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Imperfections in


Why Study Imperfections in

The properties of some materials are profoundly influenced by

the presence of imperfections. Consequently, it is important to

have a knowledge about the types of imperfections that exist and
the roles they play in affecting the behavior of materials. For
example, the mechanical properties of pure metals experience
significant alterations when alloyed (i.e., when impurity atoms
are added)for example, brass (70% copper30% zinc) is much
harder and stronger than pure copper (Section 7.9). Also,
integrated circuit microelectronic devices found in our
computers, calculators, and home appliances function because of
highly controlled concentrations of specific impurities that are
incorporated into small, localized regions of semiconducting

three basic types of

0D --- point defects,

1D --- line defects (or dislocations), and

2D --- surface defects

3D --- bulk/volume defects

Point defects are localized disruptions in otherwise
perfect atomic or ionic arrangements in a crystal
These imperfections may be introduced by movement
of the atoms or ions when they gain energy by heating,
during processing of the material, or by the intentional
or unintentional introduction of impurities.

IMPURITIES are elements or compounds that are present from raw

materials or processing. For example, silicon crystals grown in
quartz crucibles contain oxygen as an impurity.
DOPANTS, on the other hand, are elements or compounds that are
deliberately added, in known concentrations, at specific locations in
the microstructure, with an intended beneficial effect on properties
or processing














A vacancy is produced when an atom or an ion is missing from its
normal site in the crystal structure

The equilibrium number of vacancies for a given quantity of

material depends on and increases with temperature according to

The Effect of Temperature on Vacancy Concentrations
Calculate the concentration of vacancies in copper at room
temperature (25C). What temperature will be needed to heat treat
copper such that the concentration of vacancies produced will be
1000 times more than the equilibrium concentration of vacancies at
room temperature? Assume that 20,000 cal are required to produce
a mole of vacancies in copper. The lattice parameter of FCC copper
is 0.36151 nm

Vacancy Concentrations in Iron
Calculate the theoretical density of iron, and then determine the
number of vacancies needed for a BCC iron crystal to have a
density of 7.874 g cm3. The lattice parameter of iron is 2.866 *10-8
cm. Atomic Weight of Iron is 55.847g/mol

An interstitial defect is formed when an extra atom or
ion is inserted into the crystal structure at a normally
unoccupied position

Interstitial atoms or ions, although much smaller than the atoms or

ions located at the lattice points, are still larger than the interstitial
sites that they occupy; consequently, the surrounding crystal region
is compressed and distorted.
Interstitial atoms such as hydrogen are often present as impurities,
whereas carbon atoms are intentionally added to iron to produce
steel. For small concentrations, carbon atoms occupy interstitial
sites in the iron crystal structure, introducing a stress in the
localized region of the crystal in their vicinity

Sites for Carbon in Iron
In FCC iron, carbon atoms are located at octahedral sites, which
occur at the center of each edge of the unit cell at sites such as (0,
0, 1 2) and at the center of the unit cell (1 2, 1 2, 1 2). In BCC iron,
carbon atoms enter tetrahedral sites, such as (0, 1 2, 1 4). The
lattice parameter is 0.3571 nm for FCC iron and 0.2866 nm for BCC
iron. Assume that carbon atoms have a radius of 0.071 nm. (a)
Would we expect a greater distortion of the crystal by an interstitial
carbon atom in FCC or BCC iron? (b) What would be the atomic
percentage of carbon in each type of iron if all the interstitial sites
were filled?

A substitutional defectis introduced when one atom or
ion is replaced by a different type of atom or ion. The
substitutional atoms or ions occupy the normal lattice
site. Substitutional atoms or ions may either be larger
than the normal atoms or ions in the crystal structure, in
which case the surrounding interatomic spacings are
reduced, or smaller causing the surrounding atoms to
have larger interatomic spacings.


An interstitialcy is created when an atom identical to those at the
normal lattice points is located in an interstitial position. These
defects are most likely to be found in crystal structures having a low
packing factor.
A Frenkel defect is a vacancy-interstitial pair formed when an
ion jumps from a normal lattice point to an interstitial site, leaving
behind a vacancy. Although, this is usually associated with ionic
materials, a Frenkel defect can occur in metals and covalently
bonded materials

A Schottky defect is unique to ionic materials and is commonly

found in many ceramic materials. When vacancies occur in an
ionically bonded material, a stoichiometric number of anions and
cations must be missing from regular atomic positions if electrical
neutrality is to be preserved. For example, one Mg+2 vacancy and
one O-2 vacancy in MgO constitute a Schottky pair. In ZrO2, for one
Zr+4 vacancy, there will be two O-2 vacancies.

Dislocations are line imperfections in an otherwise perfect crystal.
They typically are introduced into a crystal during solidification of
the material or when the material is deformed permanently.
3 types:

the screw dislocation,


he edge dislocation, and


the mixed dislocation.

A 1D line defect in which a path spirals around a dislocation line
penetrating through otherwise individual parallel planes

---- A 1D line defect that is the edge of an extra half plane of atoms
within a crystal system

----- have both edge and screw components, with a transition region
between them. The Burgers vector, however, remains the same for
all portions of the mixed dislocation.

---- The displacement vector that closes the loop when traversing
an equal number of lattice steps around the defect

---- denoted by b
----- it is parallel in the line of dislocation in screw dislocation and is
perpendicular in the line of dislocation in edge dislocation

Burgers vector in screw


Burgers vector in edge dislocation

Calculate the length of burger vector in copper (FCC crystal

Surface defects are the boundaries, or planes, that separate a
material into regions. For example, each region may have the same
crystal structure but different orientations


Material/External Surface


Grain Boundaries


Twin Boundaries


Stacking fault

One of the most obvious boundaries is the external surface, along
which the crystal structure terminates. Surface atoms are not
bonded to the maximum number of nearest neighbors, and are
therefore in a higher energy state than the atoms at interior
positions. The bonds of these surface atoms that are not satisfied
give rise to a surface energy, expressed in units of energy per unit
area (J/m2 or erg/cm2).To reduce this energy, materials tend to
minimize, if at all possible, the total surface area. For example,
liquids assume a shape having a minimum areathe droplets
become spherical. Of course, this is not possible with solids, which
are mechanically rigid.

A grain boundary, the surface that separates the individual grains,
is a narrow zone in which the atoms are not properly spaced. That is
to say, the atoms are so close together at some locations in the
grain boundary that they cause a region of compression, and in
other areas they are so far apart that they cause a region of tension
A grain is a portion of the material within which the arrangement of
the atoms is nearly identical; however, the orientation of the atom
arrangement, or crystal structure, is different for each adjoining

One method of controlling the properties of a material is by controlling

the grain size. By reducing the grain size, we increase the number of
grains and, hence, increase the amount of grain boundary area. Any
dislocation moves only a short distance before encountering a grain
boundary, and the strength of the metallic material is increased. The
Hall-Petch equation relates the grain size to the yield strength,

where y ---- is the yield strength (the level of stress necessary to cause
a certain amount of permanent deformation),
d ------ is the average diameter of the grains, and
0 and K ------are constants for the metal

The yield strength of mild steel with an average grain size of 0.05
mm is 20,000 psi. The yield stress of the same steel with a grain
size of 0.007 mm is 40,000 psi. What will be the average grain size
of the same steel with a yield stress of 30,000 psi? Assume the HallPetch equation is valid and that changes in the observed yield
stress are due to changes in grain size.

Optical microscopy is one technique that is used to reveal microstructural

features such as grain boundaries that require less than about 2000
magnification. The process of preparing a metallic sample and observing or
recording its microstructure is called metallography. A sample of the
material is sanded and polished to a mirror-like finish. The surface is then
exposed to chemical attack, or etching, with grain boundaries being
attacked more aggressively than the remainder of the grain. Light from an
optical microscope is reflected or scattered from the sample surface,
depending on how the surface is etched. When more light is scattered from
deeply etched features such as the grain boundaries, these features appear
dark. In ceramic samples, a technique known as thermal grooving is often
used to observe grain boundaries. It involves polishing and heating a
ceramic sample to temperatures below the sintering temperature (1300C)
for a short time. Sintering is a process for forming a dense mass by
heating compacted powdered material.

One manner by which grain size is specified is the ASTM grain size
number (ASTM is the American Society for Testing and Materials).
The number of grains per square inch is determined from a
photograph of the metal taken at a magnification of 100. The ASTM
grain size number n is calculated as

Where N is the number of grains per square inch for a

magnification of
n is the number of grains per square inch.

At a magnification other than 100x use:

Where: NM is the number of grains per square inch at magnification

In addition, the inclusion of the term makes use of the fact that, while
magnification is a length parameter, area is expressed in terms of
units of length squared. As a consequence, the number of grains per
unit area increases with the square of the increase in magnification.

Computations of ASTM Grain Size Number and Number of Grains Per
Unit Area

Determine the ASTM grain size number of a metal specimen if

45 grains per square inch are measured at a magnification of


For this same specimen, how many grains per square inch will
there be at a magnification of 85x?



Suppose we count 16 grains per square inch in a photomicrograph
taken at a magnification of 250x. What is the ASTM grain size

Small Angle Grain Boundaries

A small angle grain boundary is an array of dislocations
that produces a small misorientation between the
adjoining crystals. Because the energy of the surface is
less than that of a regular grain boundary, the small
angle grain boundaries are not as effective in blocking
slip. Small angle boundaries formed by edge dislocations
are called tilt boundaries, and those caused by screw
dislocations are called twist boundaries.

Twin Boundaries
A twin boundary is a plane across which there is a special mirror
image misorientation of the crystal structure

Twins result from atomic displacements that are produced from

applied mechanical shear forces (mechanical twins), and also during
annealing heat treatments following deformation (annealing twins)
Annealing ---- A heat treatment that typically involves heating a
metallic material to a high temperature for an extended period of
time in order to lower the dislocation density and hence impart


Other defects exist in all solid materials that are much larger the
preceding defects.These include pores, cracks, foreign inclusions,
and other phases. They are normally introduced during processing
and fabrication steps