TOPIC 10:

PHASE TRANSFORMATIONS

• Transforming one phase into another takes time.

• How does the rate of transformation depend on
time and T?
• How can we control the transformation so that
we can engineering non-equilibrium structures?
• How different are the mechanical properties of
non-equilibrium structures?
IMPORTANCE OF COOLING TIME
Cu-Ni alloy

Fast cooling Slow cooling

Non-equilibrium phases Equilibrium phases

Uniform Cα:
First α to solidfy:
46wt%Ni 35wt%Ni
Last α to solidfy:
< 35wt%Ni
 COOLING AUSTENITE
Austenite

Pearlite

• Mainly interested in eutectoid cooling: γ α + Fe3C (pearlite), 0.77 wt% C

• Cooling rate can result in a wide variety of phases and microstructures
– Equilibrium phases: pearlite, bainite
– Non-equilibrium phases: martensite
 MECHANICAL PROPERTIES

• Martensite
• Tempered martensite

Ductility
Strength

• Bainite
• Fine pearlite
• Coarse pearlite

• Can control the formation of specific phases and

microstructure so that desired properties result
 FRACTION OF TRANSFORMATION
• Fraction transformed depends on time,
at constant temperature (e.g., γ pearlite)

− kt n
y = 1− e
Avrami equation
(k, n are constants)
• Transformation rate , r = 1/t0.5
EUTECTOID TRANSFORMATION RATE ~ ∆T
• Growth of pearlite from austenite:

• Reaction rate increases with ∆T.

TIME-TEMPERATURE TRANSFORMATION
(TTT) DIAGRAMS
• Fe-C system, Eutectoid composition (Co = 0.77wt%C)
• Transformation at T = 675C.

Also called
isothermal
transformation
diagram
EX: COOLING HISTORY Fe-C SYSTEM
• Eutectoid composition, Co = 0.77wt%C
• Begin at T > 727C
• Rapidly cool to 625C and hold isothermally.
• Cooling to lower temperatures results in finer microstructures
 PEARLITE MORPHOLOGY
Two cases:
• Ttransf just below TE
--Larger T: diffusion is faster
--Pearlite is coarser.
• Ttransf well below TE
--Smaller T: diffusion is slower
--Pearlite is finer.

- Smaller ∆T: - Larger ∆T:

colonies are colonies are
larger smaller
 OTHER TRANSFORMATION PRODUCTS
• Bainite:
--α strips with long, fine
rods of Fe3C
Fe3C
• Isothermal Transf. Diagram (cementite)
α (ferrite)

5 µm
(Adapted from Fig. 10.8, Callister, 6e. (Fig.
10.8 from Metals Handbook, 8th ed.,
Vol. 8, Metallography, Structures, and
Phase Diagrams, American Society for
Metals, Materials Park, OH, 1973.)

Note: reaction rate

increases with decreasing
temperature first, and then
decreases
 NUCLEATION AND GROWTH
• Reaction rate is a result of nucleation and growth
of crystals.
Nucleation rate increases with ∆T
Growth rate increases with T

• Examples:
pearlite
γ colony γ γ

T just below TE T moderately below TE T way below TE

Nucleation rate low Nucleation rate med . Nucleation rate high
Growth rate high Growth rate med. Growth rate low
 OTHER PRODUCTS: MARTENSITE
• Martensite:
--rapid cooling from above eutectoid temperature to room T
--γ(FCC) to Martensite (Body Centered Tetragonal)
--involves collective motion of a lot of atoms

• Isothermal Transf. Diagram

• γ to M transformation..
-- is rapid! At speed of sound
-- % transf. depends on T only.
 OTHER PRODUCTS: Fe-C SYSTEM (2)
• Martensite:
--γ(FCC) to Martensite (BCT)
(involves single atom jumps)

µm
x
Fe atom potential

60 µ
x x
sites x x C atom sites
x (Adapted from Fig.
10.11, Callister, 6e.

• Isothermal Transf. Diagram

800 Austenite (stable) Martentite needles
T(°C) A TE Austenite
P (Adapted from Fig. 10.12, Callister,
600 6e. (Fig. 10.12 courtesy United
S States Steel Corporation.)
Adapted
from Fig. B
10.13, 400 A
10
• γ to M transformation..
Callister 6e. 0% -- is rapid!
0%
50

0% -- % transf. depends on T only.

%

200 M+A 50%

M+A 90%
M+A
10-1 10 103 105 time (s)
11
 PRODUCTS OF COOLING AUSTENITE

• Slow cooling pearlite

• Cool rapidly to upto 550
C, and hold pearlite
• Cool rapidly to 550-225
C and hold bainite
• Cool rapidly to below
225 C martensite
 COOLING EX: Fe-C SYSTEM (1)

Rapidly cool to 350 C

Hold for 10000 seconds
Rapidly cool to room T

100% Bainite
100% Austenite

100% Bainite
 COOLING EX: Fe-C SYSTEM (2)

Rapidly cool to 250 C

Hold for 100 seconds
Rapidly cool to room T

100% Austenite
100% Austenite

Mostly Martensite + traces of Austenite

 COOLING EX: Fe-C SYSTEM (3)
Rapidly cool to 650 C
Hold for 20 seconds
50% Austenite,
Rapidly cool to 400 C
100% Austenite 50% Pearlite Hold for 1000 seconds
Rapidly cool to room T

50% Austenite, 50% Bainite, 50% Pearlite

50% Pearlite

50% Bainite, 50% Pearlite

OTHER PRODUCTS: Fe-C SYSTEM (1)
• Spheroidite:
--α crystals with spherical Fe3C α
--diffusion dependent. (ferrite)
--heat bainite or pearlite for long times
--reduces interfacial area (driving force) Fe3C
• Isothermal Transf. Diagram (cementite)
800 Austenite (stable)
T(°C) A TE
P
600 100% spheroidite 60 µm
Spheroidite (Adapted from Fig. 10.10, Callister,
6e. (Fig. 10.10 copyright United
100% spheroidite States Steel Corporation, 1971.)
400 A B
Adapted from Fig. 10.9,Callister 6e.
(Fig. 10.9 adapted from H. Boyer (Ed.) Atlas of
Isothermal Transformation and Cooling
Transformation Diagrams, American Society for
200
10
0%

Metals, 1997, p. 28.)

50

0%
%

10-1 10 103 105 time (s)

10
 TEMPERING MARTENSITE
• reduces brittleness of martensite,
• reduces internal stress caused by quenching.
TS(MPa)
YS(MPa)
1800

1600 TS
Adapted from Adapted from
YS

9 µm
Fig. 10.25, 1400 Fig. 10.24,
Callister 6e. Callister 6e.
(Fig. 10.25 (Fig. 10.24
adapted from
1200 60 copyright by
Fig. furnished United States
courtesy of 1000 50 Steel
%AR %AR
Republic Steel 40 Corporation,
Corporation.) 800 1971.)
30
200 400 600
Tempering T (°C)
• produces extremely small Fe3C particles surrounded by α.
• decreases TS, YS but increases %AR
18
 MECHANICAL PROPERTIES

• Martensite
• Tempered martensite

Ductility
Strength

• Bainite
• Fine pearlite
• Coarse pearlite
• Spheroidite

• Can control the formation of specific phases and

microstructure through a cooling schedule
so that desired properties result
HYPOEUTECTOID & HYPEREUTECTOID

• Eutectoid (0.77 wt% C)

Austenite
pearlite (ferrite & cementite
layers)
• Hypoeutectoid (< 0.77 wt%
C) pearlite & ferrite
• Hypereutectoid (> 0.77 wt%
C) pearlite & cementite
• Ferrite is soft and cementite
is hard
Pearlite
• Thus, hardness and strength
increase with carbon content
HYPEReutectiod Steel TTT Curve
Alloy Steel TTT Curve
Continuous Cooling Transformation (CCT)
Continuous Cooling Transformation (CCT)
Continuous Cooling Transformation (CCT)
MECHANICAL PROP: Fe-C SYSTEM (1)
MECHANICAL PROP: Fe-C SYSTEM (2)
• Fine Pearlite vs Martensite:

• Hardness: fine pearlite << martensite.

• Tempering martensite (holding at high temperature)
reduces brittleness and residual stresses
SUMMARY: PROCESSING OPTIONS
Adapted from
Austenite (γ) Fig. 10.27,
Callister 6e.

slow moderate rapid

cool cool quench

Pearlite Bainite Martensite

(α + Fe3C layers + a (α + Fe3C plates/needles) (BCT phase
proeutectoid phase) diffusionless
transformation)

Martensite reheat
T Martensite
Strength

bainite Ductility Tempered

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

General Trends 19
 Spheroidite AS: Alloy Steel
PCS: Plain-carbon Steel

Austenite
Rapid
Quench
Martensite

Slow
Re-
Re-heat Cooling

Moderate cooling (AS)

Isothermal treatment (PCS)

Re-
Re-heat Tempered
Martensite

coarse fine
Pearlite
Bainite
 PRECIPITATION HARDENING
• Particles impede dislocations.
700
• Ex: Al-Cu system
T(°C) L CuAl2
• Procedure:
--Pt A: solution heat treat
600
α α+L
θ+L
(get α solid solution) 500
A
θ
--Pt B: quench to room temp. 400 C α+θ
--Pt C: reheat to nucleate
small θ crystals within 300
0 B 10 20 30 40 50
α crystals. (Al) wt%Cu
composition range
• Other precipitation needed for precipitation hardening
systems: Adapted from Fig. 11.22, Callister 6e. (Fig. 11.22 adapted
• Cu-Be Temp. from J.L. Murray, International Metals Review 30,
30 p.5, 1985.)
Pt A (sol’n heat treat)
• Cu-Sn
• Mg-Al
Pt C (precipitate θ)

Adapted from Fig.

11.20, Callister 6e. Time
Pt B
16
 PRECIPITATION HARDENING

T0

T2

• Two stage heat treatment. Procedure:

--T0: solution heat treatment
(get single phase solid solution)
--Quench to T1.
--T2: reheat to nucleate precipitates
PRECIPITATION HARDENING
PRECIPITATION HARDENING
 PRECIPITATE EFFECT ON TS, %EL
• 2014 Al Alloy:
• TS peaks with • %EL reaches minimum
precipitation time. with precipitation time.
• Increasing T accelerates

ipi mall
process.

“a tates
ion

d”
pr ny s
so l.

ge

ra itate ge
lut
lid ui
tensile strength (MPa)

d” s
“o ecip lar
so n-eq

ec
30
ma

%EL (2in sample)

pr wer
no

ge
500
fe 20

ve
400
149°C
10
300 204°C 204°C 149°C

200 0
1min 1h 1day 1mo 1yr 1min 1h 1day 1mo 1yr
precipitation heat treat time (h) precipitation heat treat time (h)
Adapted from Fig. 11.25 (a) and (b), Callister 6e. (Fig. 11.25 adapted from Metals Handbook:
Properties and Selection: Nonferrous Alloys and Pure Metals, Vol. 2, 9th ed., H. Baker 17
(Managing Ed.), American Society for Metals, 1979. p. 41.)