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
Non-equilibrium phases

First to solidfy:
46wt%Ni
Last to solidfy:
< 35wt%Ni

Slow cooling
Equilibrium phases
Uniform C:
35wt%Ni

COOLING AUSTENITE
Austenite

Pearlite

Mainly interested in eutectoid cooling: + 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

Martensite
Tempered martensite
Bainite
Fine pearlite
Coarse pearlite

Ductility

Strength

MECHANICAL PROPERTIES

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., pearlite)

y 1 e

kt n

Avramiequation
(k,nareconstants)
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.

- Smaller T:
colonies are
larger

Ttransf well below TE

--Smaller T: diffusion is
slower
--Pearlite is finer.

- Larger T:
colonies are
smaller

OTHER TRANSFORMATION PRODUCTS

Bainite:
-- strips with long, fine
rods of Fe3C

Isothermal Transf. Diagram

Fe 3C
(cementite)

(ferrite)

5 m

(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
colony

T just below TE

Nucleation rate low

T moderately belowTE
Nucleation rate med

Growth rate high

Growth rate med.

T way below TE
Nucleation rate high
Growth rate low

OTHER PRODUCTS: MARTENSITE

Martensite:
--rapid cooling from above eutectoid temperature to
room T
--(FCC) to Martensite (Body Centered Tetragonal)
--involves collective motion of a lot of atoms

Isothermal Transf. Diagram

to M transformation..

-- is rapid! At speed of sound

-- % transf. depends on T
only.

OTHER PRODUCTS: Fe-C SYSTEM (2)

Martensite:
--(FCC) to Martensite (BCT)
Fe atom
sites
x

x
x

potential
C atom sites

x
x
x

(Adapted from Fig.

10.11, Callister, 6e.

60 m

(involves single atom jumps)

Isothermal Transf. Diagram

800

T(C)

Austenite (stable)

600
Adapted
from Fig.
10.13,
Callister 6e.

400

Martentite needles
Austenite

TE

(Adapted from Fig. 10.12,

Callister, 6e. (Fig. 10.12 courtesy
United States Steel Corporation.)

S
A

200

M+A
M+A
M+A
10
10-1
103

to M transformation..
0%
50%
90%

105

-- is rapid!
-- % transf. depends on T
only.

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

MostlyMartensite+tracesofAustenite

COOLING EX: Fe-C SYSTEM (3)

100%Austenite

50%Austenite,
50%Pearlite

Rapidly cool to 650 C

Hold for 20 seconds
Rapidly cool to 400 C
Hold for 1000 seconds
Rapidly cool to room T

50%Bainite,50%Pearlite

50%Austenite,
50%Pearlite

50%Bainite,50%Pearlite

OTHER PRODUCTS: Fe-C SYSTEM (1)

Spheroidite:
-- crystals with spherical Fe3C
--diffusion dependent.
--heat bainite or pearlite for long
times
--reduces interfacial area (driving
force)
800

(ferrite)
Fe 3C
(cementite)

Austenite (stable)

Isothermal Transf. Diagram

TE
T(C) A
P

600

400

100% spheroidite

Spheroidite

(Adapted from Fig. 10.10,

Callister, 6e. (Fig. 10.10 copyright
100% spheroidite
United States Steel Corporation,
1971.)
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
Metals, 1997, p. 28.)

200
10-1

10

60 m

103

105 time

(s)
10

TEMPERING MARTENSITE
reduces brittleness of martensite,
reduces internal stress caused by quenching.
TS(MPa)
YS(MPa)
1800
Adapted from
Fig. 10.25, 1400
Callister 6e.
(Fig. 10.25
1200
adapted from
Fig. furnished
courtesy of 1000
Republic Steel
Corporation.) 800

200

TS
YS
60

9 m

1600

50
%AR
40
30

%AR

400

Adapted from
Fig. 10.24,
Callister 6e.
(Fig. 10.24
copyright by
United States
Steel
Corporation,
1971.)

600

Tempering T (C)

produces extremely smallFe 3C particles surrounded by

decreases TS, YS but increases %AR

18

Martensite
Tempered martensite
Bainite
Fine pearlite
Coarse pearlite
Spheroidite

Ductility

Strength

MECHANICAL PROPERTIES

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)
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
Thus, hardness and strength
increase with carbon content

Austenite

Pearlite

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

SUMMARY: PROCESSING OPTIONS

Austenite ()
moderate
cool

slow
cool
Pearlite

Bainite

Martensite
T Martensite
bainite
fine pearlite
coarse pearlite
spheroidite

D u c tility

S tre n g th

( + Fe3C layers + a ( + Fe3C plates/needles)

proeutectoid phase)

General Trends

Adapted from
Fig. 10.27,
Callister 6e.

rapid
quench
Martensite
(BCT phase

diffusionless
transformation)

reheat
Tempered
Martensite

( + very fine
Fe 3C particles)
19

Spheroidite

Austenite

AS: Alloy Steel

PCS: Plain-carbon Steel

Rapid
Quench

Martensite

Slow
Cooling

Re-heat

Moderate cooling (AS)

Isothermal treatment (PCS)

Re-heat

coarse

Pearlite

fine

Bainite

Tempered
Martensite

PRECIPITATION HARDENING
Particles impede dislocations.
700
Ex: Al-Cu system
T(C)
Procedure:
600
+L
--Pt A: solution heat treat
A
500
(get solid solution)
--Pt B: quench to room temp.
400 C
--Pt C: reheat to nucleate
small crystals within
300
0 10
crystals.
(Al) B

+L

20

30

40

CuAl 2

50

wt%Cu

composition range
needed for precipitation hardening

Other precipitation
systems:
Cu-Be
Cu-Sn
Mg-Al

Temp.
Pt A (soln heat

Adapted from Fig. 11.22, Callister 6e. (Fig. 11.22 adapted

from J.L. Murray, International Metals Review 30, p.5,
1985.)
treat)

Pt C (precipitate )

Adapted from Fig.

11.20, Callister 6e.

Pt B

Time
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:
%EL reaches minimum
with precipitation time.

500
400
300

149C
204C

200

% E L (2 in s a m p le )

tensile strength (M Pa)

TS peaks with
precipitation time.
Increasing T
accelerates
process.

1min
1h 1day 1mo1yr
precipitation heat treat time (h)

30
20
10

204C

1min
1h 1day 1mo1yr
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 (Managing Ed.), American Society for Metals, 1979. p. 41.)

149C

17