Lecture 16.

Phase Transformation
Learning Objectives
After this lecture, you should be able to do the following:

1. Understand nucleation and growth processes in phase

transformations
2. Understand the kinetics of phase transformations.

Reading

Chapter 10: Phase Diagrams (10.110.4)

Multimedia

Virtual Materials Science & Engineering (VMSE):

http://www.wiley.com/college/callister/CL_EWSTU01031_S/vmse/

MSE 3300 / 5300 UTA Fall 2014

Lecture 16 - 1

Kinetics of Phase Transformation

MSE 3300 / 5300 UTA Fall 2014

Lecture 16 - 2

Thermodynamics of Phase
Transformation

MSE 3300 / 5300 UTA Fall 2014

Lecture 16 - 3

Solidification: Nucleation Types

Homogeneous nucleation
nuclei form in the bulk of liquid metal
requires considerable supercooling
(typically 80-300C)

Heterogeneous nucleation
much easier since stable nucleating surface is
already present e.g., mold wall, impurities in
liquid phase
only very slight supercooling (0.1-10C)

MSE 3300 / 5300 UTA Fall 2014

Lecture 16 - 4

Driving force for solidification

At any temperature below Tm there is a driving force for solidification. The liquid solidify at T
< Tm. If energy is removed quickly, the system can be significantly supercooled (or
undercooled).
MSE 3300 / 5300 UTA Fall 2014

Lecture 16 - 5

Homogeneous Nucleation

MSE 3300 / 5300 UTA Fall 2014

Lecture 16 - 6

Homogeneous Nucleation

MSE 3300 / 5300 UTA Fall 2014

Lecture 16 - 7

Homogeneous Nucleation & Energy Effects

Surface Free Energy- destabilizes
the nuclei (it takes energy to make
an interface)

= surface tension

GT = Total Free Energy

= GS + GV
Volume (Bulk) Free Energy
stabilizes the nuclei (releases energy)

r* = critical nucleus: for r < r* nuclei shrink; for r > r* nuclei grow (to reduce energy)
Adapted from Fig.10.2(b), Callister & Rethwisch 9e.
MSE 3300 / 5300 UTA Fall 2014

Lecture 16 - 8

Homogeneous Nucleation

MSE 3300 / 5300 UTA Fall 2014

Lecture 16 - 9

Solidification
r* = critical radius
= surface free energy
Tm = melting temperature
Hf = latent heat of solidification
T = Tm - T = supercooling

Note: Hf and are weakly dependent on T

r*

decreases as T increases
For typical T

MSE 3300 / 5300 UTA Fall 2014

r* ~ 10 nm

Lecture 16 - 10

Homogeneous Nucleation

Both r* and G* decrease with

increasing supercooling (T).

MSE 3300 / 5300 UTA Fall 2014

Lecture 16 - 11

Rate of Homogeneous Nucleation

MSE 3300 / 5300 UTA Fall 2014

Lecture 16 - 12

Rate of Homogeneous Nucleation

Stable particle

MSE 3300 / 5300 UTA Fall 2014

Lecture 16 - 13

Rate of Homogeneous Nucleation

Nucleation rate [nuclei per unit volume per second]

MSE 3300 / 5300 UTA Fall 2014

Lecture 16 - 14

Heterogeneous Nucleation

MSE 3300 / 5300 UTA Fall 2014

Lecture 16 - 15

Homogeneous Nucleation

MSE 3300 / 5300 UTA Fall 2014

Lecture 16 - 16

Heterogeneous Nucleation

MSE 3300 / 5300 UTA Fall 2014

Lecture 16 - 17

Heterogeneous Nucleation

MSE 3300 / 5300 UTA Fall 2014

Lecture 16 - 18

Heterogeneous Nucleation

MSE 3300 / 5300 UTA Fall 2014

Lecture 16 - 19

Growth
Particle growth occurs by long-range atomic diffusion, which involves
several stepsfor example, diffusion through the parent phase, across a phase
boundary, and then into the nucleus. The growth rate is determined by the rate
of diffusion, and its temperature dependence is the same as for the diffusion
coefficient (Equation 5.8):

MSE 3300 / 5300 UTA Fall 2014

Lecture 16 - 20

Transformation Rate

MSE 3300 / 5300 UTA Fall 2014

Lecture 16 - 21

Kinetics: Rate of Phase

Transformations
Kinetics - study of reaction rates of phase
transformations
To determine reaction rate measure degree
of transformation as function of time (while
holding temp constant)
How is degree of transformation measured?
X-ray diffraction many specimens required
electrical conductivity measurements
on single specimen
measure propagation of sound waves
on single specimen
MSE 3300 / 5300 UTA Fall 2014

Lecture 16 - 22

Fraction transformed, y

Rate of Phase Transformation

transformation complete

Fixed T

0.5

maximum rate reached now amount

unconverted decreases so rate slows
t0.5

rate increases as interfacial surface area

increases & nuclei grow

log t

Avrami equation => y = 1- exp (-kt n)

fraction
transformed

Fig. 10.10,
Callister &
Rethwisch 9e.

time

k & n are transformation specific parameters

By convention
MSE 3300 / 5300 UTA Fall 2014

rate = 1 / t0.5
Lecture 16 - 23

Temperature Dependence of
Transformation Rate
Fig. 10.11, Callister &
Rethwisch 9e.
135C 119C

10

113C 102C

88C

102

43C

104

(Reprinted with permission

from Metallurgical
Transactions, Vol. 188, 1950,
a publication of The
Metallurgical Society of AIME,
Warrendale, PA. Adapted
from B. F. Decker and D.
Harker, Recrystallization in
Rolled Copper, Trans. AIME,
188, 1950, p. 888.)

For the recrystallization of Cu, since

rate = 1/t0.5
rate increases with increasing temperature
Rate often so slow that attainment of equilibrium
state not possible!
MSE 3300 / 5300 UTA Fall 2014

Lecture 16 - 24

Summary
1. Phase transformations: nucleation and growth
2. Kinetics of phase transformations

MSE 3300 / 5300 UTA Fall 2014

Lecture 16 - 25

Homework 8
10.2, 10.4, 10.6, 10.11

* Problems from Callister, 9th Edition

MSE 3300 / 5300 UTA Fall 2014

Lecture 16 - 26