Material Science & Metallurgy

Defects in Crystals

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 allyed (i.e., when impurity atoms are added) for example,
(707% copper/30% zinc) is much harder and stronger than purecopper
brass
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 materials
Imperfections in Solids

it has been implicitly assumed that perfect order exists

throughout crystalline materials on an atomic scale.
There is no such thing as a perfect crystal.
What are these imperfections?
Why are they important?

Many of the important properties of materials are due

to the of
presence imperfections.

Imperfections in Solids
Solidification- result of casting of molten material
2 steps
Nuclei form
Nuclei grow to form crystals grain structure
Start with a molten material -all liquid

.
nuclei crystals growing grain structure
liquid
Crystals grow until they meet each other

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Polycrystalline Materials

Angle of misalignment
Grain Boundaries
regions between crystals High-angle
transition from lattice of one 9rdin
boundary
region to that of the other
| Small-angle
slightly disordered grain
boundary
low density in grain
boundaries
high mobility
high diffusivity
high chemical reactivity Angle of misalignment

Solidification
size in all directions)
Grains can be equiaxed (roughly same
- columnar (elongated grains)
8 Cm

heat
flow
Shell of
Columnar in
equiaxed grains
due to rapid
area with less
cooling (greater
undercooling A) near wall

equiaxed grains.
Grain Refiner added to make smaller, more uniform,
Where do defects come from?

Even the formation of crystals under extreme care the defects are
bound to be part of it. There is nothing as a perfect crystal
considerations
Vacancies are unavoidable, due to entropy
such as in alloys, where a
Often defects are introduced intentionally,
properties improves it.
blend of material
size
&Or strengthening or hardening a material, by decreasing grain
or strain hardening.

Theoretical shear strength of a solid

277X shear stress

Slip in a perfect, defect free lattice
T=t Sln displacement relation

G Elastic shear stress

strain relation

Shear modulus, G, of solids is in the range

of 20-150 GPa, and thus theoretical shear

27tX strength could be in range 3-30 GPa.

For small /b T=tm However, actual values of the shear stress
required for plastic deformation is only
G=T L7 about 0.5-10 Mpa.
m
a b
This is 100 1000 times larger than the measured
shear strength of solids.
 Tdeal crystal = Lattice Motif
Real crystals: deviation from idealistic arrangement (Defects or
imperfections) Controls both physical and mechanical properties.

Crystalline defect refers to a lattice irregularity having one or more of its

dimensions on the order of an atomic diameter. Classification of crystalline
imperfections is frequently made according to geometry or dimensionality
of the defect.
Classification of defects ( Based on dimensionality)
1. Zero- dimensional defects or point defect Vacancy , Interstitial
2.One dimensional or line defect or Dislocation
3. Two- dimensional or surface defect free surface, grain boundary.
twin boundary stacking fault
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Point Defects
Vacancies:
-vacant atomic sites in a structure.

Vacancy
distortion
of planes

Self-Interstitials:
"extra" atoms positioned between atomic sites.

self-
interstitial
distortion
of planes
 Equilibrium Concentration:
Point Defects
Equilibrium concentration varies with temperature!

No. of defects Activation energy

No. of potential N exp

defect sites. +N kT
Temperature
Boltzmann's constant
(1.38 x 1023 J/atom-K))
(8.62 x 10-5 eV/atom-K)
Each lattice site
is a potential
vacancy site
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Measuring Activation Energy

We can get Q, from

an experiment.
Ny exp KT
N
Measure this.. .Replot it...
Nv Ny slope
In N
N
Qy Ik
exponential
dependence

1/T
defect concentration
12
Estimating Vacancy Concentration
.Find the equilibrium number of vacancies in 1 m3 of Cu at 1000°C.
.
Given: p 8.4 g/cm ACu 63.5 g/mol
Q 0.9 eV/atom NA =
6.02 x 1023 atoms/mol
nA_
0.9 eV/atom p VoNa
Ny 2.7x 10
N K 1273K
8.62 x 105 eV/atom-K
For 1 m3, N= p x NA X1 m3= 8.0 x 1028 sites
ACu
Answe
Nv ( 2 . 7 x 104)(8.0 x 1026) sites = 2.2 x 1025 vacancies
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(b) C)

(d) (e)

Point defects: (a) vacancy, (b) interstitial atom, (c) small

substitutional atom, (d) large substitutional atom, (e) Frenkel
defect, and (f) Schottky defect. All of these defects disrupt the
perfect arrangement of the surroundina atoms. 14
Interstitial Defects
An interstitial defect is formed when an extra
atom or ion is inserted into the crystal structure
at a normaly 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.
-60-666
Interstitial atoms such as hydrogen are often
present as impurities, whereas carbon atoms are
intentionally added to iron to produce steel.

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*For small concentrations, carbon atoms

occupy interstitial sites in the iron crystal
Location of Interstitial Radius Ratio Representation
structure, introducing a stress in the inear 0-0.155

localized region of the crystal in their Conter of trianglo 0.156-0.225

vicinity. the introduction of interstitial Center of tetrahedron 0.225-0.414

atoms is one important way of increasing

the strength of metallic materials Center of octahecron 0.414-0.13

Unlike vacancies, once introduced, the Center of Cube 0.732-1.000

number of interstitial atoms or ions in the

structure remains nearly constant, even
when the temperature is changed.

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Substitutional Defects
A substitutional defect is introduced when one atom or
ion is replaced by a different type of atom or ion as in

Figure.
The substitutional atoms or ions occupy normal lattice

sites
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. In either case,
the substitutional defects disturb the surrounding crystal 17

Again, the substitutional defect can be introduced either as an

impurity or as a deliberate alloying addition, and, onceintroduced,
the number of defects is relatively independent of temperature.
Examples of substitutional defects include incorporation of
dopants such as phosphorus or boron into Si.
Similarly, if we add copper to nickel, copper atoms will occupy
crystallographic sites where nickel atoms would normally be
present
The substitutional atoms will often increase the strength of the
metallic material.

8
A Frenkel defect isa 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.
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Frenkel
defect
Cation vacancy

cationinterstitial

Schottky
defect
Cation vacancy

anion vacancy
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Point Defects in Alloys
Two outcomes if impurity (B) added to host (A):
Solid solution of B in A (ie., random dist. of point defects)

OR

Substitutional solid soln. Interstitial solid soln.

(e.g., Cu in Ni) (e.g., C in Fe)

Solid solution of B in A plus particles of a new phase (usually for a larger

amount of B)
Second phase particle
--dif ent composition
-often different structure.

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Dr Aviral Mishra, Assistant Professor,IPE Department,NIT Jalandhar

Line defect or Dislocations

Dislocation A line imperfection in a crystalline material.
A dislocation is a linear or one-dimensional defect around which some of the
atoms are misaligned.

They typically are introduced into a crystal during solidification of the

material or when the material is deformed permanently.
Although dislocations are present in all materials, including ceramics
and polymers, they are particularly useful in explaining deformation
and strengthening in metallic materials.

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 One type of dislocation is represented in
Figure: an extra portion of a plane of atoms,
or half-plane, the edge of which terminates
Burgers vector
within the crystal.
This is termed an edge dislocation; it is a
linear defect that centers on the line that is
Edge
defined along the end of the extra half-plane dislocation
ne

of atoms.
&This is sometimes termed the dislocation line,
which, for the edge dislocation in Figure, is
perpendicular to the plane of the page.
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Within the region around the dislocation line

there is some localized lattice distortion. The
atoms above the dislocation line in Figure are Burgers vector

squeezed together, and those below are pulled

apart; this is reflected in the slight curvature
for the vertical planes of atoms as they bend Edge
disiocation
line
around this extra half-plane.
The magnitude of this distortion decreases
with distance away from the dislocation line:
at positions far removed, the crystal lattice is
virtually perfect.
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 The edge dislocation in Figure is
represented by the symbol , Burgers vector

which also indicates the position

of the dislocation line.
An edge dislocation may also be
Edge
dislocation
formed by an extra halfplane of line

atoms that is included in the

bottom portion of the crystal; its
designation is a T.
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Screw dislocation
may be thought of as being formed by a shear stress that is applied to
produce the distortion shown in Figure a: The upper front region of the
crystal is shifted one atomic distance to the right relative to the
bottom portion

Dislocation
line

3urgers vector (D)

a)

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Screw Dislocations
The screw dislocation (Figure) can be illustrated by cutting partway
through a perfect crystal and then skewing the crystal by one atom
spacing.
The vector required to complete the loop is the Burgers vector b. If we
continued our rotation, we would trace out a spiral path. The axis, or line
around which we trace out this path, is the screw dislocation. The
Burgers vector is parallel to the screw dislocation.

Disloca
ation
line Burgers
(6)
vector o

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The atomic distortion associated with a screw dislocation is also linear and along a
dislocation line, line AB in Figure b. The screw dislocation derives its name from
the spiral or helical path or ramp that is traced around the dislocation line by the
atomic planes of atoms. Sometimes the symbol is used to designate a screw
dislocation.

Dislocation
ine

Burgers vector (D)

a)

8
Surface Defects or INTERFACIAL DEFECTS
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.

1. Material Surface
The exterior dimensions of the material represent surfaces at which the crystal
abruptly ends. Each atom at the surface no longer has the proper coordination
number, and atomic bonding is disrupted. The exterior surface may also be very
rough, may contain tiny notches, and may be much more reactive than the bulk of
the material.

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2. Grain Boundaries
The microstructure of many engineered ceramic
and metallic materials consists of many grains.
A grain is a portion of the material within which
Grain

the arrangement of the atoms is nearly boundary

identical.
Three grains are shown schematically in Figure
(a): the arrangement of atoms in each grain is
identical but the grains are oriented

differently.
Figure (b) shows a micrograph of grains in a

stainless steel sample.

(6)
0
 A grain boundary, the surface that separates the
individual grains.
I t is a narrow zone in which the atoms are not

properly spaced.
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.

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Angle of misalignment
Various degrees of
crystallographic misalignment
between adjacent grains are
High--angle
grain boundary
possible (Figure).
When this orientation Small-angle
grain boundary
mismatch is slight, on the
order of a few degrees, then
the term small- (or low-)
angle grain boundary is used.
Angle of misalignment

32
These boundaries can be described in terms
of dislocation arrays.
One simple small-angle grain boundary is
formed when edge dislocations are aligned in
the manner of Figure. This type is called a tilt
boundary: the angle of misorientation, 8, is
also indicated in the figure.
When the angle of misorientation is parallel
to the boundary, a twist boundary results,
which can be described by an array of screw
dislocations.
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The atoms are bonded less regularly along a grain boundary and
consequently there is an interfacial or grain boundary energy.
The magnitude of this energy is a function of the degree of
misorientation, being larger for high-angle boundaries.
Grain boundaries are more chemically reactive than the grains
themselves consequence of this boundary energy.
as a

Furthermore, impurity atoms often preferentially segregate along

these boundaries because of their higher energy state.

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The total interfacial energy is lower in large or coarse-grained
materials than in fine-grained ones because there is less total
boundary area in the former.
Grains grow at elevated temperatures to reduce the total boundary
energy.
I n spite of this disordered arrangement of atoms and lack of
regular bonding along grain boundaries, a polycrystalline material is
still very strong: cohesive forces within and across the boundary
are present

&Furthermore, the density of a polycrystalline specimen is virtually

identical to that of a single crystal of the same material.
5

3. Phase Boundaries

Phase boundaries exist in multiphase materials in which a

different phase exists on each side of the boundary:
I n addition, each of the constituent phases has its own
distinctive physical and/or chemical characteristics.
&As we shall see in subsequent chapters, phase boundaries
play an important role in determining the mechanical
characteristics of some multiphase metal alloys.

6
 4. Twin Boundaries
A twin boundary is a special type of

grain boundary across which there is a Twin plane (boundary)

specific mirror lattice symmetry: that

is, atoms on one side of the boundary
are located in mirror-image positions
to those of the atoms on the other
side (Figure)
The region of material between these
boundaries is appropriately termed a
twin.
37

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).
Twinning occurs on a definite crystallographic plane and in a
specific direction, both of which depend on the crystal structure.
Annealing twins are typically found in metals that have the FCC
crystal structure, whereas mechanical twins are observed in BCC
and HCP metals.

38
Annealing twins may be observed in
the photomicrograph of the
polycrystalline brass specimen
shown n Figure. The twins
correspond to those regions having
relatively straight and parallel
sides and a different visual
contrast than the un-twinned
regions of the grains within which
they reside.

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5. BULK OR VOLUME DEFECTSs

Other defects exist in all solid materials that are much larger than
those discussed.
These include pores, cracks, foreign inclusions, and other phases.
They are normally introduced during processing and fabrication
steps.
Some of these defects and their effects on the properties of
materials are discussed in subsequent chapters.

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