Defects in crystals

In an ideal crystal structure every unit cell is identical and

each had a specific shape, size and cell content. However in a real
crystal structure there are always some local variations or defects in
this perfect arrangement.

The defects has effect on many mineral properties.

Mainly three types of defects occur in minerals:

 Point defects

 Line defects

 Planar defects
Point defects

 In many cases, point defects are responsible for the color of

gemstones when impurity atoms are present in an otherwise perfect
structure.

 All crystals at temperature above

absolute zero contain some point
defects which are generally vacant
atomic sites or substituted by
impurity atoms.

 Up to certain concentration, the

presence of point defects actually
reduces the free energy of a crystal.
 The creation of vacancy or other point defects requires energy and
hence increase the enthalpy of the crystal.

 The structure is locally distorted and the bonding requirements are less
well satisfied.

 This increase in enthalpy is accompanied by an increase in entropy

because the defect increase the disorder in the otherwise perfect crystal.

 The value of entropy change is associated with the number of ways of

distributing defects with in the structure, and for small defect
concentrations the entropy increase is greater than the enthalpy
increase.

 The free energy minimum occurs at a higher defect concentration.

 So the crystal structure will have more defects and tends to more
disordered state at higher temperatures. Thus at higher temperatures
there are more vacancies, a grater accommodation of impure atoms and
a greater degree of cation disorder.
There are mainly two different types of point defects:

1. Schottky defect

This is the simplest case in which a vacant cation site in a

structure is balanced by a vacant anion site to maintain electrical
neutrality. Such a pair of vacancies is called Schottky defect.

Here the two vacancies are not necessarily directly associated

with each other in anyway.
2. Frenkel defect

This type of point defect occurs when an atom from a site,

leaving a vacancy, and is placed in an alternative interstitial site which is
normally unoccupied. This is called Frenkel defect. It leaves the overall
charge balance and stoichiometry unaffected.
 Schottky and Frenkel defects are referred to as intrinsic defects since
their numbers are controlled by intrinsic properties of the structure,
related to the size of the inter-atomic forces.

 The presence of impurities, variations in oxidation states etc. also

constitute defects which are extrinsic and can vary from one crystal to
another.
 Minerals are never pure compounds and many contains a wide variety
of substituted atoms. These substitutions are considered same way as
defects.

 Some minerals only allow small deviation from their pure end member
composition, eg. SiO2, while others show a complete solid slution
between two extreme compositions, eg. Olivine (Fo-Fa)

 Normally the point defect act as a color centre and imparts a

characteristic color to the mineral.

 The point defects, ie the vacancies has a major role in controlling

diffusion.

 Schottky and Frenkel defects, both are stoichiometric, ie they do not

alter the cation : anion ratio. But some compounds can accommodate
relatively large number of vacant sites, especially at high temperatures,
and this has the effect of significantly changing the cation : anion ratio.
 Line defects

 If the mineral is stressed beyond its elastic limits it becomes permanently

deformed.

 Under slow strain rates and relatively high temperatures crystalline

materials can deform by a process of slip where one part of the crystal is
translated relative to an adjacent part.

 Ultimately the deformation of individual minerals, as well as the

movement of one mineral grain over another is responsible for the large-
scale translation of materials.

 The theory of single crystal deformation was developed in metals, where

it was established that slip takes place on specific crystallographic planes,
generally close packed planes, with slip directions parallel to the shortest
lattice vectors.

 The slip plane and slip direction together define the slip system. For eg. In
olivine the common slip system is (100) [001], means that slip occurs on
(100) planes in the [001] direction.
 The concept ‘dislocation’ is used to explain the simultaneous
movement of atoms over a slip plane.

In a simplest form the dislocation is a narrow line defect in which

a plane of atoms stops within the crystal producing a line of dangling
bonds. The dislocation lines is defined by the edge of this extra plane
of atoms and in the immediate vicinity of the dislocation line the
structure is distorted.

 When the stress is applied to a crystal, dislocations are generated

with in it and these move through the crystal such that the dangling
bond is moved from one atomic plane to the next.

At any instant only those atoms around the dislocation line are
disturbed.
 The deformation is propagated along the slip plane by the movement
of the dislocation line until it reaches the surface of the crystal and a
small slip step is produced.

 The stress required to move the dislocation line is very much less
than that needed to move a whole plane of atoms simultaneously over
one another.

The Burgers vector

The displacement and direction of deformation associated with a

dislocation is defined by the Burgers vector.

In a perfect dislocation the Burgers vector is always equal to a

translation vector of the lattice, and the dislocation with least energy
are those with the smallest Burgers vectors.
There are mainly two different types of line defects/dislocations:

A dislocation is described by specifying both the Burgers vector

and the direction of the dislocation line.

1. Edge dislocation

If the Burgers vector is right angle to the dislocation line and if

both of these directions lie in the slip plane over which the atomic
displacements takes place, termed as edge dislocation.
2. Screw dislocation

If the Burgers vector and the dislocation line are parallel to each
other then it is termed as Screw dislocation.

For the Screw dislocation to move through the crystal the

applied stress must have a component parallel to the Burgers vector.
 Since the dislocation line defines the boundary between one region of
the crystal in which the slip has already been taken place and another
which has not yet slipped, it follows that it can not terminate with in the
crystal.

 A dislocation line can form a closed dislocation loop or its two ends can
terminate at the surface of the crystal.

 Dislocation loops are quite common in crystals.

 With in a dislocation loop the Burgers vector remains the same, but the
dislocation line changes direction. Thus in one part of the loop the
dislocation will be a pure edge dislocation, while at that part at right angle
to it will have pure Screw dislocation character.
 When deformation takes place at a temperature high enough for
atomic diffusion to take place, point defect such as vacant sites can
migrate through a structure and hence interact with dislocation lines. This
allows the edge dislocation to move from one slip plane to another.

Screw dislocation, on the other hand, involved pure shear and do

not interact with vacancies.

When dislocation moves along a single slip plane, the process is

termed dislocation glide while the movement of an edge dislocation out of
its slip plane is termed dislocation climb.

Partial dislocation

When a perfect dislocation passes through the crystal it leaves

the structure intact merely translating one part of the crystal by a whole
unit cell. The Burgers vector is always a lattice vector.

But in more complex and realistic structure the Burgers vector

which are some fraction of a lattice repeat are allowed. These are called
the partial dislocation and these do not replace the translated part of the
structure in the correct position to re-establish perfect long-range order.
Planar defects
Planar defects involves a violation of the long-range order and
crystal symmetry along a two dimensional surface.

Not all the two dimensional defects are planar, some may be
curved in quite complex ways.

There are mainly four different types of planar defects:

1. Stacking faults
This is a planar defect which involves a displacement of the
structure by a displacement vector (R) which lies in the fault plane.

The glide of a partial dislocation through a structure produces

stacking faults.

Stacking faults can occur during the growth of the crystal, or

during a structural transformation from one layer structure to a different
structure made up of similar layers, or during deformation by the glide of
partial dislocations.
Stacking faults are
particularly common
in chain silicates and
sheet silicates.
2. Wadsley defect

When the displacement vector associated with the planar

stacking fault is at an angle to the fault plane, the local structure around
the fault is different from that in the bulk structure. The presence of such
defects changes the stoichiometry of the crystal.

In such non-stoichiometric crystals the high concentration of

vacancies or point defects is not tolerated by the structure and there will
be an assimilation of defects to incorporate them as a structural
element.

Here the point defects has been eliminated by the formation of Wadsley
defect.

Ordered Wadsley defects are termed as crystallographic shear

(CS) planes and the structure which use this principle to change their
stoichiometry are called CS structure.
3. Antiphase domain boundaries

An antiphase boundary is an interface with in a crystal across

which there is a mistake in the translation symmetry. The interface
which is generally curved arises when a crystal transforms from a higher
to a lower symmetry retaining a similar structure but with the loss of
some translational symmetry elements.

Eg. (i) The high-low pigeonite transformation

(ii) Cation ordering in omphacite
(iii) Al-Si ordering in Ca-rich plagioclase
4. Twin boundaries

Twin boundaries are analogous in a sense to antiphase

boundaries while antiphase boundaries relate two domains by a
displacement vector and hence involve a mistake in the translational
symmetry, the twin boundaries separates domains which are related by a
point symmetry element ie. a mirror, a rotation axis or an inversion axis.

Antiphase elements represents the translation variants associated

with a reduction in translational symmetry, and the displacement vector
across the antiphase boundary is a lattice vector lost during the
transformation.

By analogy, the twin domains represents the orientational variants

associated with a reduction in the point group symmetry, and the
geometric relationship between the domains is defined by the symmetry
element lost during the transformation.

Eg. (i) The cubic-tetragonal transformation in leucite

(ii) The monoclinic-triclinic transformation in K-feldspar
(iii) Growth twinning (iv) Deformation (glide) twinning