Lecture 5-6

Phase Transformations
& TTT Diagrams

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 Outline
• Phase transformations
- Diffusive transformation
- Displacive transformation
• Rate of transformation
• Time-Temperature Transformation (TTT) diagrams
• Mechanical properties of non-equilibrium structures

Fe Fe C
g Eutectoid 3
transformation (cementite)
(Austenite) +
a
C FCC (BCC)
(ferrite)

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 Phase diagram
• Equilibrium Phase of alloy
• At point B, L, α and CuAl2
3 phases coexist since
phase transformation
occurs
A B C • BUT, strengthening is often
about creating
METASTABLE phases
(non-equilibrium)

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 Phase transformations
• Phase transformations include both diffusive transformation and
displacive transformation.
• Diffusive transformations require the diffusion of atoms (molecules)
through the materials
• Two types of diffusive transformations:
➢ Maintaining the type and number of phases: e.g., solidification, allotropic
transformation, recrystallization, grain growth.
➢ Alteration of phase composition: e.g., eutectoid reactions
• Most structural changes occurs by diffusive transformation.
• Overall, diffusive transformation rate is a function of temperature (semi-
schematic).
• Typical diffusive transformation bcc bcc fcc fcc
stable α-Fe
stable bcc
stable γ-Fe fcc
stable
example: f.c.c.(γ-Fe ) → b.c.c.(α-Fe) stable stable
transformation in iron:

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 Nucleations
• Phase transformations realized via nucleation in solids.
• Nucleation
– nuclei (seeds) act as templates on which crystals grow
– The formation rate of additional atoms to nucleus must be
faster than rate of loss
– once nucleated, growth proceeds until equilibrium is attained
• Driving force to nucleate: temperature changes
– supercooling (eutectic, eutectoid)
– superheating (peritectic)

• Small supercooling → slow nucleation rate → large crystals

• Large supercooling → rapid nucleation rate → small crystals
• Heterogeneous nucleation and Homogeneous
nucleation are two main types of nucleation in solids.
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 Solidification: Nucleation types
• Homogeneous nucleation
– nuclei form in the bulk of liquid metal
– requires considerable supercooling (typically 80-300°C)
– occur in defect-free regions
• Heterogeneous nucleation
– much easier since stable “nucleating surface” is already
present — e.g., mold wall, impurities in liquid phase
– only very slight supercooling (0.1-10ºC)
– Occur at defects like dislocations, grain boundaries,
interface phases and free surfaces

Heterogeneous Homogeneous
nucleation nucleation

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 Homogeneous nucleation & energy effects
Surface Free Energy- destabilizes
the nuclei (it takes energy to make
an interface)
DGS = 4r 2g (2)
g = average surface free energy
r = nucleus radius

DGT = Total Free Energy

= DGS + DGV (1)
Volume (Bulk) Free Energy –
stabilizes the nuclei (releases energy)
4
DGV = pr 3 DGu (3)
3
Aver. Vol. DG = volume free energy
u
free energy unit volume
r* = critical nucleus radius: for r < r* nuclei shrink; for r >r* nuclei grow (to reduce energy)
r* is the nucleus radius that can achieve the 7
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maximum total free energy
 Solidification
r* = critical radius
- 2gTm g = surface free energy
r* = (4)
DHf DT Tm = melting temperature
DHf = latent heat of solidification
DT = Tm - T = supercooling
Note: DHf and g are weakly dependent on DT

 r* decreases as DT increases
For typical DT r* ~ 10 nm
• Small supercooling (DT small) → slow nucleation rate →
few nuclei → large crystals
• Large supercooling (DT large) → rapid nucleation rate →
many nuclei → small crystals 8
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 Rate of phase transformations
Kinetics - study of reaction rates of phase
transformations
• To determine reaction rate – to measure degree
of transformation as a function of time (while
holding temperature constant)
How is the degree of transformation measured?
X-ray diffraction – many specimens required
electrical conductivity measurements –
on single specimen
measure propagation of sound waves –
on single specimen
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 Rate of phase transformation
Fraction transformed, y
transformation complete
Fixed T
0.5 maximum rate reached – now amount
unconverted decreases so rate slows
rate increases as interfacial surface area
t0.5 increases & nuclei grow

log t
Avrami equation: y = 1- exp (-kt n) (5)
fraction transformed time

• Fraction transformed depends on time.

• Phase transformation rate curve is “S-curve”, depends on T.
(6) 10
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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, since

(6)
• Transformation rate increases with increasing temperature
– Rate often so slow that attainment of equilibrium state is not
possible!- particularly at lower temperature
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 Transformations & undercooling
• Eutectoid transf. (Fe-Fe3C system): g  a + Fe3C
• For transf. to occur, must 0.76 wt% C 6.7 wt% C
cool to below 727 ºC slowly 0.022 wt% C
(i.e., must “undercool”)
T(ºC)
1600
d
1400 L
g g +L
1200 L+Fe3C

Fe3C (cementite)
1148 ºC
(austenite)
1000
a Eutectoid: g +Fe3C
ferrite 800 Equil. Cooling: Ttransf. = 727 ºC
727°C
DT a +Fe3C
600
Undercooling by DT: Ttransf. < 727 C
0.022

0.76

400
0 1 2 3 4 5 6 6.7
(Fe) C, wt%C 12
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 Fe-Fe3C Eutectoid transformation
• Transformation of austenite (g) to pearlite:
Diffusion of C
Austenite (g) cementite (Fe3C) during transformation
grain a Ferrite (a)
boundary a g a
g a Pearlite
a growth g
a g
direction a
a
a
• For this transformation, 100 Carbon
reaction rate increases with y (% pearlite) 600oC diffusion
(DT larger)
[Teutectoid – T ] (i.e., DT). 50 650oC
675oC
(DT smaller)
0

• Transformed at higher T → ΔΤ small → form coarse pearlite → relatively soft

• Transformed at lower T → ΔΤ big → form fine pearlite → relatively hard
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 Nucleation and growth
• Reaction rate is a result of nucleation and growth
of crystals.

• Examples:

Large Fine & small

crystals crystals

(T is high, ΔT is small) (T is low, ΔT is big) 14

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 TTT diagrams
➢ Diffusion rates of atoms at Troom are very slow. Hence
quenching “freezes-in” a non-equilibrium phase, which is
metastable
➢ In a non-equilibrium situation, we need to know how long a
metastable (or unstable) phase will last at a particular
temperature.
➢ This is described by …

• Time-Temperature-
Transformation diagrams
• Also called Isothermal
Transformation diagrams
• Or called C-Curves Cu-Al diagram
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 Why ‘C’ curve
• At higher temperatures: rapid diffusion, particles dissolve,
solid solution alone is stable
• At lower temperatures: formed particles are stable, but
diffusion is very slow. - Need longer time to nucleate
• The curve displays the time required for the phase
transformation at various temperature

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Generation of isothermal transformation diagrams
Consider:
• The Fe-Fe3C system, for C0 = 0.76 wt% C
• Transformation at temperature of 675 ºC.
% transformed

100
T = 675 ºC
y,

50

0
1 10 2 10 4 time (s)
T(ºC)
Austenite (stable)
TE (727 C)
700 Austenite
(unstable) isothermal transformation at 675 ºC
600 Pearlite

500

400
time (s) 17
1 10 10 2 10 3 10 4 10 5 ECM3160
Austenite-to-Pearlite Isothermal Transformation
• Eutectoid composition, C0 = 0.76 wt% C
• Begin at T > 727 ºC
• Rapidly cool to 625 ºC
• Hold at T (625 ºC) constant (isothermal treatment)
T(ºC) Austenite (stable)
TE (727 ºC)
700 Austenite
(unstable)

600
g
Pearlite
g
g g g g
500

400

1 10 10 2 10 3 10 4 10 5
time (s) 18
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 Pearlite morphology
Two cases:
• Ttransf just below TE
--Higher T: diffusion is faster
--Pearlite is coarser.
Coarse pearlite
• Ttransf well below TE
--Lower T: diffusion is slower
--Pearlite is finer.
Fine pearlite

- Smaller DT: - Larger DT:

colonies are colonies are
larger smaller

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 Fe-C Phase equilibria
• Ferrite: BCC α-Fe Relatively soft and ductile; magnetic at RT.
Max C solubility 0.022%
• Austenite: FCC γ-Fe Ductile only at elevated temperatures;
non-magnetic at high temperatures. Max C solubility 2.1%
• Cementite: Fe3C, a Compound, not an alloy. 6.69% C.
• Martensite: - a grain structure not a phase.
- Crystal structure is formed by displacive transformation
- formed by rapid cooling/quenching of austenite that traps carbon atoms
- is a specifically form of ferrite supersaturated with C, very hard steel
- Martensite “phases” show memory effects

Pearlite 20
Ferrite Austenite Cementite (Ferrite + Cementite)
 Bainite: another Fe-Fe3C
• Bainite:
transformation product
-- elongated Fe3C particles in
α-ferrite matrix
-- diffusion controlled a
• Isothermal Transf. Diagram,
C0 = 0.76 wt% C Fe3C
800 Austenite (stable) (cementite)
T(ºC) A
TE a (ferrite)
P
600 100% pearlite
Pearlite / bainite boundary
100% bainite
400 B 5 mm
A

200

10-1 10 103 105

time (s) 21
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 Spheroidite: another microstructure for
the Fe-Fe3C system
• Spheroidite:
-- Fe3C particles within an a-ferrite a
matrix with sphere morphology (ferrite)
-- formation requires diffusion
-- heat bainite or pearlite at temperature Fe3C
(cementite)
just below eutectoid for long times
-- driving force – reduction of a-
ferrite/Fe3C interfacial area
60 mm
• Isothermal
transf.
diagram

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 Transformations involving
non-eutectoid compositions
Consider C0 = 1.13 wt% C
T(ºC) T(ºC)
900 1600
d
A 1400 L

Fe3C (cementite)
800
A TE (727 ºC) g +L
+ 1200 g L+Fe3C
700 A C (austenite)
P 1000
A
+ P a g +Fe3C
600
800
727°C
DT a +Fe3C
500 600

0.022
0.76
1 10 102 103 104 400

1.13
time (s) 0 1 2 3 4 5 6 6.7
(Fe)
C, wt%C
- Here C is the proeutectoid cementite

Hypereutectoid composition – proeutectoid cementite

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 Martensite: A non-equilibrium
transformation product
• Martensite (M): - a grain structure,
not a phase
-- g(FCC) to Martensite (BCT, body

60 mm
x centered tetragonal )
Fe atom potential
x x
sites x x C atom sites
x

• Isothermal Transf. Diagram

Martensite needles
800 Austenite (stable) Austenite
T(ºC) A TE
P
600 • g to martensite transformation.
-- is rapid! (diffusionless)
400 A B -- % transf. depends only on T
to which rapidly cooled
0%
200 M+A 50%
M+A 90%
M+A
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-1 10 3 5 ECM3160
10 10 10 time (s)
Displacive transformation: a different way

• If we quench f.c.c. γ-Fe from 914 oC to

room temperature at a rate of about 105
oC s−1 we expect to prevent the diffusive

f.c.c. → b.c.c. transformation from

taking place.
• In reality, below 550 oC the iron will
transform to b.c.c. by a displacive
transformation instead. 25
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 Displacive transformation
• Temperature drop produces unrelieved
strain.
• All atoms undergo a massive, sudden,
cooperative rearrangement.
• At the speed of sound – very fast
• BCC Fe with special “lens” shaped
“Martensite” structures.
• Displacive transformation is also
known as “Martensitic transformation”
or diffusionless transformation.

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Comparison of displacive & diffusive transformation

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Iron TTT diagram with martensite

MS: temperature at which martensite starts to form

MF: temp. at which martensite transformation finishes 28
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Steel TTT diagram with martensite
Iron (C-free) Steel (Containing C)

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 Martensite
• Martensite transformation (Displacive transfromation)
is very important in the heat treatment of steel.
Martensite is very hard and brittle.
• “Martensitic transformation” is often used for any such
displacive transformations.
─ e. g. Displactive transformation of partially stabilized
zirconia (PSZ) ceramic (tetragonal) to stable monoclinic used for
toughening of engineering ceramics
• Most alloys do not demonstrate such transformation
─ Irony: such a rare and little understood transformation, but
it is so important in the structural alloys (steel)
• Strickly speaking, “martensite” is bcc Fe formed by a
displacive transformation. 30
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 Martensite formation
g-Fe (FCC)
slow cooling
(Austenite) a-Fe (BCC) + Fe3C
quench (Ferrite) (Cementite)

tempering
M (BCT)

Martensite (M): – single grain structure, not a phase

– has body centered tetragonal (BCT)
crystal structure
– hard, brittle

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Cooling experiment: Fe-C system (1)
• Start from an eutectoid temperature (760 oC)

Adapted
from Fig.
10.15,
Callister 6e.

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Cooling experiment: Fe-C system (2)
• Start from an eutectoid temperature (760 oC)

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Cooling experiment: Fe-C system (3)
• Start from an eutectoid temperature (760 oC)

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 Phase transformations of alloys
• Effect of adding other elements TTT diagram for an alloy steel
─ Change transition temp.
• Cr, Ni, Mo, Si, Mn
─ retard g → a + Fe3C, namely,
shifting to longer times the nose of the
austenite-to-pearlite transformation
─ the formation of a separate bainite
nose
Fe-C TTT Diagram
800 Austenite (stable)
T(ºC) A TE
600
P

400 A B

0%
200 M+A 50%
M+A 90%
M+A 35
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10-1 102 103 105 (s)
 Continuous cooling
transformation diagrams
Conversion of isothermal
transformation diagram
to continuous cooling
transformation diagram

• In continuous cooling, the

time required for a reaction
to begin and end is delayed

• The isothermal curves shift

to longer times and lower
temperature
Cooling curve

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Example problems: Isothermal
heat treatment
On the isothermal transformation diagram
for a 0.45 wt% C, Fe-C alloy, sketch and
label the time-temperature paths to
produce the following microstructures:
a) 42% proeutectoid ferrite and 58% coarse
pearlite
b) 50% fine pearlite and 50% bainite
c) 100% martensite
d) 50% martensite and 50% austenite
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 Solution to example problem (a)
a) 42% proeutectoid ferrite and 58% coarse pearlite
1600
d

Fe3C (cementite)
1400 L
o g+L Fe-Fe3C phase diagram,
1200 g
T( C) L+Fe3C
(austenite) 1148oC T (ºC) for C0 = 0.45 wt% C
1000
g + Fe3C 800
727oC A+a
800 A
600 a+ Fe3C
4000 1 2 3 4 5 6 6.7 A+P
C, wt% C 600 P
B
Isothermally treat at ~ 680 ºC
A+B
-- all austenite transforms A
to proeutectoid a and 400
M (start)
50%
coarse pearlite. M (50%)
C0 - 0.022 M (90%)
Wpearlite = = Wγ 200
0.76 - 0.022

0.45 - 0.022
= = 0.58 0
0.76 - 0.022 0.1 10 103 105
time (s) 38
Wa ¢ = 1 - 0.58 = 0.42 ECM3160
 Solution to example problem (b)
b)50% fine pearlite and 50% bainite
Fe-Fe3C phase diagram,
T (oC) for C0 = 0.45 wt% C
800 A+a
Isothermally treat at ~ 590 ºC A
– 50% of austenite transforms
to fine pearlite. P
A+P
600
Then isothermally treat B
at ~ 470 ºC A+B
A
– all remaining austenite 50%
400
transforms to bainite. M (start)
- (then cool down to room M (50%)
M (90%)
temperature)
200

0
0.1 10 103 105
time (s) 39
Solutions to example problem (c) & (d)
c) 100% martensite – rapidly quench to room
temperature Fe-Fe3C phase diagram,
T (oC) for C0 = 0.45 wt% C
800 A+a
d) 50% martensite A

& 50% austenite P

A+P
600
-- rapidly quench to B
~ 290 ºC, hold at this A+B
A
temperature 400 50%
M (start)
M (50%)
M (90%)
d)
200

c)
0
0.1 10 103 4010
5
time (s)ECM3160
Effect of C content on mechanical properties
Pearlite (med)
Pearlite (med) Cementite
ferrite (soft) (hard)
C0 < 0.76 wt% C C0 > 0.76 wt% C
Hypoeutectoid Hypereutectoid
Hypo Hyper Hypo Hyper
TS(MPa) %EL 80
1100

Impact energy (Izod, ft-lb)

YS(MPa) 100
900
hardness
40
700
50
500
0
300
0
0.76

0.76
0 0.5 0 0.5 1
wt% C wt% C
• Increase C content: TS,YS and hardness increase, ductility decreases
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 Mechanical Props: Fine Pearlite vs.
Coarse Pearlite vs. Spheroidite
Hypo Hyper 90 Hypo Hyper
320 fine
pearlite
spheroidite

Ductility (%RA)
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 pearlite > coarse pearlite > spheroidite
• %RA (reduction in area): fine pearlite < coarse pearlite < spheroidite

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 Mechanical Props: Pearlite vs.
Bainite and Martensite

• Hardness: pearlite < bainite

• Hardness: fine pearlite < tempered martensite < martensite.
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 Tempered martensite
Heat treat martensite to form tempered martensite
• tempered martensite is less brittle than martensite
• tempering reduces internal stresses caused by quenching
TS(MPa)
YS(MPa)
1800

1600 TS

9 mm
1400 YS

1200 60
1000 50
%RA %RA
40
800 30
200 400 600
Tempering T (oC)
• tempering produces extremely small Fe3C particles surrounded by a.
• tempering decreases TS, YS but increases %RA 44
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Summary of possible transformations
Austenite (g)
slow rapid
cool moderate quench
cool
Pearlite Bainite Martensite
(a + Fe3C layers + a (a + elong. Fe3C particles) (BCT phase
proeutectoid phase) diffusionless
transformation)
heat at <TE
Martensite reheat
Spheroidite Temp. Martensite
Strength

Ductility
(spherical Fe3C in a-ferrite) bainite Tempered
fine pearlite Martensite
(a + very fine
coarse pearlite Fe3C particles)
spheroidite
General Trends ECM3160
45
 Precipitation hardening
• Particles impede dislocation motion.
• Ex: Al-Cu system 700
T(ºC) L CuAl2
• Procedure: L
-- Point A: solution heat treatment
600
a a+L q+L
A
(get a solid solution) 500 q
-- Point B: quench to room temp. a+q
400 C
(retain a solid solution)
-- Point C: Precipitation heat treatment 300
reheat to nucleate small q particles (Al) 0 B 10 20 30 40 50
wt% Cu
within a phase. composition range
available for precipitation hardening
• Other alloys that precipitation
harden: Temp.
• Cu-Be Pt A (sol’n heat treat)

• Cu-Sn
• Mg-Al Pt C (precipitate q)

Time
Pt B 46
• Precipitation hardening commonly used in Al alloys. ECM3160
 Influence of precipitation heat
treatment on TS, %EL
• 2014 Al Alloy:
• Maxima on TS curves. • Minima on %EL curves.
• Increasing T accelerates
process.
tensile strength (MPa)

30

%EL (2 in sample)
400
20
300
149oC 10
200 204oC 149oC
204oC
100 0
1min 1h 1day 1mo 1yr 1min 1h 1day 1mo 1yr
precipitation heat treat time precipitation heat treat time
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 Summary
• Heat treatments of Fe-C alloys produce microstructures
including:
-- pearlite, bainite, spheroidite, martensite,
-- tempered martensite
• Precipitation hardening
-- hardening, strengthening due to formation of
precipitate particles.
-- Al, Mg alloys precipitation hardenable.
Reading:
• Callister & Rethwisch: Fundamentals of Materials
Science & Engineering Chap. 11
Homework:
• Continue “Teaching yourself phase diagrams”
• Coursework 1 – Phase diagrams 48
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