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 [111] - The twin axis perpendicular to an octahedral face adds

three fold rotational symmetry.

 Iron Cross [001] - The mineral pyrite (FeS2) often shows the
iron cross made of the interpenetration of two pyritohedrons.
Since this occurs in the class 2/m , with no 4-fold rotation axes,
the [001] twin axis gives the mineral apparent 4-fold symmetry
about 3 perpendicular axes.

Polymorphism

Polymorphism means "many forms". In mineralogy it means that a single chemical

composition can exist with two or more different crystal structures. As we will see when we
look more closely at crystal structures, if a crystal is subjected to different pressures and
temperatures, the arrangement of atoms depends on the sizes of the atoms, and the sizes change
with temperature and pressure. In general, as pressure increases the volume of a crystal will
decrease and a point may be reached where a more compact crystal structure is more stable.
The crystal structure will then change to that of the more stable structure, and a different
mineral will be in existence. Similarly, if the temperature is increased, the atoms on the crystal
structure will tend to vibrate more and increase their effective size. In this case, a point may be
reached where a less compact crystal structure is more stable. When the crystal structure
changes to the more stable structure a different mineral will form.

The change that takes place between crystal structures of the same chemical compound are
called polymorphic transformations.

Types of Polymorphic Transformations

Stability of crystal structures is generally referred to in terms of the energy of the crystal
structure. In general terms this can be thought of as the bond strength (enthalpy), and entropy
(degree of order or randomness) of the structure. In general, the structure with the lowest
energy is the most stable at any given temperature and pressure.

This results in three types of transformations.

1. Reconstructive Transformations - these involve

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extensive rearrangement of the crystal structure and

requires breaking of chemical bonds and reassembling
the atoms into a different crystal structure. This
usually involves a large change in energy of the
structure which must occur at the transformation
temperature or pressure. Because of the extensive
rearrangement involved, the rate at which this type of
transformation occurs may be very slow. If the rate of
the transformation is very slow, unstable polymorphs
(metastable) may exist for long periods of time.

For example, diamond is a metastable polymorph of Carbon at the pressures and

temperatures present at the Earth's surface, yet, as the saying goes "diamonds are
forever". Not really, it's just that the rate at which diamond can rearrange its crystal
structure to become graphite, the polymorph stable at low P and T, is very slow at the
low temperatures found near the Earth's surface.
2. Displacive Transformations - these involve only
small adjustments to the crystal structure. Generally
no bonds are broken, but the angles between the
atoms may change slightly. Because there is little
rearrangement, displacive transformations involve no
change in energy at the transformation temperature or
pressure, and the transformations are instantaneous
and reversible. Thus, no unstable polymorphs will
occur.

For example, at 1 atmosphere pressure high quartz ( quartz) is the stable form of quartz
above 580o C. When high quartz is brought to a temperature below 580o it immediately
is transformed into low quartz ( quartz). Thus, high quartz is never seen in rocks at the
surface of the Earth.

3. Order - Disorder Transformations - these involve the state of order or disorder in a

crystal structure. Perfect order can only occur at a temperature of absolute zero (-
273oC). As temperature increases, the degree of order or randomness of a crystal
structure decreases, so that the higher temperature forms of minerals are more disordered
than the lower temperature forms. Because the state of order-disorder changes gradually
with increasing temperature, there is no definite temperature at which a transformation
occurs.

An example of polymorphic transformations that involve order-disorder is the compound

KAlSi3O8. At high temperature the stable form is Sanidine (Monoclinic). At lower
temperature the structure changes to one of orthoclase (also Monoclinic), and at even
lower temperature the structure becomes that of the more ordered structure of microcline

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(also Triclinic).

There is no definite temperature at which Sanidine changes to orthoclase or orthoclase

changes to Microcline, since the structure changes gradually as temperature decreases. If
the temperature change is rapid, then unstable polymorphs can continue to exist a low
temperature.

Important Polymorphs

Many common minerals show polymorphism. We here look at some of the more common
ones.

 Carbon - has two polymorphs. At high pressure

carbon has an isometric crystal structure that is
called diamond. As temperature and/or pressure
are decreased diamond should undergo a
reconstructive transformation to the hexagonal
structure of graphite. Because this
transformation involves a drastic rearrangement
of atoms on the crystal structure, as evidenced by
the fact that diamond is the hardest naturally
occurring substance and graphite is one of the
softest) diamond is found at the T & P conditions
present at the Earth's surface, where it is
therefore only metastable.

 Al2SiO5 - has three polymorphs. The high pressure form is

kyanite (Triclinic), the high temperature form is sillimanite
(orthorhombic), and the low temperature, low pressure form
is andalusite (orthorhombic). Transformations between all
three polymorphs are reconstructive, thus all three forms can
metastably exist at the Earth's surface. Transformation rates
are somewhat faster, however, at higher temperatures in the
Earth.
 CaCO3 - has two polymorphs. The high pressure form is aragonite (orthorhombic) and
the low pressure form is calcite (hexagonal). The transformation between the two
polymorphs is reconstructive, so metastable polymorphs can exit.
 SiO2 - has 6 polymorphs. With
decreasing temperature at low pressure,
cristobalite (isometric) undergoes a
reconstructive transformation to tridymite
(hexagonal). Further lowering of
temperature results in tridymite
undergoing a reconstructive
transformation to high quartz (also
hexagonal). Lowering temperature further
results in high quartz undergoing a

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displacive transformation to low quartz.

Cristobalite and tridymite can exist metastably at the low temperatures near the Earth's
surface, and thus are found in rocks. But high quartz will also transform to low quartz
before it reaches temperatures present at the Earth's surface, so it is never found in rocks.

With increasing pressure, at low temperature low quartz undergoes a displace

transformation to coesite (Monoclinic), and coesite undergoes a reconstructive
transformation to stishovite (tetragonal) at even higher pressures. Thus, coesite and
stishovite have metastable polymorphs that can be found in rocks.
 KAlSi3O8 - As discussed above, this compound has three polymorphs that undergo
order-disorder transformations with lowering of temperature. The high temperature
polymorph is sanidine (monoclinic). It is usually only found in volcanic rocks that have
cooled very rapidly so that a higher state of order is not achieved. With slower cooling,
sanidine eventually undergoes a transformation to orthoclase (also monoclinic), and
orthoclase eventually transforms to microcline (triclinic) with further slow cooling.
Polytypism

Polytypism is a type of polymorphism wherein different polymorphs exist in different domains

of the same crystal. It has to do with the way that individual layers are stacked within a crystal
structure. Polytypism has little geologic consequence, and will thus not be discussed further
here.

Metamict Minerals

Metamict minerals are minerals whose crystal structure has been partially destroyed by
radiation from contained radioactive elements. The breakdown of the crystal structure results
from bombardment of a particles emitted by the decay of U and Th radioactive isotopes.

The mineral zircon (ZrSiO4) often has U and Th atoms substituting for Zr in the crystals
structure. Since U and Th have radioactive isotopes, Zircon is often seen to occur in various
stages of metamictization.

Mineraloids

By definition, a mineral has to have an ordered atomic arrangement, or crystalline structure.

There are some Earth materials that fit all other parts of the definition of a mineral, yet do not
have a crystalline structure. Such compounds are termed amorphous (without form).

Some of these amorphous compounds are called mineraloids. These usually form at low
temperatures and pressures during the process of chemical weathering and form mammillary,
botryoidal, and stalactitic masses with widely varying chemical compositions. Limonite [FeO.
(OH).nH2O] and allophane ( a hydrous aluminum silicate) are good examples.

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Others like volcanic glass and opal

(SiO2.nH2O) have short-range order or domains
wherein some crystalline-like order exists.

Unlike crystalline minerals that show sharp,

well defined x-ray diffraction peaks, these
mineraloids with short-range order show broad
diffraction peaks that give evidence of the
short-range order.

Pseudomorphism

Pseudomorphism is the existence of a mineral that has the appearance of another mineral.
Pseudomorph means false form. Pseudomorphism occurs when a mineral is altered in such a
way that its internal structure and chemical composition is changed but its external form is
preserved. Three mechanisms of pseudomorphism can be defined:

1. Substitution. In this mechanism chemical constituents are simultaneously removed and

replaced by other chemical constituents during alteration. An example is the replacement
of wood fibers by quartz to form petrified wood that has the outward appearance of the
original wood, but is composed of quartz. Another example is the alteration of fluorite
which forms isometric crystals and is sometimes replaced by quartz during alteration.
The resulting quartz crystals look isometric, and are said to be pseudomorphed after
fluorite.

2. Encrustation. If during the alteration process a thin crust of a new mineral forms on the
surface of a preexisting mineral, then the preexisting mineral is removed, leaving the
crust behind, we say that pseudomorphism has resulted from encrustation. In this case
the thin crust of the new mineral will have casts of the form of the original mineral.

3. Alteration. If only partial removal of the original mineral and only partial replacement
by the new mineral has taken place, then it is possible to have a the space once occupied
entirely by the original mineral be partially composed of the new mineral. This results
for example in serpentine pseudomorphed after olivine or pyroxene, anhydrite (CaSO4)
pseudomorphed after gypsum (CaSO4.2H2O), limonite [FeO.(OH).nH2O] after pyrite
(FeS2), and anglesite (PbSO4) after galena (PbS).

Examples of questions on this material that could be asked on an exam

1. Define the following : (a) Twinning, (b) twin plane, (c) twin axis, (d) composition
surface, (e) contact twin, (f) penetration twin.

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2. What are three ways that twinning can originate?

3. Why can't twinning occur parallel to axes or planes of existing symmetry in a crystal.

4. Define polymorphism.

5. Give several examples of minerals that show polymorphism, being sure to name all of
the polymorphs.

6. Describe that three different types of transformations that result in new polymorphs.

7. Define the following: (a) metamict mineral, (b) pseudomorphism, (c) mineraloid.

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