Phase Transformation - Basic Concepts!

Phenomenon! Basics!
water becomes ice at 0C! why would a phase change
water becomes vapour at (transform)?!
100C! how fast does phase
Al melts at 660C! transformation take place?!
Fe change from ferrite (BCC) at what microstructure will result?!
Solid room temperature to austenite
Phase (FCC) when heated up to
Trans- 912-1394C! Examples!
forma- Fe-C system!
tion
fine precipitates form upon
ageing in Al-Cu alloy! Al-Cu system!

Definition!
An existing phase changes in
What is the mechanism?!
amount and/or structure at a diffusional!
certain rate, and as a result of diffusionless!
phase transformation, the
material possesses a different
microstructure.! Reading: 10.1-10.4 (5th and 6th ed) + lecture notes

MCEN90014: Materials ! ! !Dr. K. Xia! ! ! !1!

Phase Transformation - Basic Concepts!

Thermodynamics! ! !H = E + PV!
Gibbs free energy (G)! ! !E: internal energy of the
a measurement of the state of system (kinetic + potential
a system (e.g. an alloy)! energies)!
Difference in free energy = the P: pressure!
work required to change a V: volume!
system from one state to (for solid and liquid, E PV.
another state! Thus H E)!
consisting of two parts! G is used to determine the stability
! !G = H TS! of a system!
! !H: enthalpy - heat content of a system with a higher G would
the system! tend to change into a system
! !S: entropy - randomness with a lower G.!
(degree of chaos) of the
system!
Additional reading:

! !T: absolute temperature!
- 1.1 in Phase Transformations in Metals and
Alloys by D. A. Porter & K. E. Easterling, 1992.

- Any textbook on thermodynamics.

MCEN90014: Materials ! ! !Dr. K. Xia! ! ! !2!

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 Phase Transformation - Basic Concepts!
Phase equilibrium! Stable and metastable state!
a system is in equilibrium if it has
Unstable Unstable
no desire to change, i.e. it is in a
state
state

state of minimum G!
mathematically, this means!
G
dG = 0
Unstable
dG = 0 (and d2G > 0)! dG = 0

equilibrium

Metastable
equilibrium

Stable equilibrium

B
A

"Structure" of the system

structure A is absolutely stable!

structure B is only relatively
stable - metastable!
structure B has the tendency to
become A to possess lower G!

MCEN90014: Materials ! ! !Dr. K. Xia! ! ! !3!

Phase Transformation - Basic Concepts!

Phase transformation!
Driving energy!
A phase (S) will change
into a new phase (F) if the
resulting system (phase)
has a lower G!
G = G2 G1 < 0!
G is the driving energy!
Activation energy!
G'

However, there is often an Ga =
transitional, activated state activation
energy

(A) between S and F.!
G

In order for transformation
SF to take place, an G1

activation energy, Ga, G = driving energy

has to be provided (usually G2

by thermal activation).!
S
A
F

(Initial State)
(Activated State)
(Final State)

MCEN90014: Materials ! ! !Dr. K. Xia! ! ! !4!

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 Phase Transformation - Basic Concepts!
Kinetics! precipitation process takes
how fast is a phase place at various rates
transformation taking place?! depending on temperature!
the transformation rate is Thermodynamics determines
proportional to! whether a phase transformation is
exp ( Ga/RT)! likely to take place (whether there
is a driving force).!
the higher the activation
But, it is the activation energy and
energy, the slower the
temperature which determine the
transformation!
rate a transformation is actually
temperature very important carried out. It is often the kinetics
(thermally activated that determines which
processes)! microstructure will exist, not
example! thermodynamics.!
diamond is metastable at
RT, but will not transform to
become graphite (the stable A transformation which takes 1 second at
T = 1000 K may take 1014 years at T =
phase) due to very high 300 K!!

activation energy!

MCEN90014: Materials ! ! !Dr. K. Xia! ! ! !5!

Phase Transformation - Basic Concepts!

Process and kinetics of phase
transformation!
How does a phase transformation
start and progress?!
Example: solidification of a pure
material (such as water and liquid
aluminium) - a transformation from
liquid phase to solid phase!
formation of small solid nuclei
from liquid phase: nucleation!
each solid crystal becomes
larger: growth!
continuing growth of these
crystals (called grains) until all
liquid is consumed!

Reading: 10.3W of the 6th ed: downloadable from

"www.wiley.com/college/callister" or from CD
available at the reserve desk of Engineering Library

MCEN90014: Materials ! ! !Dr. K. Xia! ! ! !6!

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 Phase Transformation - Basic Concepts!
Homogeneous nucleation! free energy change per volume!
a spherical particle of radius r GV = GS GL!
of a solid forms in a liquid! (GS < GL below the melting
GL: free energy per volume of point, i.e. GV is negative)!
liquid! total free energy change!
GS: free energy per volume of 4 A 3rd term
G = r 3GV + 4 r 2 related to
solid! 3 straining may be
: surface free energy per driving barrie present in solid-
force
r force
solid
area of the solid-liquid transformation

interface!
liquid

solid

solid-liquid
interface

MCEN90014: Materials ! ! !Dr. K. Xia! ! ! !7!

Appendix to the previous page!

Atoms with higher energy

G
Liquid

G

Solid

T=TsolidificationTm

undercooling

The yellow atoms are on the surface and Tsolidification

Tm
T
have less bonds compared to those in the
interior (the green ones).

Since bonding reduces the potential energy
of the atoms, the surface atoms (and thus the
surface) have higher energy.

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 Phase Transformation - Basic Concepts!
Total free energy change (G) On the other hand, a particle of
increases with r at r < r* and <r* will shrink and disappear to
decreases with r at r > r*.! reduce free energy. It is thus
A solid particle of >r* will grow not a real nucleus, only an
since an increase in size embryo.!
results in a decrease in free r* is called the critical radius.!
energy. This particle thus is a In order to form a solid particle
nucleus for crystal growth.! of the critical size, r*, a critical
free energy, G*, has to be
provided, usually through
thermal fluctuation.!
r* and G* can be obtained by
G*
letting d(G)/dr = 0!
2
r* =
r*
GV

16 3
G* =
G
3(GV )2

MCEN90014: Materials ! ! !Dr. K. Xia! ! ! !9!

Phase Transformation - Basic Concepts!

At one moment

16 3
G* =
3(GV )2
G*

r*

= Nuclei

2
r* =
GV
= Nuclei

Number of nuclei increases with

decreasing r*, i.e. decreasing T

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 Phase Transformation - Basic Concepts!
The number of solid particles The total nucleation rate (nuclei
with r r* in an undercooled per volume per second)!
liquid is! % G * ( % Q (
% G *( k: Boltzmann's constant
N exp' * exp' a *
n* exp' & kT ) & kT )
*
& kT ) T: absolute temperature

the larger G* the smaller nucleation rate is the highest
at an intermediate temperature

n*!
Transfer
G* also depends on T easier

16 3
G* = although it is implicit here. less
3(GV )2 driving # Q &
In fact, temperature affects force
exp% a (
G* more significantly $ kT '
through GV.!
For a particle of size r* to
become a true nucleus,
additional atoms have to be Transfer
transferred from liquid to solid, more
difficult
$ G * '
a process needing an exp& )
more % kT (
activation energy, Qa.! driving
G* decreases more significantly
force

Self study: Heterogeneous Nucleation
with T than T itself

Rate

MCEN90014: Materials ! ! !Dr. K. Xia! ! ! !11!

Phase Transformation - Basic Concepts!

Growth! Temperature is often Fraction of transformation, y!
the most important
growth rate! how much of the parent phase
and used to induce
$ Q ' and control a phase has been transformed!
G exp& a ) transformation

% kT ( for solid state transformation at
Qa: activation energy (often Avrami a certain temperature!
Qa= Qd for diffusion)! equation
y = 1 exp(kt n )
1
Rate of transformation : r =
t 0.5
Overall transformation rate is the
highest at an intermediate temperature

Time for the
transformation
to proceed to
halfway to
completion

MCEN90014: Materials ! ! !Dr. K. Xia! ! ! !12!

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 Phase Transformation - Basic Concepts!
Summary!
Phases in a given system may
change with external conditions
(most importantly, with
temperature).!
Thermodynamics determines
whether a phase is stable or a
transformation is possible (the
Gibbs free energy is one
measurement used for this
purpose).!
The activation energy, arising from
barriers to transformation,
determines how fast a
transformation would actually take
place.!
MCEN90014: Materials ! !
In many cases, a transformation
starts by nucleation of the new
phase in which a critical size exists
and a critical (activation) energy is
needed.!
The nuclei will grow, often through
diffusion, until the old phase is
replaced. The growth rate is the
highest at some intermediate
temperature.!
The whole phase transformation
takes some time to complete (this
can be very long indeed!).!
!Dr. K. Xia! ! ! !13!