Crystal Interface &

Microstructure
Contents in Phase
Transformation
Background to understand phase Representative Phase
transformation transformation
• Thermodynamics and • Solidification:
Phase Diagrams • Liquid → Solid
• Diffusion • Diffusional
Transformations in
• Crystal Interface and
Solid:
Microstructure • Solid → Solid
• Diffusionless
Transformations:
• Solid → Solid
Crystal Interfaces and Microstructure

• Interfacial Free Energy

• Solid/Vapor Interfaces
• Boundaries in Single-Phase Solids
a) Low-Angle and High-Angle Boundaries
b) Special High-Angle Grain Boundaries
c) Equilibrium in Polycrystalline Materials
Types of interface in metallic
system
Basically three different types of interface are important in metallic
system:
1. The free surfaces of a crystal (solid/vapor interface); Important in
vaporization and condensation transformations
2. Grain boundaries (/ interfaces); Important in recrystallization, i.e.
the transformation of a highly deformed grain structure into new
undeformed grains, and following grain coarsening and grain growth
• same composition, same crystal structure
• different orientation
3. Interphase interfaces or Interface Boundary (/ interfaces);
Important role in determining the kinetics of phase transformation/
complex
• different composition &
• crystal structure
Notes:
• The first interface, the free surfaces of a crystal (solid/vapor
interface) are owned by all crystals.
• The second interface, Grain boundaries (/ interfaces) are
boundaries that separate crystals with essentially the same
composition and crystal structure, but different orientation in
space.
• The third interface, Interphase boundaries (/ interfaces) are
interfaces that separate two different phases that can have different
crystal structures and/or compositions. Included solid/liquid
interfaces.
• The solid/vapor interface is itself important in vaporization and
condensation transformations, while 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 involved in recrystallization it does have
many features in common with phase transformations
• The great majority of phase transformations in
metals occur by the growth of a new phase (β) from
a few nucleation sites within the parent phase (α)-a
nucleation and growth process.
• The α/β interface plays an important role in
determining the kinetics of phase transformations
and is the most important. It is, however, also the
most complex and least understood
Interfacial free energy
• Interfacial energy (γ : J/m2)
• Gibbs free energy of a system containing an
interface of area A and free energy  per unit area
is given by:
Gbulk + Ginterface therefore G = G0 + A 

• G0 is the free energy of the system assuming that all

materials in the system has the properties of the bulk,
•  is the excess free energy arising from the fact that
some materials lies or close to the interface
Interfacial energy (γ ) vs. surface tension (F:
a force per unit length)
Liquid
film

F F
A A +dA

• work done : F dA = dG
• dG = γ dA + A dγ → F = γ + A dγ /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
•   The work is used to increase the free energy of the
system by dG, therefore dG = dA + Ad
• Equating this with F dA gives,

• For liquid film, d/dA = 0 (independent of A), then

F =  (surface tension = surface energy). N/m = J/m2.
• For solid d/dA ≠ 0, but, very small value
• At near melting temperature (high enough atomic
mobility) dγ /dA = 0 → F = γ (N/m = J/m2)
•  Definition: Surface energy is the energy required to
create a unit area of new surface,

where A is the surface area.

10
•  To put 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.

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Solid/Vapour Interface
• From the definition of Gibbs free energy the surface free
energy will be given by
Y = E + PV –TS
• Even if the 'PV‘ term is ignored surface entropy effects must
be taken into account. It might be expected that the surface
atoms will have more freedom of movement and therefore
a higher thermal entropy compared atoms in the bulk.
• Extra configurational entropy can also be introduced into
the surface by the formation of surface vacancies for
example. The surface of a crystal should therefore be
associated with a positive excess entropy which will partly
compensate for the high internal energy.
 Solid/Vapor interfaces
To a first approximation the structure of solid surfaces can be
discussed in terms of a hard sphere model.

(111) (200) (220)

The origin of the surface free energy is that atoms in the layers nearest the
surface are without some of their neighbors.
For example: the atoms on a {111} surface (FCC structure) are deprived of
three of their twelve neighbors.

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 }= γ {111 }= 2 √ 3 2
𝑎 √ 2 𝑎2 𝑎

14
Explanation

For FCC,
there would
be 12 nearest
neighbor.

15
Explanation

For FCC,
there would
be 12 nearest
neighbor.

16
• The nearest neighbor for plane
(100) would be 4 atoms.
• That means there would be another
8 atoms, 4 atoms in front of the
plane and 4 atoms behind the
plane.
• Either these 4 atoms will be broken
during the formation of a new
surface.

17
• The nearest neighbor for plane (111)
would be 6 atoms.
• That means there would be another
6 atoms, 3 atoms in front of the
plane and 3 atoms behind the plane.
• Either these 3 atoms will be broken
during the formation of a new
surface.

18
• The nearest neighbor for plane (111)
would be 6 atoms.
• That means there would be another
6 atoms, 3 atoms in front of the
plane and 3 atoms behind the plane.
• Either these 3 atoms will be broken
during the formation of a new
surface.

19
• The nearest neighbor for plane
(110) would be 2 atoms.
• That means there would be
another 10 atoms, 5 atoms in front
of the plane and 5 atoms behind
the plane.
• Either these 5 atoms will be broken
during the formation of a new
surface.

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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
Grain Boundaries

• 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 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.
Grain Boundaries

• When the misorientation is large (high-angle grain

boundary), more complicated structures are
involved.
• The grain boundaries are therefore:
• where grains meet in a solid.
• transition regions between the neighboring crystals.
• where there is a disturbance in the atomic packing
• These transition regions (grain boundaries) may
consist of various kinds of dislocation
arrangements.
Role of Grain Boundaries
• Grain boundaries have very important role in plastic deformation
of polycrystalline materials.
• At low temperature (T<0.5 Tm, 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.
• There exists a condition of compatibility among the neighboring
grains during the deformation of polycrystals; that is, if the
development of voids or cracks is not permitted, the deformation
in each grain must be accommodated by its neighbors. This
accommodation is realized by multiple slip in the vicinity of the
boundaries which leads to a high strain hardening rate.
• 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
Role of Grain Boundaries
• 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.
• 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.
• 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.
• The sizes of individual grains vary from submicrometer (for
nanocrystalline structures) to millimeters and even centimeters (for
materials especially processed for high-temperature creep
resistance).
• 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 softer (strength is expressed in units of stress (MN/m2))
• grain size of a material can be altered (increased) by annealing
Boundaries in single-phase
solids
Tilt and Twist boundaries: The relative
orientations of the crystals and the
boundary 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
Low-angle and high-angle boundaries

 
Low-angle tilt b

boundary is an ┴

array of parallel  
𝐷=
𝑏
𝜃
edge dislocations
┴

┴
Low-angle twist
boundary is a cross-
grid of two sets of
screw dislocations: O
atoms in crystal
below boundary, 
atoms in crystal
above boundary
• The energy of low-angle grain boundary is simply the total
energy of the dislocations within unit area of boundary, which
is dependent to the spacing of the dislocations, D = b/
• At very small of  the dislocation spacing is very large and the
grain boundary energy is approximately proportional to the
density of dislocation in the boundary (1/D), i.e.   .
• As  increases the strain field of the dislocation cancel out so
that  increases at a decreasing rate.
• When  exceeds 10-15o the dislocation spacing is so small that
dislocation cores overlap and it is impossible to physically
identify the individual dislocation.
• When  > 10-15o the boundary is known as a random high-
angle grain boundary, which contains large areas of poor fit
and have a relatively open structure.
An unsymmetric tilt
boundary: dislocations
with two different
Burgers vectors are
present.
 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
Migration of grain boundary

• The overall result of boundary migration is to

reduce the number of grains, thereby increasing
the mean grain size and reducing the total grain
boundary energy.
• This phenomenon is known as grain growth or grain
coarsening, occurs in metals at temperatures above
0.5 Tm where boundaries have significant mobility.
Two-dimensional grain
boundary
configurations. The
arrow indicate the
direction boundaries
will migrate during grain
growth
• How could a boundary
disappear?
• Boundaries between different 1
orientated grains could 2
0
disappear by gradual
migration
3 4
 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

Step-like structure
where close-packed
planes protrude into
the boundary
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:
1. Coherent interface
2. Semicoherent interface
3. Incoherent interface

• The major differences between them regarding the

chemical and structural (strain) contribution to the surface
energy: γinterface =γch + γst.
• Becker’s model for description of the coherent interface:
surface energy is proportional to the square of the
composition (concentration) gradient:
General consideration of interface (between
α and β phase)
• When β particle precipitates from α phase, a new interface forms.
For a spherical particle of radius r, the total surface energy is the
sum of the two sources: surface energy, (i.e., γch
contributed by chemical bonding at interface), and the strain
energy,

where c is elastic constant, and ε is the relative strain due to misfit

of lattice:

Where aα and aβ are the unstressed interplanar spacings of the

matching planes in the α- and β-phase, respectively.
• For example for the above dislocation (a type of misfit), if a α = 1.0 Å, aβ = 1.2 Å,
then ε = 20% (i.e. every 5 continuous planes in the β phase will take a dislocation
to accommodate the misfit of the two lattice). However, if aα = 1.0 Å, aβ = 1.01 Å,
i.e., no significant difference between the two phase lattice, then ε = 1% (i.e. the
dislocation density decreases to every 100 planes in the β phase, approaching to
the case of coherent interface;
• on the other hand, if the two phases differ dramatically in lattice, say a α = 1.0 Å, aβ
= 1.5 Å, then ε = 50% (i.e., now every 2 continuous planes in the β phase will take
a dislocation, very worse for the two phases to match or fit, thus falling to the
category of incoherent interface.) for the interface with intermediate ε < 25%,
usually called semicoherent 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 A'
B B'
 

a a
(a) (b)
• Strain-free coherent interfaces. (a) Each crystal structure has a
different chemical composition but the same crystal structure. (b)
The two phases have different lattices.
• 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.
• For a coherent interface the only contribution is  (coherent) = ch
• The resultant lattice distortions are known as coherency strains with
energies as low as 1 mJ m-2 up to about 200 mJ m-2.
 

A coherent interface with lattice

mismatch leads to coherency
strains in the adjoining lattices.
 Semicoherent interfaces
• 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 semicoherent interface, characterized
by the energies in the range of 200-500 mJ m -2.

d D

The misfit parallel 

to the interface is
accommodated by ┴ ┴
a series of edge
dislocations 

d
• 
For small :

where b = (d+d)/2 is the Burger vector of the

dislocations.
d D

┴ ┴

d
    > 0.35, i.e. one dislocation every four interplanar spacings, the
•• When
region of poor fit around the dislocation cores overlap and the interface
becomes incoherent.
• The interfacial energy of a semicoherent interface can be approximately
considered as the sum of two parts: (a) a chemical contribution and (b) a
structural term.
• A chemical contribution, ch, is as for a fully coherent interface, and a
structural term, st, is the extra energy due to the structural distortions
caused by the misfit dislocations, i.e.
 (semicoherent) = ch + st
• For small , st = 
• st increases less rapidly as  becomes larger and it levels out when  0.25 in
a similar way to the variation of grain-boundary energy with 
• The reason for such behavior is that the misfit dislocation spacing decreases,
the associated strain fields increasingly overlap and annul each other.
• When  > 0.25, i.e. one dislocation every four interplanar spacings, the
regions of poor fit around the dislocation cores overlap and the interface
cannot be considered as coherent. i.e. it is incoherent
Incoherent precipitates

• When the two phases have completely different

crystal structures, or when the two lattices are in a
random orientation, it is unlikely that any coherent
or semicoherent interfaces form and the precipitate
is said to be incoherent.
• Since the interfacial energy should be high for all
interfacial planes, the -plot and the equilibrium
inclusion shape will be roughly spherical.
 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.
• In general, incoherent
interfaces result when two
randomly-oriented crystals
are joined across any
interfacial plane as shown in
previous figure.
• They may, however, also exist
between crystals with an
orientation relationship if the
interface has a different
structure in the two crystals. An incoherent interface
 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

• This situation arises during the early

stages of many precipitation
hardening heat treatments, and the 
phase is then termed a fully coherent
precipitate or a GP zone (GP for
Guinier and Preston)
 Partially coherent precipitates
• When the precipitate and matrix have different crystal structures it is
usually difficult to find a lattice plane that is common to both phases.
• Nevertheless, for certain phase combinations there may be one plane
that is more or less identical in each crystal, and by choosing the correct
orientation relationship it is then possible for a low-energy coherent or
semicoherent interface to be formed.
• However, usually no other planes of good matching and the precipitate
must consequently also be bounded by high-energy incoherent
interfaces.
• The equilibrium shape to be a disc with a thickness/diameter ratio of c/i
where c and i are the energies of the (semi-) coherent and incoherent
interfaces.
A section through a -plot for a
precipitate showing one coherent or c
semicoherent interface, together with 0 i
the equilibrium shape (a disc)
Equilibrium
shape
Grain-boundary precipitates

Grain-boundary precipitates
 Interfaces

• An  precipitate at a
grain boundary triple
point in an - Cu-In
A
Alloy.
• Interface A and B are
incoherent while C is C
semicoherent. B
 Liquid Liquid
Solid

interface
(a)

Diffuse
Liquid

Solid
(c) (b) Solid

Solid/liquid interfaces: (a) atomically smooth, (b) and

(c) atomically rough, or diffuse interfaces
Interface migration

Composition changes in a
substitutional alloy caused
by interface migration
when two adjoining phases
have different
compositions.
Interface migration with
long range diffusion.
(a) Composition profiles
across the interface.
(b) The origin of the
driving force for
boundary migration
into the  phase.
• Phase transformation in metals and alloys usually
occurs through nucleation and growth.
• New phase (β) first appears within the matrix and
then grows
• An interface is created during nucleation stage and
migrates into surrounding matrix during the growth
stage
• This results in transfer of atoms across the moving
new phase/matrix interface.
Two different types of interface
Glissile Non-glissile
• migrate by dislocation glide • migrate by random jumps of
that results in the shearing of individual atoms across the
parent lattice into the product interface ~ migration of
 athermal. random high angle grain
boundary  need thermal
activation.
• Coordinated motion of atoms • Motion across the interface is
crossing the interface. random.
• The parent and the product • The parent and the product
have the same composition may or may not have the
and no diffusion. same composition.
• Martensitic transformation, • Diffusion controlled.
formation of twinning and
mechanical twinning.
 Homophase vs. Heterophase
• There is a useful comparison that can be made between grain
boundaries (homophase) and interphase boundaries
(heterophase).

Structure               G.B.                         Interface
atoms no boundary coherent
match 1 interface
dislocations low angle g.b. semi-
coherent
disordered high angle g.b. incoherent
Remember:
• for a grain boundary to exist, there must be a difference in the lattice position
(rotationally) between the two grains.
• An interface can exist even when the lattices are the same structure and in the
same (rotational) position because of the chemical difference.
59