IMPERFECTS (DEFECTS) IN CRYSTALS
Up to now, we have described perfectly regular crystal struct
ures, called ideal crystals and obtained by combining a basis with an
infinite space lattice. In ideal crystals atoms were arranged in a
regular way. In actual crystals, however, imperfections or defects are
always present and their nature and effects are very important in
understanding the properties of crystals. These imperfections,
electrical properties etc, to a great extent.
Natural crystals always contain defects, often in abundance,
due to the uncontrolled conditions under which they were formed.
The presence of defects which affect the color can make these
crystals valuable as gems, as in ruby (chromium replacing a small
fraction of the aluminium in aluminium oxide: Al 2 O 3 ). Crystal
prepared in laboratory will also always contain defects.
Imperfections are found in all crystals unless some special
means are used to reduce them to a low level. The atoms do not have
their full quota of electrons in the lowest energy level. But the atoms
vibrate due to thermal effect and the electrons also change their
positions. There is much other type of defects found in the structure
of the crystals.
The crystallographic defects are classified on the basis of their
geometry as follows:
1. Point Defects
A. vacancy defects
B. schottky imperfections
C. interstitial defects
D. Frenkel defect
E. compositional defects
(a) Substitutional impurity
(b) Interstitial impurity
F. electronic defects
2. Line Defects
A. edge dislocation
B. screw dislocation
3. Surface Defects
a. External Defects
b. Internal Defetcs
A. grain boundaries
B. tilts boundaries
C. twin boundaries
D. stacking fault
4. Volume Defects
Point Defects
The defects which take place due to imperfect packing of atom
during crystallization are known as point defects. The po int defect
also takes place due to vibrations of atoms at high temperatures,
quenching, by severe deformation of the crystal lattice; e.g., By
hammering or rolling. Point imperfections are completely local in
effect, e.g., A vacant lattice site. Point defe cts are always present in
crystals and their present results in a decrease in the free energy.
A. Vacancy defect
B. Schottky imperfections
C. Interstitial defects
D. Frenkel defects
E. Compositional defects
F. Electronic defects
Vacancy defect
A vacancy is the simplest point defect and involves one or more
atoms are missing from a normally occupying position as shown in
the Fig. The defect caused is known as vacancy. Such defects can be
a result of imperfect packing during formation of crystals or from
thermal vibration of the atoms at high temperature. In the latter
case, when the thermal energy due to vibration is increased, there is
always an increased probability that individual atoms will jump out
of their positions of lowest energy.
Schottky imperfections
These are closely related to vacancy defect but are found in
compounds which must maintain a charge balance. They involve
vacancies of pair of icons of opposite charge. This type of
imperfection maintains a charge neutrality in crystal. This type is
dominent in alkali halides.
Both vacancies and schottky defects facilitate atomic diffusion.
Interstitial defects
Whenever an extra atom occupies interstitial position [i.e.,
voids] in the crystal system without dislodging the parent atoms as
shown in Fig. the defect caused is known as interstitial defects. This
happens when the atomic packing factor is low. This atom which
occupies the interstitial position is generally smaller than the parent
atom.
In close packed structures e.g. F.C.C and H.C.P, the largest
size of an atom that can fit in the interstitial void or space have a
radius about 22.5% of the radii of parent atoms. Interstitialcies may
also be single interstitial, di-interstitials, and tri-interstitials.
Frenkel defects
Whenever a missing atom [responsible for vacancy] occupies
interstitial position as shown in Fig then that defect is k nown as
Frenkel defect. Noted that a frenkel defect is a combination
of vacancy and interstitial defects. The interstitial and
frenkel defects are less in number than vacancy and schottky
defects, because additional energy is required to force the atom into
the new position.
Compositional defects
These defects arise from impurity atom during
original crystallization. Impurity atoms considered as defects in a
perfect lattice are responsible for the functioning of most
semiconductor devices.
A substitutional impurity is created when a foreign atom
substitutes for a parent atom in the lattice as shown in Fig.
Ex: In brass, zinc is a substitutional atom in the copper lattice.
An interstitial impurity is a small sized atom occupying an
interstice or space between the regularly positioned atoms; as shown
in Fig.
Ex: In steel, carbon atoms occupy the interstitial position in the iron
lattice.
Electronic defects
Electronic defects are the errors in charge distribution in solids.
These so called electronic imperfections are preliminary
necessary to explain electrical conductivity and related phenomenon
in solids. An important example of this is the creation of p -n
junctions and transistors.
LINE DEFECTS
Line imperfections are called dislocations. A linear disturban
ce of the atomic arrangement, which can move very easily on the slip
plane through the crystal, is known as dislocation. The dislocation
may be caused during growth of crystals from a melt or fo rm
a vapor or they may occur during a slip.
The defect which
takes place due to dislocation of atoms along a line in same direction
is called line defects. The line defects also takes place when a central
portion of a crystal lattice slips without affecting the outer portion.
These are two types of line defects:
a. Edge Dislocation
b. Screw Dislocation.
Both these defects are the most striking imperfections and are
responsible for the useful property of ductility in metals, ceramics
and crystalline polymers.
Edge Dislocation
An edge dislocation may be described as an extra plane of
atoms within a crystal structure. It is accompanied by zones of
compression and of tension so that there is a net increase in energy
along a dislocation.
The displacement distance for atoms around the dislocation is
called 'burger's vector'. This vector is at right angle to the edge
dislocation.
Whenever a half plane of atom is inserted between the planes
of atoms in a perfect crystals then this defect is produced Fig a:
Shows a cross section of a crystal where dots represent atoms
arranged in an orderly manner. Fig b: Shows the displacement of
atoms when an extra half plane is inserted from the top. It may be
noted from this Fig that top and bottom of the crystal above and
below the line X-Y appears perfect. If the extra half plane is inserted
from top the defect so produced is represented by ┴ [inverted T] as
shown in Fig. and if the extra half plane is inserted from the bottom,
the defect so produced is represented by T.
The criterion of distortion is what is called the burgers vector.
It can be determined if a closed contour is drawn around a zone in
an ideal crystal by passing from one site to another as shown in Fig.
(a) and then the procedure is repeated a zone in a real crystal
containing a dislocation. As may be seen from Fig. (b), the contour
described in real crystal turns out to be unclosed. The vector
required for the closing the contour is the Burgers vector. The
Burger's vector of an edge dislocation is equal to the inter atomic
space and perpendicular to the dislocation line.
Screw Dislocation
Whenever the atoms are displaced in two separate planes
perpendicular to each other then the defect so produced is known as
screw dislocation. Fig a: represents an isometric view of a perfect
crystal. Fig b: shows the displacement of atoms appear like that of a
screw or helical surfaces.
In this type of dislocation shear stresses are associated with
adjacent atoms and extra energy is involved, along the dislocation.
The successive atom planes are transformed into the surface of the
helix of screw by this dislocation which accounts for its name as
screw dislocation. A screw dislocation has its displacement of
Burger's vector parallel to the linear defect but there is distortion of
the plane.
Surface defects
Surface defects are the two dimensional regions in a crystal.
The defect which takes place on the surface of a material is known
as surface defects. It may be noted that surface defects takes place
either due to imperfect packing of atoms during crystallisation or
defective orientation of the surface. The types of surface defects are:
1) External defects
2) Internal defects
External defects
The external surface of a material is an imperfection itself be
cause the atomic bonds do not extend beyond it. The surface atoms
have neighbor on one side only while atoms inside the crystal
have neighbors on either side of them. Since surface atoms are not
entirely surrounded by others, they possess higher energy than that
of internal atoms. For most metals, the energy of surface atoms is of
the order 1 J/m 2 .
Internal defects
The internal defects are classified as follows:
1. Grain boundaries
2. Twin boundaries
3. Tilt boundary
[Link] boundaries
5. Engineering materials may be either polycrystalline or s
ingle crystal type. A polycrystalline alloy contains an enormous
quantity of fine grains. Grain boundary imperfections are those
surface imperfections when ever crystals or grains of different
orientation separate the general pattern of atoms and exhibits
a boundary during nucleation or crystallization. This type of
defect generally takes place during the solidification of the
liquid metal.
[Link] Boundary
7. This is another planar surface [Link]
the boundaries in which the atomic arrangement on one side
of the boundary is a somewhat mirror image of th e
arrangement of atoms of the other side, as shown in Fig. The
defect caused is known as Twin boundary. The region in which
a twin boundary defect occurs is between the twinning panes
as shown in Fig. The region of material between these
boundaries is approximately termed as "Twin".
8. Twins result from atomic displacements that are
produced from applied mechanical shear forces, and also
during annealing heat treatments following deformation.
Annealing twins are typically found in crystals that have the
F.C.C. crystal structure. While mechanical twins are observed
in B.C.C. and H.C.P metals.
Tilt Boundary
This is another type of surface defect called low-
angle boundary as the orientation difference between
two neighboring crystals is less than 10°. This is why the disruption
in the boundary is not so drastic as in the high angle boundary. This
type of boundary is associated with relatively little energy and is
composed of edge dislocations lying one above the other. In general,
one can described low-angle boundaries by suitable arrays of
dislocation. The angle or tilt,
Where b is the magnitude of Burgers vector, and
D is the average vertical distance between dislocations.
VOLUME IMPERFECTIONS
Volume imperfections, e.g. cracks may arise when there is on
ly small electrostatic dissimilarity between the stacking sequences
of close packed planes in metals. Moreover, when clusters of atoms
are missing, a large vacancy or void is got which is also a volume
imperfection. Foreign particle inclusions, large voids or non -
crystalline regions which have the dimensions of the order of 0.20
nm are also termed volume imperfections. Bulk or volume defects
are normally introduced during processing and fabrication steps.
Volume or Bulk defects includes pores, cracks, foreign inclusion,
and other phases.
Note: A color centre is lattice defect that absorbs visible light. The
usual place to find color centre is in ionic crystals.
Alloy
A substance which is composed of two or more than two che
mical elements such that metallic atoms predominates in
composition and the metallic bond predominates is called an
"Alloy". The element which is present in largest proportion is called
"base metal" and all other elements present are known as
"alloying elements".
Alloys are classified as binary alloys, composed of two
components; as ternary alloys, composed of three components; or
as multicomponent alloys. Most commercial alloys are
multicomponent. The composition of an alloy is described by giving
the percentage (either by weight or by atoms) of each element in it.
Metal alloys by virtue of composition, are often grouped into
two classes : Ferrous and Non-Ferrous. Ferrous alloys are those in
which iron is the principal constituent, include steels and cast irons.
The non-ferrous alloys are all alloys that are not iron based.
Alloys are widely used in industry because their physical and
chemical properties can be easily varied to suit the exact individual
requirement. One can achieve this by preparing alloys of different
metals.
SOLID SOLUTION
A homogeneous crystalline structure in which one or more ty
pes of atoms or molecules may be partly substituted for the original
atoms and molecules without changing the structure is called
'solid solution'.
(Or)
A solid solution is a solid state solution of one or more solutes
in a solvent. Such a mixture is considered a solution rather than a
compound when the crystal structure of the solvent remains
unchanged by addition of the solutes, and when the mixture remains
in a single homogeneous phase.
In a solid solution the atoms occur in a definite geometrical
pattern, which is usually a slightly distorted form of one of the
constituent metals.
Solid solutions are conductors, but not so good as the pure
metals on which they are based.
Example:
1. Cu-Zn alloys (brasses)
2. Ni-Cu alloys (Monel metal)
3. Au-Ag alloys
4. Ag-Cu alloys
5. Fe-C alloys.
Substitutional Solid Solutions
If the atoms of the solvent or parent metal are replaced in the
crystal lattice by atoms of the solute metal then the solid solution is
known as 'Substitutional solid solution'.
For example, copper atoms may substitute for nickel atoms without
disturbing the F.C.C. structure of nickel (Fig. a). In the
substitutional solid solutions, the substitution can be either
disordered or ordered.
Fig. b shows disordered substitutional solid solution. Here the
solute atoms have substituted disorderly for the solvent atoms on
their lattice site.
Fig. c shows an ordered substitutional solid solution. Here the solute
atoms have substituted in an orderly manner for the solvent atoms
on their lattice site.
Hume Rothery rules for the formation of substitutional solid
solutions:
By studying a number of alloy systems, Hume Rothery
formulated certain rules which govern the formation of
substitutional solid solutions. These are:
(a) Crystal structure factor:
For complete solid solubility, the two elements should have
the same type of crystal structure i.e., both elements should have
either F.C.C or B.C.C or H.C.P structure.
(b) Relative size factor:
As the size (atomic radii) difference between two elements
increases, the solid solubility becomes more restricted. For
extensive solid solubility the difference in atomic radii of two
elements should be less than about 15%. If the relative size factor is
more than 15%, solid solubility is limited. For example, both silver
and lead have F.C.C Structure and the relative size factor is about
20%. Therefore the solubility of lead in solid silver is about 1.5% and
he solubility of silver in solid lead is about 0.1%. Copper and Nickel
are completely soluble in each other in all proportions. They have
the same type of crystal structure (F.C.C) and differ in atomic radii
by about 2%.
(c) Chemical affinity factor:
Solid solubility is favored when the two metals have lesser
chemical affinity. If the chemical affinity of the two metals is greater
then greater is the tendency towards compound formation.
Generally, if the two metals are separated in the periodic table
widely then they possess greater chemical affinity and are very likely
to form some type of compound instead of solid solution.
(d) Relative valence factor:
It is found that a metal of lower valance tends to dissolve more
of a metal of higher valance than vice versa. For example in
Aluminium-nickel alloy system, nickel (lower valance) dissolve 5%
aluminium but aluminium (higher valance) dissolve 0.04 % nickel.
Interstitial Solid Solutions
In interstitial solid solutions, the solute atom does not displace
a solvent atom, but rather it enters one of the holes or interstices
between the solvent atoms.
An example is Iron-carbon system which is shown in Fig.
In this system the carbon (solute atom) atom occupies an
interstitial position between iron (solvent atom) atoms. Normally,
atoms which have atomic radii less than one angstrom are likely to
form interstitial solid solutions. Examples are atoms of carbon
(0.77 A°), Nitrogen (0.71 A°), Hydrogen (0.46 A°), Oxygen (0.60 A°)
etc.
Phase
It is a homogeneous portion of a system that has uniform
physical and chemical characteristics. The number of phases in a
system is the number of different substances that exist in it in a
homogeneous system. A homogeneous liquid solution is a single -
phase system; a mixture of crystals of two types, differing in
composition and structure separated by an interface, or the
coexistence of the liquid alloy and its crystals comprise two-phase
system.
Phase diagram
A graphical representation of the relationship between
environmental constraints (e.g. temperature and sometimes
pressure), composition, and region of phase stability, ordinarily
under conditions of equilibrium.
Most phase diagrams are prepared by using slow cooling
conditions whereby phases are in equilibrium. One can get following
important information's from the phase diagrams
• Phases at different composition and temperature
• Equilibrium solubility of one element or compound in
another element
• Melting points of different phases in an alloy
• Temperature of solidification or range of solidification
of an alloy.
GIBB’S PHASE RULE OR THE PHASE RULE OR
CONDENSED PHASE RULE
This expresses mathematically the general relationships for
the existence of stable phases corresponding to the equilibrium
conditions (external conditions like temperature and pressure). It
enables us to predict and check the process es that occur in alloys
during heating or cooling. Using this rule, it is possible to determine
whether the solidification process takes place at a constant
temperature or within a certain temperature interval; it can also
indicate the number of phases that can exist simultaneously in a
system.
The phase rule enunciated by J.W. Gibbs. The phase rule
establishes the relationship between the number of phases P,
number of components C, and number of degrees of freedom F. It is
expresses mathematically as a simple form:
P+F=C+n
(1) In studying chemical equilibrium, temperature and pressure are
regarded as external factors determining the state of the system so,
P+F=C+2 (1)
n = number of external factors = 2 (temperature and pressure)
In applying the phase rule to metal systems the effect of
pressure is neglected, leaving only one variable factor, --
temperature. Equation (1) reduces to
F=C+1-P 1(a)
The number of degrees of freedom is essentially the number
of independent variables, both internal (composition and phases)
and external ones (temperature, pressure, concentration etc.,),
which can be changed without changing the number of phases in
equilibrium. The number of independent variables cannot be more
than the number of variables, i.e.,
F = C - P + 2 £ P(C-1) + 2 (2)
Where P(C - 1) denotes the total number of compositional
variables when P phases are there in the system. Including the two
external variables (pressure and temperature), the total number of
variables is P(C - 1) + 2 .
In equilibrium all factors have definite values, hence the
degree of freedom cannot be less than zero, C - P + 1 ³0
then P £ C + 1
Obviously, the number of phases in a system cannot exceed the
number of components plus one.
The components of a system may be elements, ions or
compounds. The components refer to the independent chemical
species that comprises the system. In the ice -stream system, the
component is H 2 O, in the Cu-Ni system the components are the
elements Cu and Ni, whereas in the Al 2 O 3 -Cr 2 O 3 system, one can
take the two oxides to be components, nut it may be convenient to
choose Fe and Fe 3 C (Iron carbide) as the components.
As follows from the phase rule, the number of phases existing
simultaneously in a binary system cannot be more than three. These
three phases can only exist at a definite phase composition and a
definite temperature. If the number of phases in a binary system
turns out to be more than three, this means that either the alloy is
not in the equilibrium state or the number of phases and
constituents has been determined incorrectly. In a ternary system
no more than four phases may be in equilibrium. When only one
phase is present in a system, the degree of freedom are equal to the
total variable, with the increase in number of phases, the degree of
freedom decrease. The degree of freedom cannot be less than zero.
Obviously, we have an upper limit to the number of phases that can
exist in equilibrium in a given system.
At solidification temperature, a pure metal is a one-component
system consisting of two phases of identical composition.
F=1+2-2=0
Clearly, the number of phases and number of degrees of
freedom equals zero, i.e., F = 0. This is known as non-variant
equilibrium. When the number of phases is less than the maximum
possible number by one, the number of degrees of freedom will also
increase by one (F = 1). Such type of system is called as monovariant.
An alloy of two metals is a two-phase and two-component
system at solidification, F = 1. When F = 2, the system is said to be
a divarient. Obviously, a system may be in equilibrium at different
temperatures and concentrations.
One can represent all transformations occurring in alloys and
depending on temperature and concentration (C = 2) by equilibrium
diagrams. The equilibrium diagrams are plotted with concentration
as the abscissa and temperature as ordinate.
Long-Range and Short-Range Order
orderliness in the arrangement of atoms and molecules in solids and liquids. Orderliness ove
r distances comparable to interatomic distances is called short-
range order, whereas orderliness repeated over infinitely great distances is called long-
range order. In an ideal gas. the arrangement of an atom at any point in space is independe
nt of the arrangement of other atoms. Thus, both long-range and short-
range order are absent in the ideal gas, but liquids and amorphous solids exhibit short-
range order—
a certain regularity in the arrangement of the neighboring atoms. At great distances the order
becomes “blurred” and gradually gives way to “disorder.” which means that long-
range order does not exist in liquids and amorphous solids.
In crystals, the atoms are arranged in regular rows or networks (in three-
dimensional lattices), and a regular alternation of atoms separated by the same distances is
repeated for atoms separated by any distance—that is, both long-range and short-
range order exist. The basic criteria of long-
range order are the symmetry and regularity of arrangement of particles, which repeat at any
distance from a given atom. The presence of long-range and short-
range order is due to the interaction between the particles. A completely ordered state, howe
ver, is only possible at absolute zero, since order is disturbed by thermal motion.
The concepts of long-range and short-
range order are important in the theory of alloys, in which they characterize the degree of ord
ering of an alloy—
for example. in an alloy consisting of two components, complete ordering leads to alternation
of the two types of atoms; in other words, the nearest neighbors of each atom are only atom
s of the other type. Incomplete order is reflected by the fact that atoms of the same type app
ear among the nearest neighbors. Depending on the thermal and mechanical treatment, vari
ous degrees of ordering may be attained in an alloy; in this case. the physical properties of t
he alloy are also changed.
Long-range and short-
range order exist in terms other than the mutual arrangement of the particles (coordination or
der). For example, a liquid consisting of asymmetric molecules exhibits short-
range order (in the case of liquid crystals, long-
range order) in the orientation of molecules (orienta-
tional order). Ferromagnetic and antiferromagnetic materials exhibit short-range and long-
range order in the orientation of magnetic moments.