Crystal

Interfaces
So, what is a crystal ?
 A crystal is a solid consisting of a three-dimensional periodic ordering of
atoms, ions or molecules.
 This kind of solid is then termed as: crystalline solid, while at the other
end, the solid, which does not have a periodical ordering of atoms, is
called amorphous solid.
 Most metals (Al, steel, Cu and their alloy are crystalline. While glass and
most polymers (plastics, rubber, etc) are amorphous.
Three types of basic interface:
The solid/vapor interface is itself
important in vaporization and
condensation transformations

Grain boundaries are important

in recrystallization, i.e. the
transformation of a highly
deformed grain structure into
new undeformed grains.

Although no new phase is

separate crystals interfaces that separate involved in recrystallization it
with essentially the two different phases does have many features in
same composition that can have different common with phase
and crystal structure, crystal structures and/or transformations
but different compositions. Included
orientation in space. solid/liquid interfaces
Interfacial free energy
• The free energy of a system containing an interface of area A and free
energy  per unit area is given by:
G = G0 + A 
• In this instance, G0 is the free energy of the system assuming that all
materials in the system has the properties of the bulk,  is therefore
the excess free energy arising from the fact that some materials lies
or close to the interface
 Liquid
film

F F
A A +dA

 From the figure, a force F is needed to keep
the bar in position.
 If this force move small distance so that the
total area of the film is increased by dA, the
work done is FdA, that is used to increase
free energy of the system by dG, or dG =
FdA
• From
   previous equation, G = G0 + A 
dG = dA + Ad
Equating this with FdA gives,
For liquid film, d/dA = 0, then F = 
(surface tension, in J/m2).
For solid d/dA ≠ 0
 Origin of surface energy
The extra energy possessed by the surface atoms is described as
surface energy or surface free energy.
 Toput a separated atom backs to its original position, an extra energy is
needed.
The energy required will be equal to the number of broken bonds, Nb,
multiply by half of the bond strength, :

where a is the surface atomic density, the number of atoms per unit
area on the new surface.
6
 (111) (200) (220)

Atomic configuration in FCC crystals: note how the density of

atoms decreases as (h2+k2+l2) increases
Surface energy in FCC

  4𝜀  
5 𝜀   𝜀
γ {100 }= 2 γ {110 }= 2
γ {111 }= 2 √ 3 2
𝑎 2
√ 𝑎 𝑎

8
Crystalline solids (most materials) generally
consist of millions of individual grains
separated by boundaries.
Each grain (or subgrain) is a single crystal.
Within each individual grain there is a
systematic packing of atoms. Therefore each
grain has different orientation (see Figure 16-
1) and is separated from the neighboring
grain by grain boundary.
When the misorientation between two
grains is small, the grain boundary can be
described by a relatively simple configuration
of dislocations (e.g., an edge dislocation wall)
and is, fittingly, called a low-angle boundary.
• There is class of defects called interfacial
or planar defects:
• They occupy an area or surface and are
therefore bidimensional.
• They are of great importance in
mechanical metallurgy.
• Examples of these form of defects include:
• grain boundaries
• twin boundaries
• interphase boundaries
• free surface of materials
• Of all these, the grain boundaries are the
most important from the mechanical
properties point of view.
Average surface free energies
Crystal Tm/oC sv/mJ m-2
Sn 232 680
Al 660 1080
Ag 961 1120
Au 1063 1390
Cu 1084 1720
-Fe 1536 2080
Pt 1796 2280
W 3407 2650
Boundaries in single-phase solids
Tilt and Twist boundaries: The
relative orientations of the
crystals and the boundary Edge Dislocation
forming (a) a tilt boundary, occurs
when the axis of rotation is
parallel to the plane of the
boundary and (b) a twist
boundary, occurs when the
rotation axis is perpendicular to
the boundary Screw Dislocation
 Grain
boundary
transition
zone

Free volume along the disordered grain

boundary: disordered grain boundary
(schematic)
Special high-angle boundaries

Twinning
 plane

A coherent twin An incoherent twin

boundary boundary
Role of Grain Boundaries
• Grain boundaries have very important role
in plastic deformation of polycrystalline
materials.
• We outline below the important aspects of
the role of grain boundaries:
1. At low temperature (T<0.5Tm, where Tm is
the melting point in K), the grain
boundaries act as strong obstacles to
dislocation motion. Mobile dislocations
can pile up against the grain boundaries
and thus give rise to stress concentrations
that can be relaxed by initiating locally
multiple slip.
2. The smaller the grain size, the larger will be the total boundary surface area per
unit volume.
• In other words, for a given deformation in the beginning of the stress-strain
curve, the total volume occupied by the work-hardened material increases with
the decreasing grain size.
• This implies a greater hardening due to dislocation interactions induced by
multiple slip.

3. At high temperatures the grain boundaries function as sites of weakness.

• Grain boundary sliding may occur, leading to plastic flow and/or opening up of
voids along the boundaries.
4. Grain boundaries can act as sources and sinks for vacancies at high
temperatures, leading to diffusion currents as, for example, in the
Nabarro Herring creep mechanism.

5. In polycrystalline materials, the individual grains usually have a

random orientation with respect to one another.
• The term polycrystalline refers to any material which is composed of many
individual grains.
• However, some materials are actually used in their single crystal state: silicon for
integrated circuits and nickel alloys for aircraft engine turbine blades are two
examples.
• The sizes of individual grains vary from sub
micrometer (for nanocrystalline structures) to
millimeters and even centimeters (for materials
especially processed for high-temperature creep
resistance).
• This figure shows typical equiaxed grain
configurations for polycrystalline tantalum and
titanium carbide.
• One example of a material property that is
dependent on grain size is the strength of a
material; as grain size is increased the material
becomes weaker. Note that
• strength is expressed in units of stress
(MN/m2)
• grain size of a material can be altered
(increased) by annealing
 Twin Boundary

• The atomic arrangement on one side of the twin boundary is

related to the other side by a symmetry operation (usually a mirror)
• Twin boundaries usually occur in pairs such that the orientation
difference introduced by one is restored by the other
• The region between the regions is called the twinned region

Annealing twins (formed during recrystallization)

Twin

Deformation twins (formed during plastic deformation)

A twin boundary separates two Pairs of twin boundaries. the
crystalline regions that are, orientation difference introduced by
structurally, mirror images of each one is restored by the other
other.
 Twin boundary in Fe doped SrTiO3 bicrystals (artificially prepared)
High-resolution micrograph

Mirror related
variants

Twin plane

[1] S. Hutt, O. Kienzle, F. Ernst and M. Rühle, Z Metallkd, 92 (2001) 2

Twinning
 Migration of grain
boundary
• The overall result of boundary
1 migration is to reduce the number of
2 grains, thereby increasing the mean
0 grain size and reducing the total grain
boundary energy.
3 4 • This phenomenon is known as grain
growth or grain coarsening, occurs in
metals at temperatures above 0.5 Tm
where boundaries have significant
mobility.
 Boundary
motion
 The atomic
mechanism of
boundary
migration.
 The boundary
migrates to the left
if the jump rate
from grain 1  2 is
greater than 2  1 Grain 1 Grain 2

Grain growth
Two
dimensional
cells of a soap 11 49 ½ 52 ¼ 52 ¾

solution
showing grain
growth.
Numbers are 53 ¼ 53 ½ 156 225

time in minutes.
Interphase interfaces
On the basis of their atomic structure,
interphase boundaries in solids may be
divided into three types:
• Coherent interface
• Semicoherent interface
• Incoherent interface
Fully coherent interface
• A coherent interface arises
when the two crystals match
perfectly at the interface
plane.
• In this instance, the two
lattices are continuous across
the interface.
• The interfacial plane has the
same atomic configuration in
both phases.
a

A A'
B B'

a
Each crystal structure has a different
chemical composition but the same
crystal structure.
• It  is required that the two
crystals to be oriented relative
to each other in a special way.
• E.g. Interface between the
HCP silicon-rich  phase and
the FCC copper-rich -matrix
in Cu-Si alloys.
• This gives an orientation
relationship:
(111)//(0001)
[]//[11 0]
• When the distance between
the atoms in the interface is 
not identical, it is still
possible to maintain
coherency by straining one
or both of the two lattices. 
• The resultant lattice
distortions are known as
coherency strains with
energies as low as 1 mJ m-2 A coherent interface with lattice
up to about 200 mJ m-2. mismatch leads to coherency
strains in the adjoining lattices.
Semicoherent interfaces d D

• The strain associated with a 

coherent interface raise the
total energy of the system. ┴ ┴
• If the atomic misfit is large, it

is more favorable to replace
the coherent interface with a
d
semicoherent interface,
characterized by the energies
 
in the range of 200-500 mJ m-
2.
For small :
• For example, (111)fcc and
(110)bcc, almost parallel to
each other. where b = (d+d)/2 is the Burger
vector of the dislocations.
Incoherent interfaces

• When the interfacial plane has a

very different atomic
configuration in the two adjoining
phases, there is no possibility of
good matching across the
interface.
• In this instance, the interface
becomes incoherent, characterized
by a high energy of ~500-1000 mJ
m-2.
Fully coherent precipitates
If the precipitate (P) has the same
crystal structure and a similar
lattice parameter to the parent a
phase the two phases can form
low-energy coherent interfaces
on all sides-provided the two
lattices are in a parallel
orientation relationship
Partially coherent precipitates
An  precipitate at a grain
boundary triple point in an
- Cu-In Alloy. Interface A A
and B are incoherent while C
is semicoherent.

C
B
Interface migration
Composition changes in a
substitutional alloy caused
by interface migration
when two adjoining
phases have different
compositions.
Two different types of interface:
• Glissile: migrate by dislocation glide that results in the shearing of
parent lattice into the product  athermal.
• Non-glissile: migrate by random jumps of individual atoms across the
interface ~ migration of random high angle grain boundary  need
thermal activation.
Two different types of interface:
Glissile interface:
• Coordinated motion of atoms
crossing the interface.
• The parent and the product have
the same composition and no
diffusion.
• Martensitic transformation,
formation of twinning and
mechanical twinning.
Non-glissile interface:
• Motion across the interface
is random.
• The parent and the product
may or may not have the
same composition.
• Diffusion controlled.