Chapter 10: What is it about?

This is an equilibrium diagram:

phases present here had all the time they needed to form…
T(°C)
1600
δ
1400 L
γ γ +L
1200
(austenite)
1148°C L+Fe3C

Fe3C (cementite)
1000
γ +Fe
3C
800
α
600
α +Fe3C
400
0 1 2 3 4 5 6 6.7
(Fe)
C, wt% C
Chapter 10 -
 Chapter 10: Phase Transformations

ISSUES TO ADDRESS...
• Transforming one phase into another takes time.

Fe Fe C
3
Eutectoid
γ transformation (cementite)
(Austenite) +
α
C FCC BCC
(ferrite)

• How does the rate of transformation depend on

time and temperature ?
• Is it possible to manage transformations so that
non-equilibrium structures are formed?
• Are the mechanical properties of non-equilibrium
structures more desirable than equilibrium ones?
Chapter 10 - 2
 Phase Transformations
Nucleation
- nuclei (seeds) act as templates on which crystals grow
- for nucleus to form, the rate of addition of
atoms to nucleus must be faster than the
rate of loss. If rate of loss > rate of addition,
the nuclei vanishes

nucleation growth crystal

- once nucleated, growth proceeds until equilibrium is attained

nucleation growth crystal

Chapter 10 - 3
 Phase Transformations
Nucleation

Driving force to nucleate increases as we increase ΔT

– supercooling (eutectic, eutectoid)

Small supercooling

slow nucleation rate

few nuclei
large crystals

Large supercooling

rapid nucleation rate

many nuclei
small crystals

Chapter 10 - 4
 Solidification: Nucleation Types
• Homogeneous nucleation
– nuclei form in the bulk of liquid metal
– requires considerable supercooling
(typically 100-300°C)

higher supercooling lower supercooling

(higher DT) (lower DT)

Chapter 10 - 5
 Solidification: Nucleation Types
• Homogeneous nucleation
– nuclei form in the bulk of liquid metal
– requires considerable supercooling
(typically 100-300°C)
• Heterogeneous nucleation
– much easier since stable “nucleating surface” is already present —
e.g., mold wall, impurities in liquid phase
– only very slight supercooling (0.1-10°C)

higher supercooling lower supercooling

(higher DT) (lower DT)

Chapter 10 - 6
 Homogeneous Nucleation & Energy Effects
Surface Free Energy- destabilizes
the nuclei (it takes energy to make
an interface)
>0 γ = surface tension
ΔGT = Total Free Energy
= ΔGS + ΔGV
For r > r*, dDGT/dr < 0
Volume (Bulk) Free Energy –
stabilizes the nuclei (releases energy)
4 3
DGV = p r DGu < 0
3
volume free energy
DGu =
unit volume

r* = critical nucleus: for r < r* nuclei shrink;

for r > r* nuclei grow (to reduce energy) Chapter 10 - 7
 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 temperature 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

Chapter 10 - 8
 Rate of Phase Transformation
Fraction transformed, y

transformation complete
Fixed T
0.5 maximum rate reached – from now on, the amount
of unconverted phase decreases and the rate slows

rate increases as the interfacial surface

t0.5 area increases & nuclei grow

log t

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

fraction time
transformed
– k & n are transformation specific parameters

By convention rate = 1 / t0.5

Chapter 10 - 9
 Temperature Dependence of Transformation Rate

135C 119C 113C 102C 88C 43C

1 10 102 104

• For the recrystallization of Cu (rate = 1/t0.5)

rate increases with increasing temperature

Rate often so slow that attainment of equilibrium state not possible!

Chapter 10 - 10
 Transformations & Undercooling
Upon crossing a phase boundary on the composition-temperature phase diagram,
phase transformation towards equilibrium state is induced. For instance,

Eutectic transformation: Lα + b A

But the nucleation and growth of the equilibrium structure

(a + b) takes time so that as the system is cooled down
B
the transformation is delayed
Pb Sn
The phase transformations therefore occur at temperatures
lower than predicted by phase diagram: supercooling
(In the same way, during heating, The phase transformations therefore occur at
temperatures higher than predicted by phase diagram: superheating)

The degree of supercooling/superheating increases with the rate of cooling/heating:

The faster the system is cooled, the lower will be the temperature in
which transformation will take pace

Microstructures are strongly affected by the rate of cooling: metastable

states can even be formed due to fast temperature changes.

Example with 10% Sn cooled down from 250 ⁰ to room temperature (A →B)

Chapter 10 - 11
 Transformations & Undercooling

• Eutectoid transf. (Fe-Fe3C system): γ  α + Fe3C

• For transf. to occur, must 0.76 wt% C 6.7 wt% C
cool to below 727 C 0.022 wt% C

T(C)
1600
δ
1400 L
γ γ +L
1200 1148 C L+Fe3C

Fe3C (cementite)
(austenite)
1000
α γ +Fe3C
Eutectoid:
ferrite 800 Equil. Cooling: Ttransf. = 727 C
727 C
α +Fe3C
600
0.022

0.76

400
0 1 2 3 4 5 6 6.7
(Fe) C, wt%C
Chapter 10 - 12
 Transformations & Undercooling

• Eutectoid transf. (Fe-Fe3C system): γ  α + Fe3C

• For transf. to occur, must 0.76 wt% C 6.7 wt% C
cool to below 727 ⁰C 0.022 wt% C

T(⁰C)
1600
δ
1400 L
γ γ +L
1200 1148 C L+Fe3C

Fe3C (cementite)
(austenite)
1000
α γ +Fe3C
Eutectoid:
ferrite 800 Equil. Cooling: Ttransf. = 727 C
727C
ΔT α +Fe3C
600 Undercooling by Ttransf. < 727 C
0.022

0.76

400
0 1 2 3 4 5 6 6.7
(Fe) C, wt%C
Chapter 10 - 13
 The Fe-Fe3C Eutectoid Transformation
Transformation of austenite to pearlite:
C diffusion during transformation

Austenite (γ) cementite (Fe3C) α

grain α Ferrite (α)
α γ
boundary γ γ
γ α α
α pearlite growth
α
α direction α
Carbon
diffusion

100 650 ⁰C

y (% pearlite)
600 ⁰C
the g – pearlite transformation (ΔT
larger)
rate increases with 50
675 ⁰C
ΔT = [T – Teutectoid (727 ⁰C)]. (ΔT
smaller)
0

Chapter 10 - 14
 Back to slide #3… Phase Transformations
Nucleation

Driving force to nucleate increases as we increase ΔT

– supercooling (eutectic, eutectoid)

Small supercooling

slow nucleation rate

few nuclei
large crystals

Large supercooling

rapid nucleation rate

many nuclei
small crystals

Chapter 10 - 15
 The Fe-Fe3C Eutectoid Transformation
Transformation of austenite to pearlite:
C diffusion during transformation

Austenite (γ) cementite (Fe3C) α

grain α Ferrite (α)
α γ
boundary γ γ
γ α α
α pearlite growth
α
α direction α
Carbon
diffusion

100 650 ⁰C

y (% pearlite)
600 ⁰C
the g – pearlite transformation (ΔT
larger)
rate increases with 50
675 ⁰C
ΔT = [T – Teutectoid (727 ⁰C)]. (ΔT
smaller)
0

Coarse pearlite forms at higher temperatures – relatively soft

The a, Fe3C layers thickness depend on the transformation temperature:

10 mm The higher the temperature, the thicker the layers.

Fine pearlite forms at lower temperatures – relatively hard 10 -mm

Chapter 10 16
 Generation of Isothermal Transformation Diagrams
(or Time-Temperature-Transformation, TTT diagrams)
Consider:
• The Fe-Fe3C system, for C0 = 0.76 wt% C
• A transformation temperature of 675 ºC.
% transformed

100
T = 675 ⁰C
y,

50

0
1 10 2 10 4 time (s)
T( ⁰C)
Austenite (stable)
TE (727 ⁰C)
700 Austenite
(unstable)

600 Pearlite

isothermal transformation at 675°C

500

400
time (s)
1 10 10 2 10 3 10 4 10 5 Chapter 10 - 17
Austenite-to-Pearlite Isothermal Transformation
• Eutectoid composition, C0 = 0.76 wt% C
• Begin at 727°C
• Rapidly cool to 625°C
• Hold T (625°C) constant (isothermal treatment)
T(ºC) Austenite (stable)
TE (727 ⁰C)
700 Austenite
(unstable)

600 Pearlite
γ γ
γ γ γ γ
500

400

1 10 10 2 10 3 10 4 10 5
time (s)
Chapter 10 - 18
 Martensite: a highly important microstructure
Let us first consider that austenite dissolves
up to ~2%C while ferrite only dissolves 0.022% max.
Now, what happens if an austenitic structure with
medium to high-carbon is quenched (rapidly cooled)
down to temperatures in which g is not stable?

Due to the fast cooling, the C atoms do not have time to diffuse
out of the FCC g and remain trapped in solid solution. They
thus force the crystal reorganization forming an elongated
body-centered tetragonal phase (BCT) called martensite

iron Thanks to this crystalline distorted structure, martensite

is a very hard phase (thus brittle) yielding steels to be used where
very high-strength is requested
carbon

Martensite is a metastable phase that

does not appear in the phase diagram

Martensite BCT crystal unit

 Martensite Microstructure
• Diffusionless transformation:
g→ a-martensite (very fast)

60 μm
• Needle-like or lath-like appearance
• microstructure almost always contains
retained austenite (the part of austenite that
did not transform into martensite) Martensite needles and laths
Austenite
• microstructural development of martensite
defined by transformation curves as TTT Isothermal Transf. Diagram (TTT curve)
• alloying elements affect the 800 Austenite (stable)
ease of martensite formation T(⁰C) TE
A
P
600
The system must be cooled fast enough to
avoid entering the g -transforming region 400 B
A

0%
200 M+A 50%
% transformation depends only on T M+A 90%
to which the system is rapidly cooled M
10-1 10 103 105 time (s)
 Tempered Martensite
Heat treat martensite to form tempered martensite
(remember martensite is a metastable (non-equilibrium) phase)

tempered martensite less brittle than martensite

TS(MPa)
YS(MPa)
1800

1600 TS
tempering decreases
Tensile strength, Yield strength, 1400 YS
but increases ductility,
here represented by %RA 1200

9 μm
60
(reduction of area)
1000 50
%RA %RA
40
800 30
200 400 600
Tempering T ( ⁰C)

tempering produces small Fe3C particles surrounded by α.

Chapter 10 -
 Bainite: Another Fe-Fe3C Transformation Product
obtained at moderate cooling rates, between pearlite (slow) and martensite (fast)
Bainite:
-- plate-like (elongated) Fe3C particles in α-ferrite matrix formed at temperatures
lower than pearlite
-- diffusion controlled transformation
-- the a-ferrite has a high dislocations density which therefore makes bainite
harder than pearlite
α (ferrite)

TTT Diagram, C0 = 0.76 wt% C

800 Austenite (stable)
T(⁰C) A
TE
P
600 100% pearlite

100% bainite Note that in some TTT diagrams in the literature,

400 B Austenite is referred to as A instead of g.
A P and B refer to Pearlite and Bainite, respectively.

200

10-1 10 103 105

time (s) Chapter 10 - 22
 Spheroidite: Another Microstructure for the Fe-Fe3C System

• Spheroidite: α
(ferrite)
-- Fe3C particles within an α-ferrite matrix
-- formation requires diffusion
Fe3C
(cementite)

Obtained by heating bainite or pearlite at

temperature just below eutectoid 60 μm
for long times
The softest (most ductile) steel
microstructure. We thus proceed to
spheroidization to increase steels formability

Chapter 10 - 23
 Precipitation Hardening
• Particles hinder or impede dislocations movement.
• Things that slow down/hinder/impede dislocation movement
will increase y and TS

• Including other phases - especially very small, well dispersed particles.

In some alloys, we can get small, uniform particles to precipitate out of
(solid) solution. Hence named “precipitation hardening” also known as
"AGE" - hardening. Examples include:
✓ Al-Cu
✓ Cu-Be
✓ Cu-S
✓ Mg-Al
✓ Some alloy and stainless steels

• Many Al-alloys are precipitation hardenable

• Al - Cu is best known alloy, e.g. Al - 4%Cu
 Precipitation Hardening
We consider a A + B binary alloy with C0 wt% of B, microstructure a + b at room T
Procedure:
• Heat to To and hold until only a - phase
present.
•Quench (rapid cooling) to T1
because no diffusion has time to occur,
B atoms remain “trapped” in a:
A super-saturated solid solution (SSSS) of
a forms. Not thermodynamically stable.
•Reheat to T2 where diffusion can occur
and small precipitates of b-phase form.
M = Max. solubility of
metal B in metal A.
Solid solubility decreases
to N as T

0
Summary of Possible Transformations
Austenite (γ)

slow moderate rapid

cool cool quench

Pearlite Bainite Martensite

(α + Fe3C layers + a (α + elong. Fe3C particles) (BCT phase
proeutectoid phase) diffusionless
transformation)

Martensite reheat
T Martensite
Strength

Ductility
bainite Tempered
fine pearlite Martensite
coarse pearlite (α + very fine
spheroidite Fe3C particles)

General Trends
Chapter 10 - 26
 Isothermal Heat Treatment Example
Problems
On the isothermal transformation diagram for a 0.76 wt% C, Fe-C
alloy, sketch and label the time-temperature paths to produce the
following microstructures:
a) 100% martensite
b) coarse pearlite
c) 50% fine pearlite and 50% bainite

Chapter 10 - 27
 Solutions to Part (a) Example Problem
a) 100% martensite

Chapter 10 - 28
 Solution to Part (b) of Example
Problem
b) coarse pearlite

Chapter 10 - 29
 Solution to Part (c) of Example
Problem
c) 50% fine pearlite and 50% bainite

Chapter 10 - 30