T7008T

Phase Transformations in Metals and Alloys

John Ion
Division of Engineering Materials
E-mail: [Link]@[Link]
Office: E316
Phone: 491249

T7008T Phase Transformations 2010 John C. Ion

 Lecture 3

Crystal Interfaces and Microstructure

T7008T Phase Transformations 2010 John C. Ion

 Issues to address...

What are the most important interfaces in metallic systems?

Why are crystal interfaces and microstructure important in phase
transformations?
How do we achieve equilibrium in polycrystalline materials?
How do interfaces control kinetic transformations such as grain
growth?
What are interphase interfaces in solids?
How do we classify the different types of phase transformation?

T7008T Phase Transformations 2010 John C. Ion

Count Alois von Beckh Widmanstätten
13 July 1753 – 10 June 1849
Austrian printer and scientist [Link]
Director of the Imperial Porcelain es/Count-Alois-von-Beckh-
works in Vienna Widmanstatten/14342953900
In 1808 Widmanstätten was flame 3005
heating iron meteorites and
noticed special patterns…
The discovery was acknowledged by
Carl von Schreibers, director of the
Vienna Mineral and Zoology Cabinet,
who named the structure after
Widmanstätten
However, the discovery should be
assigned to the Englishman G.
Thomson, as four years earlier he was
using nitric acid to clean the rust off
meteorites, noticed the same patterns,
but published his findings in Italian (he
was living in Naples at the time)
T7008T Phase Transformations 2010 John C. Ion
 André Guinier George Dawson Preston

1911 - 3 July 2000 8 August 1896 – 22 June 1972

French physicist, born in Nancy British physicist, born in Oundle

Simultaneously discovered
Guinier-Preston (GP) zones in
age hardening aluminium
copper alloys in 1938

T7008T Phase Transformations 2010 John C. Ion

 Cyril Stanley Smith

4 October 1903 – 25 August 1992

Born in Birmingham, England

Renowned metallurgist and historian

of science

Studied metallurgy at the University

of Birmingham (BSc) and at the
Massachusetts Institute of
Technology (Sc.D)
c. 1952: Smith is holding a
small glass capsule full of Perhaps most famous for his work
soap bubbles that he used to on the Manhattan Project where he
illustrate how surface forces was responsible for the production
control the growth of grains of fissionable metals
in solid materials
T7008T Phase Transformations 2010 John C. Ion
 Georg (Yuri Viktorovich) Wulff

Russian mineralogist

In 1878, Gibbs proposed that for

the equilibrium shape of a
crystal, the total surface Gibbs
free energy of formation should
be a minimum for a constant
volume of crystal

In 1953 the American Conyers

Herring gave a proof of the Wulff (1901):
theorem and a method for “The length of a vector drawn
determining the equilibrium normal to a crystal face will be
shape of a crystal proportional to its surface energy“
(the Gibbs-Wulff theorem)
T7008T Phase Transformations 2010 John C. Ion
Types of interface in metallic systems
Three types are important in metallic systems:
1. free surfaces of a crystal (solid/vapour interface)
2. grain boundaries (α/α interfaces)
3. interfaces between phases (interphase interfaces, α/γ)

All crystals possess the first type

The second type separates crystals with essentially the same

composition and crystal structure, but a different orientation in space

The third separates two different phases that may have different
crystal structures and/or compositions (and therefore includes
solid/liquid interfaces)

The majority of phase transformations in metels occur by the growth

of a new phase (β) from a few nucleation sites within the parent
phase (α)

T7008T Phase Transformations 2010 John C. Ion

 Interfacial free energy
The free energy of a system containing an interface of area A and
free energy γ per unit area is:
𝐺 = 𝐺0 + 𝐴𝛾
where 𝐺0 is the free energy of the bulk system

Consider a wire frame suspending a liquid film with a movable bar:

If a force F moves a small
distance dA, the work done is FdA

The free energy of the system is

increased by dG:
𝑑𝐺 = 𝛾𝑑𝐴 + 𝐴𝑑𝛾 = 𝐹𝑑𝐴
𝑑𝛾
∴𝐹 =𝛾+𝐴
𝑑𝐴
𝑑𝛾
Assuming = 0, 𝐹 = 𝛾
𝑑𝐴

T7008T Phase Transformations 2010 John C. Ion

 Solid/vapour interfaces
Assume that the structure of solids may be discussed in terms of
a hard sphere model
The atomic configurations on the three closes packed planes in
fcc crystals are:

Atoms in the layers nearest the surface are without some of their
neighbours
Atoms on a {111} surface, for example, are missing three of their
twelve nearest neighbours
This may be used to calculate the energy of a surface
T7008T Phase Transformations 2010 John C. Ion
 Surface energy

If the bond strength of the metal is ε, then each bond may be

𝜀
considered to lower the internal energy of each atom by
2

Every surface atom with three ”broken bonds” has an excess internal
3𝜀
energy of compared with atoms in the bulk
2

For a pure metal, ε may be estimated from the latent heat of

sublimation 𝐿𝑠 (the sum of the latent heats of fusion and vaporisation):
𝜀
𝐿𝑠 = 12𝑁𝑎
2

for an fcc structure in which 12𝑁𝑎 broken bonds are formed

The energy of a {111} surface 𝐸𝑠𝑣 is therefore approximately

𝐸𝑠𝑣 = 0.25 𝐿𝑠 /𝑁𝑎

T7008T Phase Transformations 2010 John C. Ion

 Variation of surface energy with plane orientation
The energy E of different planes in a crystal varies systematically with
the orientation of the plane θ, taking a minimum corresponding to the
orientation of a close packed plane

T7008T Phase Transformations 2010 John C. Ion

 Wulff construction

Possible section
through the plane
energy plot of an fcc
crystal

Length OA
represents the free
energy of a surface
plane whose normal
lies in the direction
OA

OB = 𝛾 001
OC = 𝛾 111
T7008T Phase Transformations 2010 John C. Ion
 Boundaries in single-phase solids

The grains in a single-phase polycrystalline specimen are generally

in many different orientations and many different types of grain
boundary are therefore possible
The lattices of any two grains may be made to coincide by rotating
one of them about a single axis

Pure tilt boundary Pure twist boundary

T7008T Phase Transformations 2010 John C. Ion
 Grains
Metallographic specimens are two dimensional sections of a three
dimensional structure

Two grains meet in a plane (a grain boundary)

Three grains meet in a line (a grain edge)
Four grains meet at a point (a grain corner)
T7008T Phase Transformations 2010 John C. Ion
 Low and high angle grain boundaries

Lower density of atoms means:

high mobility
high diffusivity
high chemical reactivity
T7008T Phase Transformations 2010 John C. Ion
Soap bubble analogy: several grains of varying misorientation

row of
dislocations
(low angle)

disordered structure
(high angle)

T7008T Phase Transformations 2010 John C. Ion

 Twins

The stacking sequence across a coherent twin boundary in the

fcc lattice is:

ABCABACBA

The twin plane is a plane of mirror symmetry (the crystals on

either side of it are twins)

The nearest neighbour packing is correct through the twin

plane; only the second nearest neighbours lie in the wrong sites

T7008T Phase Transformations 2010 John C. Ion

 Twin boundaries

coherent e.g. {111} plane incoherent

in FCC

grain boundary
energy γ as a
function of grain
boundary
misorientation φ

T7008T Phase Transformations 2010 John C. Ion

 Measured boundary free energies for twin crystals

Crystal Coherent Incoherent Grain boundary

(mJ m-2) (mJ m-2) (mJ m-2)

Cu 21 498 623
Ag 8 126 377
Fe-Cr-Ni 19 209 835

Al Al

tilt parallel to <100> tilt parallel to <110>

T7008T Phase Transformations 2010 John C. Ion
 Equilibrium in polycrystalline materials (I)
How do different grain boundary energies affect the microstructure of
a polycrystalline material?
high angle
grain
boundary incoherent
annealing
twin boundary

coherent
low angle annealing
grain twin boundary
boundary

Annealed (recrystallized) austenitic stainless steel

T7008T Phase Transformations 2010 John C. Ion

 Single crystal and polycrystalline materials

Turbine blades in jet

engines may:
• be polycrystalline
• have a columnar
grain structure
• be a single crystal

Polycrystalline blades are formed using a ceramic mould

Columnar grain structured blades are created using directional
solidification techniques and have grains parallel to the major stress
axes
Single-crystal superalloys are formed as a single crystal using a
modified version of the directional solidification technique, so there
are no grain boundaries in the material
T7008T Phase Transformations 2010 John C. Ion
 Equilibrium in polycrystalline materials (II)

Consider the factors that control grain shapes in a recrystallised

polycrystal

Why do grain boundaries exist at all in annealed materials?

Boundaries are all high energy regions that increase the free energy of
a polycrystal relative to a single crystal

Therefore a polycrystalline material is never a true equilibrium structure

Grain boundaries in a polycrystal can adjust themselves during

annealing to produce a metastable equilibrium at the grain boundary
intersections

The conditions for equilibrium at a grain boundary junction may be

obtained by considering the forces that each boundary exerts on the
junction
T7008T Phase Transformations 2010 John C. Ion
 Equilibrium in polycrystalline materials (III)

If the boundary energy is independent of orientation, there will be no

torque forces acting since the energy is a minimum in that orientation

The grain boundary then behaves like a soap film

For metastable equilibrium the boundary tensions must balance:
𝛾23 𝛾 𝛾
+ 13 = 12
sin 𝜃1 sin 𝜃2 sin 𝜃3
T7008T Phase Transformations 2010 John C. Ion
 Thermally activated migration of grain boundaries

A cylindrical Tension forces balance in

boundary is acted three dimensions if the
𝛾
on by a force boundary is planar or if it is
𝑟
curved with equal radii in
opposite directions
In real metals there are always grain boundaries with net curvature
in one direction
Consequently a random grain structure is inherently unstable:
boundaries will tend to migrate towards ther centre of curvature
T7008T Phase Transformations 2010 John C. Ion
 Two dimensional grain boundary configurations

Arrows indicate directions of boundary migration during grain growth

T7008T Phase Transformations 2010 John C. Ion

 Grain growth in a soap solution (C.S. Smith)

Numbers are time in minutes

The higher pressure on the concave side of the films induces air
molecules in the smaller cells to diffuse through the film into the
larger cells, so that the smaller cells eventually dissolve
T7008T Phase Transformations 2010 John C. Ion
 Grain growth in a polycrystalline metal

If atom Ⓒ jumps from grain 1 to

grain 2 the boundary locally
advances a small distance

The effect of the pressure difference caused by a curved

boundary is to create a difference in free energy ∆𝐺 or chemical
potential ∆𝜇

In a pure metal ∆𝐺 = ∆𝜇:

2𝛾𝑉𝑚
∆𝐺 = = ∆𝜇
𝑟
T7008T Phase Transformations 2010 John C. Ion
The kinetics of grain growth

Assume that the mean radius of curvature of grain boundaries is

proportional to the mean grain diameter 𝐷

2𝛾
The mean driving force for grain growth is proportional to giving:
𝐷
2𝛾 d𝐷
𝜈 = 𝛼𝑀 =
𝐷 d𝑡

where: 𝜈 = average grain boundary velocity

𝛼 = proportionality constant of the order 1
𝑀 = grain boundary mobility (strongly dependent on temperature)

Integrating, taking 𝐷 = 𝐷0 when 𝑡 = 0:

𝐷 2 = 𝐷0 2 + 𝑘𝑡

where: 𝑘 = 4𝛼𝑀𝛾

T7008T Phase Transformations 2010 John C. Ion

 Pinning of grain boundaries by precipitates (I)

Second
phase
particles pin
grain
boundaries
(precipitation
hardening)

A grain boundary is attached to a particle along a length 2𝜋𝑟 cos 𝜃

It feels a pull of (2𝜋𝑟 cos 𝜃 γ) sin 𝜃

If there is a volume fraction 𝑓 of particles all with a radius 𝑟, the mean

3𝑓
number of particles intersecting unit area of a random plane is such
2𝜋𝑟 2
that the restraining force 𝑃 per unit area of grain boundary is
3𝑓 3𝑓𝛾
𝑃= . 𝜋𝑟𝛾 =
2𝜋𝑟 2 2𝑟
T7008T Phase Transformations 2010 John C. Ion
 Pinning of grain boundaries by precipitates (II)

2𝛾
The force 𝑃 opposes the driving force for grain growth
𝐷

When 𝐷 is small 𝑃 is relatively insignificant, but as 𝐷 increases the

2𝛾
driving force decreases until
𝐷
2𝛾 3𝑓𝛾
=
𝐷 2𝑟

when the driving force becomes insufficient to overcome the drag, giving:
4𝑟
𝐷max =
3𝑓
T7008T Phase Transformations 2010 John C. Ion
 Effect of second phase particles on grain growth

A large volume fraction of stable small particles is required to

stabilise a fine grain grain size during heating at high temperatures

T7008T Phase Transformations 2010 John C. Ion

 Interphase interfaces in solids

So far we have considered the structure and properties of

boundaries between crystals of the same solid phase

Now we will consider the boundaries between different solid

phases

We consider adjoining crystals that have:

• different crystal structures
• different compositions
• both

Interphase boundaries in solids may be divided on the basis of

their atomic structure into:
• coherent
• semicoherent
• incoherent

T7008T Phase Transformations 2010 John C. Ion

 Interface coherence

A coherent interface arises when the two crystals match perfectly

at the interface plane such that the two lattices are continuous
across the interface

Same crystal structure Different crystal structures

Different compositions Different compositions

T7008T Phase Transformations 2010 John C. Ion

 Fully coherent interface (I)
Consider Cu-Si alloys in which:
the hcp Si-rich κ phase and
the fcc Cu-rich α matrix
have identical hexagonally close packed planes: (111)fcc : 0001hcp
and identical interatomic distances

Orientation relationship:
111 𝛼 // 0001 𝜅
110 𝛼 // 1120 𝜅

The only contribution to

interfacial energy is a
chemical component
(1 mJ m-2 for the α-κ
interface)

T7008T Phase Transformations 2010 John C. Ion

 Orientation relationships and habit planes
Orientation relationship:

Crystallographic texture is one of the main characteristics of a

polycrystalline material: it determines its functional properties

An orientation relationship between two crystals of the phases α

and β defines the planes and directions that lie in a common plane
between two crystals and is written:

(hkl)α // (hkl)β , [uvw]α // [uvw]β

Habit plane:

The crystallographic plane or system of planes along which certain

phenomena (such as twinning) occur

The habit plane is a common plane between two crystals

T7008T Phase Transformations 2010 John C. Ion
 Fully coherent interface (II)
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 lattices

T7008T Phase Transformations 2010 John C. Ion

 Semicoherent interface
Strains at a coherent interface raise the total energy of the system

For sufficiently large atomic misfit, or interfacial area, it becomes

energetically more favourable to replace a coherent interface with a
semicoherent interface containing periodic misfit dislocations (200-
500 mJ m-2)

When more than one

dislocation is present
for every four
interplanar spacings,
regions of poor fit
around the dislocation
cores overlap and the
interface cannot be
considered coherent
any longer
T7008T Phase Transformations 2010 John C. Ion
 Incoherent interface
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

The pattern of atoms may either be very different in the two phases or,
if it is similar, the interatomic distances may differ by more than 25%

An incoherent interface then arises

Incoherent interfaces have high energy

(500-1000 mJ m-2)

T7008T Phase Transformations 2010 John C. Ion

 Second phase shape: interfacial energy effects

In a two phase microstructure one of the phases is often dispersed

within the other, e.g. β precipitates in an α matrix

Consider for simplicity a system containing one β precipitate

embedded in a single α crystal, and assume for simplicity that both the
precipitate and matrix are strain-free

Such a system will have a minimum free energy when the shape of the
precipitate and its orientation relationship with the matrix are optimised
to give the lowest total interfactial free energy

How may this be achieved for different types of precipitate?

T7008T Phase Transformations 2010 John C. Ion

 Fully coherent precipitates

A zone with no misfit

e.g. ⃝ Al and ∙ Ag

Ag-rich zones (GP) zones in an

Al-4 at% Ag alloy (TEM)

Since the two crystal structures match across all interfacial

planes the zone may be any shape and remain coherent
T7008T Phase Transformations 2010 John C. Ion
 Partially coherent precipitates (I)

Unit cell of θ’
precipitate in
Al-Cu alloys

Unit cell of
matrix in Al-
Cu alloys

Coherent plate of θ’ in Orientation relationship:

Al-3.9wt%Cu alloy 001 𝜃′ // 001 𝛼
100 𝜃′ // 100 𝛼
T7008T Phase Transformations 2010 John C. Ion
 Partially coherent precipitates (II)
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 common to both phases

By choosing the correct

orientation relationship
orientation a low energy coherent
or semicoherent interface to be
formed

Widmanstätten morphology of γ’
precipitates in Al-4at% Ag alloy
(TEM, H = GP zone)
T7008T Phase Transformations 2010 John C. Ion
 Widmanstätten morphologies
Widmanstätten patterns (also called Thomson structures) are
microstructural features characterised by a cross-hatched
appearance due to one phase having formed along certain
crystallographic planes

Crystalline intergrowth of
two Fe-Ni alloys,
kamacite and taenite

T7008T Phase Transformations 2010 John C. Ion

 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 precipitates
are said to be incoherent

Incoherent
precipitates of θ in
an Al-Cu alloy
(TEM)

T7008T Phase Transformations 2010 John C. Ion

 Solid / liquid interfaces

Two types of atomic structure in solid / liquid interfaces:

• Atomically flat close packed (as solid / vapour interfaces, a))
• Atomically diffuse (transition over several atom layers, b) and c))

T7008T Phase Transformations 2010 John C. Ion

 Examples of solid / liquid interfaces in metallic systems

Nonfaceted dendrites of Faceted cuboids of β’

silver in a Cu-Ag eutectic SnSb compound in a
matrix matrix of Sn-rich material
T7008T Phase Transformations 2010 John C. Ion
 Interface migration
Many phase transformations occur by a process known as
nucleation and growth

The new phase (β) first appears at certain sites in the metastable
parent (α) phase (nucleation), which grow into the surrounding
matrix

An interface is created during nucleation, which migrates into the

surrounding parent phase during growth

Nucleation is important, but most of the transformation product is

formed during the growth stage by the transfer of atoms across a
moving parent/product interface

There are two basic types of interface:

• glissile (migrate by dislocation glide, athermal, military)
• non-glissile (migrate by random jumps of atoms, thermal,
civilian)
T7008T Phase Transformations 2010 John C. Ion
 Military transformations

Nearest neighbours of any atom are essentially unchanged

Parent and product phases have the same composition (no
diffusion)
Examples:
martensite forming from austenite in steels
formation of mechanical twins

T7008T Phase Transformations 2010 John C. Ion

 Civilian transformations

Parent and product phases may or may not have the same
composition

If there is no change in composition, e.g. ferrite (α) → austenite (γ)

in pure iron, the new phase grows as fast as atoms cross the
interface (interface controlled)
If the parent and product phases
have different compositions growth of
the new phase will require long range
diffusion:

The growth of a B-rich β phase into

an A-rich α phase can only occur if
diffusion is able to transport A away
from the interface, and B towards the
advancing interface (diffusion
controlled growth)
T7008T Phase Transformations 2010 John C. Ion
T7008T Phase Transformations 2010 John C. Ion
 Summary

The three most important interfaces in metals and alloys:

free surfaces of a crystal (solid/vapour interface)
grain boundaries (α/α interfaces)
interfaces between phases (interphase interfaces, α/γ)
Equilibrium in polycrystalline materials is achieved by minimising
surface energy
Coherent, semicoherent and incoherent interfaces may be formed
between phases
Atomic migration resulting from differences in free energy control
kinetic transformations
Phase transformations may be classified in many ways
Military or civilian
Diffusionless or diffusion-controlled
Athermal or thermally activated
Interfaces play an important role in all types of phase
transformation

T7008T Phase Transformations 2010 John C. Ion