculite is used in the friction brake linings market, high
temperature insulation, loft insulation, fire proofing, sound proofing,
various construction products, and animal feeds,
The cation exchange properties of vermiculite, and its layered structure and surface
characteristics, are utilized in products such as intumescent coatings and gaskets, and the
treatment of toxic wastes.
Vermiculite mines are located in Australia, Brazil, China, Kenya, South Africa, Zimbabwe,
and the states of South Carolina and Montana. Vermiculite mines are surface operations
where ore is separated from other minerals, and then screened or classified into several
basic particle sizes.

Sources of Negative Charge .

1) Soil Humus
Soil organic matter will under go disassociation of the H ion from the COOH group or
carboxyl group (a carboxyl group consists of a carbon atom joined to an oxygen atom by a
double bond and to a hydroxyl group, OH, by a single bond). The H+ ion will now exist in
the soil solution and the COO - (organic matter ) will have a negative charge site which can
attract cations.
RCOOH <> RCOO- + H+
The creation of the negative charge on the carboxyl group is pH dependent, or as the pH
increases more OH- are available, more H+ leaves the COOH group , and therefore, more
CEC is created. Conversely acid soils have a lower CEC from OM because the H stays in
the COOH group.
2) Silicate Clay Minerals
1) Broken bonds at edge of clay minerals. All clays have a finite size, and at the edge of the
mineral there are some oxygen atoms that do not have their negative charges satisfied by
cations in mineral structure, thus at the edge of the mineral negative charges exist.
2) Isomorphous Substitution - internal charge not satisfied because of ionic substitution of
Al 3+ for Si 4+ or Mg2+ for Al 3+
In vermiculite the replacement of Si4+ with Al+3 in 25% of tetrahedrals creates 1 negative
site for each substitution.
In smectite Mg2+ replaces Al3+ in Octahedral layers about 1/4 of the time and creates
negative sites
Summary - Kaolinite clays only have the edges contributing to CEC, while 2:1 clays have
the edges and isomorphous substitution.
Lab Units