Development of Microstructure and

Alteration of Material Properties

Phase
Transformations

The Kinetics of Phases

Transformations
Most phase transformations do not occur
instantaneously
The progress of a phase transformation can
be divided into two stages:
Nucleation
Growth

The transformation is complete when the

equilibrium fraction is reached.

Phase Transformations
Examples:
Liquid solid alpha,
Liquid eutectic

Liquid Al-30%wtCu
Alpha solid

Eutectic

Phase Transformations
The properties of solid materials are altered
by thermomechanical processing
This involves a combination of
thermal processing - heat treatment
mechanical processing deformation
role if to alter materials microstructure and controls
its properties.

During a heat treatment

the nature and amount of a phase changes,
moving toward an equilibrium state
These processes are time dependent
Understanding the kinetics of a process is important.
6

Variety of Alloy Microstructures

Arrangement
of phases

Concentration
of phase

Amount
of phase

Kinetics of Solid-State Reactions

Most reactions involve nucleation and growth
Nucleation is an incubation process
It requires time

Growth is limited by the diffusion process

It also requires time

Avrami Equation

y 1 exp(kt )
n

fraction transformed

Nucleation
There are 2 types of nucleation:
Homogeneous nucleation
A solid particle begins to form when atoms in
the liquid cluster together growth of the
cluster will continue if the cluster reaches the
critical radius (r*)
A cluster of radius < r* will shrink and
redissolve
A cluster of radius r*, will grow.

Heterogeneous nucleation
Activation energy is lowered when nuclei form
on pre-existing surfaces

G* activation free energy- energy

required for the formation of a stable
nucleus

Free-energy vs. Radius plot for

homo/heterogeneous nucleation

Supercooling
http://www.youtube.com/watch?v=pTdiTe3x0
Bo&feature=related

Forces Controlling Nucleation

and Growth
During an undercooling
process (during which
the temperature drops
below TE)
the available reaction
energy increases
the rate of diffusion
decreases

These are competing

effects
11

-G

TE

Rate is Temperature Dependent

Example: Hypothetical metal changes from FCC to HCP when
it is cooled below 200oC
100

150oC

100oC

190oC

190

80

Temperature (oC)

Fraction Transformed (%)

90

70
60
50
40

150

30

100

20
10
10

100

0
0.1

10

100

Time (s)

Transformation rate:
12

1000

1
Q
r A exp

t0.5
RT

Time for 50% trans.

Thermally-activated
process

If r is too small the system will never reach equilibrium

Metastable versus Equilibrium

States
The speed or rate of the transformation is
often important in the relationship between
the heat treatment and the development of the
microstructure
True equilibrium states are rarely achieved
Supercooling: cooling to below a phase
transition temperature without the occurrence
of the transformation
Superheating: heating to above a transition
temperature without the occurrence of the
transformation

Microstructural and
Property Changes in
Iron-Carbon Alloys

Isothermal Transformation
Diagrams
Eutectoid Transformation:
(0.76wt %C)

cooling

heating

(0.022wt %C) Fe3C(6.7wt %C)

T(C)
1600

1400

1000

austenite

Eutectoid:
600
400
0
(Fe)

L+Fe3C
+Fe3C

Equil. cooling: Ttransf. = 727C

727C
DT
+Fe3C
Undercooling by T
0.77

800

0.022

ferrite

+L

Co, wt% C

Fe3C
cementite
6.7

1200

Adapted from Fig. 9.21,Callister

6e. (Fig. 9.21 adapted from
Binary Alloy Phase Diagrams,
2nd ed., Vol. 1, T.B. Massalski
(Ed.-in-Chief), ASM
International, Materials Park,
OH, 1990.)

Isothermal Transformation
Diagrams
Temperature plays an important role in
austenite-to-pearlite transformation
Data collected
for a specimen
composed of
100% austenite
rapidly cooled to
indicated
temperatures

Isothermal Transformation
Diagrams
Plot of temperature vs.
logarithm of time for a steel
alloy of definite composition
Determine when
transformations begin and
end for an isothermal heat
treatment (constant
temperature) of a previously
austenitized alloy
Also called timetemperature-transformation
(TTT) plots

Pearlite Transformation Rate

The Effect of Undercooling

Example: Growth of pearlite from austenite

Austenite ( )
grain
boundary

cementite (Fe3C)
ferrite ()

Diffusive flow
of C needed

pearlite
growth
direction

Adapted from Fig.

9.13, Callister 6e.

The reaction rate increases

with undercooling (DT)

Adapted from Fig.

10.3, Callister 6e.

18

Austenite - Pearlite
Transformation in the Fe-C System

Eutectoid composition, Co = 0.77 wt% C

Start at T > 727C

Rapidly cool to 625C and hold the material there isothermally

Microstructures
before, during
and after the
austenite-topearlite
transformation

19

Complete Isothermal
Transformation Diagram
A Austenite
B Bainite
M Martensite

New possibilities:
Bainite
Martensite

Complete Isothermal
Transformation Diagram
A Austenite
B Bainite
M Martensite

Martensitic Transformation:
a reaction that is not
thermally activated
Diffusionless
Transformation occurs at
high speed
Independent of time
Reaction depends ONLY on
temperature
Example: martensitic
transformation

Martensite Formation
Austenite (FCC) transforms into martensite (BCT)

Huang et al, Met. Trans A, 43A, OCTOBER 20123517

23

Products of Austenitic Transformations

Microconstituents

Description

Pearlite

Transformation rate increases with decreasing temperature

Coarse pearlite: alternating ferrite and cementite layers are relatively
thick
Fine pearlite: alternating ferrite and cementite layers are relatively thin
Formed between 540 C to 727 C (above the nose)

Bainite

Forms at temperatures between those at which pearlite and martensite

transformation occurs
microstructure consists of -ferrite and fine dispersion of cementite
Formed between 215 C to 540 C (below the nose)

Spheroidite

Steel alloy composed of either pearlitic or bainitic microstructures is heated

and held at a temperature below the eutectoid point for a long time (example:
700 C for 18 24 h)
Sphere-like particles

Martensite

A metastable iron phase supersaturated in carbon that is the product of a

diffusionless transformation from austenite
Quenched to a relatively low temperature

Mechanical Properties of Steels

adapted from fig. 10.20, Callister 6e. see text for references.

As the weight percent of carbon increases

the tensile strength (TS) increases

the yield strength (YS) increases
the percent elongation (%EL) decreases
25

Microconstituent

Phases Present

Arrangement of Phases

Mechanical Properties
(Relative)

Spheroidite

Ferrite + Fe3C

Relatively small Fe3C

sphere-like particles in an ferrite matrix

Soft and ductile

Coarse Pearlite

Ferrite + Fe3C

Alternating layers of -ferrite

and Fe3C that are relatively
thick

Harder and stronger than

spherodite, but not as ductile as
spherodite

Fine Pearlite

Ferrite + Fe3C

Alternating layers of -ferrite

and Fe3C that are relatively thin

Harder and stronger than

coarse pearlite, but not as
ductile as coarse pearlite

Bainite

Ferrite + Fe3C

Very fine and elongated

particles of Fe3C in a -ferrite
matrix

Hardness and strength greater

than fine pearlite; hardness less
than martensite; ductility
greater than martensite

Tempered Martensite

Ferrite + Fe3C

Very small Fe3C sphere-like

particles in an -ferrite matrix

Strong; not as hard as

martensite, but much more
ductile than martensite

Body-centered tetragonal,
single phase

Needle-shaped grains

Very hard and very brittle

Martensite

Suspension Bridge Materials

A roadway hung from
cables made from fine
steel wire woven into a
rope
The maximum span is
related to the
materials strength

http://www.prosoft.force9.co.uk/backgrounds/america/
http://www.goldengate.org/

The Golden Gate Bridge

San Francisco
27

Suspension Bridge Materials

Rio-Antirio: Suspension Bridge

28

(Greece)

Suspension Bridge Materials

See Scientific American,

December 1997

Suspension Bridge Materials

See Scientific American,

December 1997

Chapter 10
Practice Problems

Practice Problems
1. Consider the TTT diagram following this question.
The low carbon steel, initially at 800C, is quickly
cooled to 650C and held there for 30 seconds. The
sample is then quickly cooled to room temperature.
What phase will be present in the final
microstructure?
a) Pearlite (P) and Martensite (M)
b) Pearlite (P), Bainite (B) and Martensite (M)
c) Pearlite (P) only.
d) Pearlite (P), Martensite (M) and Austenite (A).

Practice Problems

Practice Problems

Practice Problems

Practice Problems

Practice Problems
Homogenized
at 800C

Answer:
Pearlite

Held for
30 sec

Martensite

Quenched

Pearlite (P)
and
Martensite
(M) or a)

Practice Problems
2. The kinetics of a certain transformation
obeys the Avrami equation. The n
parameter is known to be 1.05. The
reaction is 50% complete after 105 s.
a) What is the transformation rate (s-1)?
b) How long (in s) will it take for the
transformation to be 97.3% complete?

Practice Problems
Answer:
a) Use the given data to solve for the transformation rate.
1
1
r

9.5 103 / s
t 0.5 105s
b) We begin by using the avramiequation to solve for the constant k.
Set y 0.5 and n 1.05.Solve.
y 1- exp(-ktn )
0.5 1 - exp(-k1051.05 )
0.69314718
3
k

5
.
230903365

10
1051.05

Practice Problems
Next, we solve for the time (in s) for the transformation to be 97.3%
complete.
0.973 1 - exp(5.230903365103 t1.05 )
t 1.05

3.611918413
505.8 s
3
5.23090336510