CHAPTER 9

PHASE
TRANSFORMATION
ISSUE TO ADDRESS
• Transforming one phase into another takes time.

Fe Fe 3 C
 Eutectoid
transformation (cementite)
(Austenite) +
C

FCC (BCC)
(ferrite)

• How does the rate of transformation depend on

time and T?
• How can we slow down the transformation so that
we can engineering non-equilibrium structures?
• Are the mechanical properties of non-equilibrium
structures better?
 INTRO cont...

Iron carbide system

In their simplest form, steels are alloys of Iron (Fe) and Carbon (C). The Fe-C phase diagram is a fairly
complex one, but we will only consider the steel part of the diagram, up to around 7% Carbon.
 INTRO cont...

Figure 1: shows the equilibrium diagram for combinations of carbon in a solid solution of iron. The
diagram shows iron and carbons combined to form Fe-Fe3C at the 6.67%C end of the diagram
PHASE TRANSFORMATION
o Phase transformation can be devided into 3 category

Diffusion-dependent with no change in phase

composition or number of phases present (e.g.
melting, solidification of pure metal, allotropic
transformations, recrystallization, etc.)

Diffusion-dependent with changes in phase

compositions and/or number of phases (e.g. eutectoid
transformations)

Diffusionless phase transformation - produces a

metastable phase by cooperative small displacements of
all atoms in structure (e.g. martensitic transformation
discussed in later in this chapter)
 Phase transformation cont..

Transformation and undercooling

• Eutectoid transf. (Fe-C System):     Fe 3 C
• Can make it occur at: 0.77wt%C 6.7 wt%C
...727ºC (cool it slowly) 0.022wt%C
...below 727ºC (“undercool” it!)
T(°C)
1600

1400 L
+L
1200  L+Fe 3 C
austenite
1000
 Eutectoid: +Fe 3 C
ferrite
+

800 Equil. cooling: T transf. = 727ºC Fe 3 C

727°C


T +Fe 3 C cementite
6 00 Undercooling by T: T transf. < 727ºC
0.022

0.77

4 00
6.7
0 1 2 3 4 5 6
(Fe) C o , wt% C
 Phase transformation cont..

Eutectoid transformation rate

• Growth of pearlite from austenite:
Diffusive flow
of C needed
Austenite ( ) cementite (Fe 3 C)
grain  ferrite () 
boundary 

  

 pearlite 

 growth
direction 

• Reaction rate 10 0 0

y (% pearlite)
600°C

% austenite
increases with (T larger)
650°C
50 50
T. 675°C
(T smaller)
0 10 0
1 10 10 2 10 3
time (s)
 Phase transformation cont..

Pearlite Morphology
• Ttransf just below TE • Ttransf well below TE
--Larger T: diffusion is faster --Smaller T: diffusion is slower
--Pearlite is coarser. --Pearlite is finer.

10 m
- Smaller T: - Larger T:
colonies are colonies are
larger smaller
Pearlite Morphology

- temperature plays an important role in the rate of the

austenite- to- pearlite transformation

- The temperature dependence for an iron- carbon alloy of

eutectoid composition is indicated in Figure A, which plots S-
shaped curves of the percentage transformation versus the
logarithm of time at three different temperatures.
Figure A:
For an iron- carbon
alloy of eutectoid composition
(0.76 wt% C), isothermal
fraction reacted versus the
logarithm of time for the
austenite-to-pearlite
transformation.
 A more convenient way- representing both
the time & temperature dependence of
this transformation is in the bottom
portion (Fig.B)

 Two solid curves;

1. represents the time required at each
temp. for the initiation (start of
transformation)
2. transformation conclusion

 Dashed curve;
- 50% of transformation completion

 These curves were generated from a

series of plots of the percentage
tranformation versus the logarithm of
time taken over a range of temperatures
 Isothermal transformation diagram
 Also called as time- temperature- transformation
(T-T-T) plots.

 The family of S-shaped curves at different T are

used to construct the TTT diagrams.

 The TTT diagrams are for the isothermal (constant

T) transformations (material is cooled quickly to a
given temperature before the transformation occurs,
and then keep it at that temperature).
The thickness of the ferrite and cementite layers in pearlite is ~ 8:1.
The absolute layer thickness depends on the temperature of the
transformation. The higher the temperature, the thicker the layers.
 Near- vertical line AB; very rapid cooling of austenite to a
temperature indicated

 Horizontal segment- BCD; isothermal treatment at this

temperature

 Point C; transformation of austenite to pearlite begins

 Point D; transformation completed

 Slow diffusion at low temperatures leads to fine-grained

microstructure with thin-layered structure of pearlite (fine
pearlite)

 At higher temperatures, high diffusion rates allow for larger grain

growth and formation of thick layered structure of pearlite (coarse
pearlite).
 Phase transformation cont..

Isothermal transformation diagram

(T-T-T diagram)
• Fe-C system, Co = 0.77wt%C
• Transformation at T = 675C.
1 00
% transformed

T=675°C
y,

50

0
1 10 2 10 4 time (s)
T(°C) Austenite (stable)
TE (727°C)
7 00 Austenite
(unstable) isothermal transformation at 675°C
6 00 Pearlite
100

5 00
5 0%pearlit
0%

400
time (s)
e

1 10 10 2 10 3 10 4 10 5
 Phase transformation cont..

Ex: Cooling history

• Eutectoid composition, Co = 0.77wt%C
• Begin at T > 727C
• Rapidly cool to 625C and hold isothermally.
T(°C)
Austenite (stable)
TE (727°C)
7 00

Pearlite
6 00
  
   
0%

100
5 0%

5 00
pea

%
rlite

1 10 10 2 10 3 10 4 10 5 time (s)
 Bainite Morphology
 Is a product of the austenitic transformation, besides
pearlite, and consist of ferrite and cementite phases

 Forms as a needles or plates, depending on the

temperature of the transformation

 In the bainite region, transformation rate is controlled

by microstructure growth (diffusion) rather than
nucleation. Since diffusion is slow at low temperatures,
this phase has a very fine (microscopic) microstructure.

 Pearlite and bainite transformations are competitive;

transformation between pearlite and bainite not possible
without first reheating to form austenite
 Phase transformation cont..

Bainite Morphology
• Bainite:
-- lathes (strips) with long
rods of Fe3C
Fe 3 C
--diffusion controlled.
(cementite)
• Isothermal Transf. Diagram (ferrite)
8 00 Austenite (stable)
T(°C) A
TE
P
6 00 100% pearlite
pearlite/bainite boundary 5 m
100% bainite
4 00 A B

2 00
100
0%

5 0%

10 -1 10 10 3 10 5
time (s)
 For T ~ 300-540°C,
300-540°C upper bainite consists of needles of ferrite separated by long
cementite particles

 For T ~ 200-300°C,
200-300°C lower bainite consists of thin plates of ferrite

 containing very fine rods or blades of cementite
 Phase transformation cont..

Spheroidite Morphology
• Spheroidite:
-- crystals with spherical Fe3C 
--diffusion dependent. (ferrite)
--heat bainite or pearlite for long times
--reduces interfacial area (driving force) Fe 3 C
• Isothermal Transf. Diagram (cementite)
8 00 Austenite (stable)
T(°C) A TE
P
6 00 100% spheroidite 60 m
Spheroidite
100% spheroidite
4 00 A B

2 00
100
0%

5 0%

10 -1 10 10 3 10 5 time (s)
 Phase transformation cont..

Martensite Morphology
• Martensite:
--(FCC) to Martensite (BCT)
(involves single atom jumps)
x

60 m
Fe atom potential
x x
sites x x C atom sites
x

• Isothermal Transf. Diagram

8 00 Austenite (stable) Martentite needles
T(°C) A
TE Austenite
P
6 00
S

4 00 A B
10
0%
0%
50

0%
%

2 00 M +A 50%
M +A 9 0%
M +A
10 -1 10 10 3 10 5 time (s)
 Phase transformation cont..

Ex: Cooling Fe- C system I

• C o = C eutectoid Rapid Hold Rapid Hold Rapid
• Three histories... cool to: for: cool to: for: cool to:

350°C 10 4 s Troom 10 4 s Troom

Case I 250°C 10 2 s Troom 10 2 s Troom
8 00 Austenite (stable)
T(°C)
650°C 20s 400°C 10 3 s Troom
A
P
6 00
S
A B
4 00
100%A 10 100%B
0%
0%
50

0%
%

2 00 M+A 50%
M+A 9 0%
M+A
100% Bainite
10 -1 10 10 3 10 5 time (s)
 Phase transformation cont..

Ex: Cooling Fe- C system II

• C o = C eutectoid Rapid Hold Rapid Hold Rapid
• Three histories... cool to: for: cool to: for: cool to:

350°C 10 4 s Troom 10 4 s Troom

Case II 250°C 10 2 s Troom 10 2 s Troom
8 00 Austenite (stable)
650°C 20s 400°C 10 3 s Troom
T(°C) A
P
6 00
S
A B
4 00
0% 10
0%
100%A
50

0%
%

2 00 M+A
M+A 50%
9 0%
M+A M + trace of A
10 -1 10 10 3 10 5 time (s)
 Phase transformation cont..

Ex: Cooling Fe- C system III

• C o = C eutectoid Rapid Hold Rapid Hold Rapid
• Three histories... cool to: for: cool to: for: cool to:

350°C 10 4 s Troom 10 4 s Troom

Case III 250°C 10 2 s Troom 10 2 s Troom
8 00 Austenite (stable)
T(°C) 650°C 20s 400°C 10 3 s Troom
A
10 0%A 50%P, 50%A
6 00 P
S
A B
4 00 50%P, 50%B
50%P, 50%A 10
0%
0%
50

0%
%

2 00 M+A 50%
M+A 9 0%
M+A 50
10 -1 10 10 3% P, 10 5 time (s)
50
%B
 Phase transformation cont..

Mechanical Properties Fe-C (I)

• Effect of wt%C Pearlite (med)
Pearlite (med) Cementite
ferrite (soft) (hard)
C o <0.77wt%C C o >0.77wt%C
Hypo eutectoid Hyper eutectoid

TS(MPa)
Hypo Hyper Hypo Hyper
11 00 %EL 80
YS(MPa) 1 00

Impact energy (Izod, ft-lb)

9 00
hardness
40
7 00
50
5 00
0
300
0
0 0.5 1 0 0.5 1
0.77

0.77
wt%C wt%C
• More wt%C: TS and YS increase , %EL decreases.
 Phase transformation cont..

Mechanical Properties Fe-C (II)

• Fine vs coarse pearlite vs spheroidite
Hypo Hyper 90 Hypo Hyper
320
fine

Ductility (%AR)
spheroidite
pearlite 60
Brinell hardness

240 coarse
pearlite
spheroidite
160 30 coarse
pearlite
fine
80 pearlite
0
0 0.5 1 0 0.5 1
wt%C wt%C
• Hardness : fine > coarse > spheroidite
• %AR: fine < coarse < spheroidite
 Phase transformation cont..

Mechanical Properties Fe-C (III)

• Fine Pearlite vs Martensite:
Hypo Hyper

6 00
martensite
Brinell hardness

Adapted from Fig. 10.23, Callister

6e. (Fig. 10.23 adapted from Edgar
4 00 C. Bain, Functions of the Alloying
Elements in Steel, American Society
for Metals, 1939, p. 36; and R.A.
Grange, C.R. Hribal, and L.F.
2 00 Porter, Metall. Trans. A, Vol. 8A, p.
fine pearlite 1776.)

0
0 0.5 1
wt%C
• Hardness: fine pearlite << martensite.
 Phase transformation cont..

Tempering Martensite
• reduces brittleness of martensite,
• reduces internal stress caused by quenching.
TS(MPa)
YS(MPa)
180 0

160 0 TS
Adapted from Fig.
140 0
10.25, Callister 6e.
YS

9 m
(Fig. 10.25
adapted from Fig.
120 0 60
furnished courtesy
of Republic Steel
Corporation.) 100 0 50
%AR %AR
40
8 00
30
2 00 4 00 600
Tempering T (°C)
• produces extremely small Fe 3 C particles surrounded by 
• decreases TS, YS but increases %AR
 Phase transformation cont..

Summary
Austenite ( )

slow moderate rapid

cool cool quench

Pearlite Bainite Martensite

( + Fe 3 C layers + a ( + Fe 3 C plates/needles) (BCT phase
proeutectoid phase) diffusionless
transformation)

Martensite reheat
T Martensite Ductility
Strength

bainite Tempered
fine pearlite Martensite
coarse pearlite ( + very fine
spheroidite Fe 3 C particles)

General Trends