Ferrite - BCC

Martensite - BCT

Austenite - FCC

Chapter 1

Phase
Transformations in
Fe3C (cementite)- orthorhombic
Metals
Why do we study phase transformations?
 The tensile strength of an Fe-C alloy of eutectoid
composition can be varied between 700-2000 MPa
depending on HT process adopted.
 Desirable mechanical properties of a material can be
obtained as a result of phase transformations using the
right HTprocess.
 In order to design a HT for some alloy with desired RT
properties, time & temperature dependencies of some
phase transformations can be represented on modified
phase diagrams.
Based on this, we will learn:
A. Phase transformations in metals
B. Microstructure and property dependence in Fe-C alloy system
C. Precipitation Hardening
 Topics to be covered:
Transformation rate
Kinetics of Phase Transformation
Nucleation: homogeneous, heterogeneous
Free Energy, Growth
Isothermal Transformations (TTT diagrams)
Pearlite, Martensite, Spheroidite, Bainite
Continuous Cooling
Mechanical Behavior
Precipitation Hardening
 Phase Transformations
Phase transformations – change in the number or
character of phases.
 Simple diffusion-dependent

No change in # of phases

No change in composition

Example: solidification of a pure metal, allotropic transformation, re-
crystallization, grain growth

More complicated diffusion-dependent

Change in # of phases

Change in composition

Example: eutectoid reaction
 Diffusion-less

Example: meta-stable phase : martensite
Phase Transformations -Stages
Most phase transformations begin with the formation of
numerous small particles of the new phase that increase in size
until the transformation is complete.
Nucleation is the process whereby nuclei (seeds) act as templates
for crystal growth.
1. Homogeneous nucleation - nuclei form uniformly throughout the
parent phase; requires considerable supercooling (typically 80-
300°C).
2. Heterogeneous nucleation - form at structural in-homogeneities
(container surfaces, impurities, grain boundaries, dislocations) in
liquid phase much easier since stable “nucleating surface” is
already present; requires slight super-cooling (0.1-10ºC).
Supercooling
 During the cooling of a liquid, solidification (nucleation)
will begin only after the temperature has been lowered
below the equilibrium solidification (or melting)
temperature Tm. This phenomenon is termed super-cooling
or under-cooling.

The driving force to nucleate increases as ∆T increases

Small super-cooling  slow nucleation rate - few nuclei -
large crystals

Large super-cooling  rapid nucleation rate - many nuclei
- small crystals
Kinetics of Solid State Reactions
Transformations involving diffusion depend on time.
Time is also necessary for the energy increase associated with
the phase boundaries between parent and product phases.
Moreover, nucleation, growth of the nuclei, formation of grains
and grain boundaries and establishment of equilibrium take
time.
As a result we can say the transformation rate is a function of
time.
The fraction of reaction completed is measured as a function of
time at constant T.
Tranformation progress can be measured by microscopic
examination or measuring a physical property (e.g.,
conductivity).
The obtained data is plotted as fraction of the transformation
versus logarithm of time.
FRACTION OF TRANSFORMATION
• Fraction transformed depends on time.
1
Avrami Eqn. y
= − −ktn
y 1 e
fraction 0.5 Fixed
transformed time
T
0 t log (t)
• Transformation rate depends on T. 0.5

activation energy Ex: recrystallization of Cu

119°C
103°C
C
y (%)

°C

°C
1 −

5°

2°
r= = Ae Q /RT

13

11

88

43
100
t 0.5
50
0
• r often small: equil not possible 1 10 102 104
log (t) min
2
Percent recrystallization as a function of time
and at constant temperature for pure copper.
 Transformations & Undercooling
Eutectoid transformation (Fe-Fe3C system):
γ ⇒ α + Fe3C
For transformation to occur,
must cool to below 727°C 0.76 wt% C 6.7 wt% C
0.022 wt% C
T(°C)
1600
δ
1400 L
γ γ +L
1200 1148°C L+Fe3C
(austenite)

Fe3C (cementite)
1000
α γ +Fe3C
Eutectoid:
ferrite 800 Equil. Cooling: Ttransf. = 727ºC
727°C
∆T α +Fe C 3
600
Undercooling by Ttransf. < 727°C
0.022

0.76

400
0 1 2 3 4 5 6 6.7
(Fe) C, wt% C
Generation of Isothermal Transformation Diagrams
• The Fe-Fe3C system, for Co = 0.76 wt% C
• A transformation temperature of 675°C.

% transformed
100
T = 675°C
50

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

600 Pearlite
isothermal transformation at 675°C
100

500
50%pearli
0%

400
time (s)
te

1 10 10 2 10 3 10 4 10 5
 Eutectoid Transformation Rate ~ ∆T
• Transformation of austenite to pearlite: Diffusion of C
during transformation
Austenite (γ) cementite (Fe3C)
grain α Ferrite (α) α
boundary α γ
γ α γ
γ
α pearlite α
α
α growth
direction α Carbon
diffusion
• For this transformation, 100
rate increases with ( ∆T) 600°C
[Teutectoid – T ]. (∆T larger)
% pearlite

650°C
50
675°C
(∆T smaller)

Coarse pearlite  formed at higher temperatures – relatively soft

Fine pearlite  formed at lower temperatures – relatively hard
Eutectoid Transformation Rate
 At T just below 727°C, very long times (on the order of 10 5 s) are
required for 50% transformation and therefore transformation rate is
slow.
 The transformation rate increases as T decreases, for example, at
540°C 3 s is required for 50% completion.
This observation is in clearactivation energy
contradiction with the equation of
1 −
r= = Ae Q /RT
t 0.5

This is because in T range of 540°C-727°C, the transformation

rate is mainly controlled by the rate of pearlite nucleation and
nucleation rate decreases with increasing T. Q in this equation
is the activation energy for nucleation and it increases with T
increase.
It has been found that at lower T, the austenite decomposition
is diffusion controlled and the rate behavior can be calculated
using Q for diffusion which is independent of T.
 Nucleation and Growth
• Reaction rate is a result of nucleation and growth of crystals.
100 Nucleation rate increases w/ ∆T
% Pearlite Growth
regime Growth rate increases w/ T
50 Nucleation
regime

0 t50 log (time)

• 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

5
 Isothermal Transformation Diagrams
solid curves are plotted:
 one represents the time required at each
temperature for the start of the
transformation;
 the other is for transformation
completion.
 The dashed curve corresponds to 50%
completion.
The austenite to pearlite transformation
will occur only if the alloy is
supercooled to below the eutectoid
temperature (727˚C).
Time for process to complete depends on
the temperature.
 Isothermal Transformation Diagram
• Eutectoid iron-carbon alloy; composition, Co = 0.76 wt% C
• Begin at T > 727˚C
• Rapidly cool to 625˚C and hold isothermally.

Austenite-to-Pearlite
Transformations Involving Noneutectoid Compositions
Consider C0 = 1.13 wt% C
T(°C)
1600
δ
1400 L

Fe3C (cementite)
γ γ +L
1200 L+Fe3C
(austenite)
1000
γ +Fe3C
800
727°C
∆T α +Fe3C
600
0.022
0.76

400
0 1 2 3 4 5 6 6.7
1.13

(Fe)
C, wt%C

Hypereutectoid composition – proeutectoid cementite

 Possible Transformations

Martensite
T Martensite
Strength

Ductility

bainite
fine pearlite
coarse pearlite
spheroidite
General Trends
Coarse pearlite (high diffusion rate) and (b) fine pearlite

- Smaller ∆T: - Larger ∆T:

colonies are colonies are
larger smaller
 Bainite: Non-Equilibrium Transformation Products
 elongated Fe3C particles in α-ferrite matrix
 diffusion controlled
 α lathes (strips) with long rods of Fe3C

800 Austenite (stable) Martensite

T(°C) A
TE
P
600
100% pearlite

400 A B 100% bainite

Cementite
200
100
0%

50%

10-1 10 103 105 Ferrite

time (s)
 Bainite Microstructure
Bainite: formed as a result of transformation of
austenite.
Bainite consists of ferrite and cementite and diffusion
processes take place as a result.
This structure looks like needles or plates. There is no
proeutectoid phase in bainite.
Bainite consists of acicular (needle-like) ferrite with
very small cementite particles dispersed throughout.
The carbon content is typically greater than 0.1%.
Bainite transforms to iron and cementite with
sufficient time and temperature.
 Spheroidite: Nonequilibrium Transformation
 Fe3C particles within an α-ferrite matrix
 diffusion dependent
 heat bainite or pearlite at temperature just below eutectoid for long times
 driving force – reduction of α-ferrite/Fe3C interfacial area

800 Austenite (stable)

T(°C) A TE
P
600 100% spheroidite
Spheroidite
100% spheroidite
400 A B

200
100
0%

50%

10-1 10 103 105 time (s)

10
Pearlitic Steel partially transformed to Spheroidite
 Design a heat treatment to produce the pearlite structure
shown in Figure

micrograph of the pearlite

lamellae (x 2000)

7.14

The effect of the austenite

transformation temperature on
the interlamellar spacing in
pearlite.
A

B C
D

E
A

B C
The Martensitic Reaction and Tempering
Martensiteis : is result of a diffusionless solid-state transfomation .
•The growth rate is so high → nucleation is controlling step.
• is an athermal transformation (i.e. the reaction depends only
on the temperature, not on the time)
upon quenching, nonequilibrium supersaturated
In steels (< 0.2% C) BCC martensite structure
FCC austenite
upon quenching, BCT (body-centered tetragonal)
In steels (>0.2% C)
FCC austenite martensite
BCT caused by the Carbon
atoms in the (1/2, 0, 0) site
being trapped during the
transformation to the BCC
%C(martensite) = %C (the starting austenite)
 Martensite Formation
800 Austenite (stable)
T(°C) A TE
P
600

400 A B 10
5 0%
0% 0%
0%
200 M+A 50%
M+A 90%
M+A
10-1 10 103 105 time (s)
Martensite needles
 single phase
Austenite
 body centered tetragonal (BCT) crystal structure
 BCT if C0 > 0.15 wt% C
 Diffusion-less transformation
 BCT  few slip planes  hard, brittle
 % transformation depends only on T of rapid cooling
An micrograph of austenite that was polished flat and then allowed to
transform into martensite.
The different colors indicate the displacements caused when martensite
forms.
Iron-carbon alloy
with eutectoid
composition.


A: Austenite

P: Pearlite
 B: Bainite

M: Martensite
 Effect of Adding 4340 Steel
Other Elements
 Other elements (Cr, Ni, Mo, Si and
W) may cause significant changes
in the positions and shapes of the
TTT curves:

Change transition temperature;

Shift the nose of the austenite-to- nose
pearlite transformation to longer
plain
times;

Shift the pearlite and bainite noses carbon
to longer times (decrease critical steel
cooling rate);
 Form a separate bainite nose;
 Plain carbon steel: primary
alloying element is carbon.
Example 1:
 Iron-carbon alloy with eutectoid
composition.
 Specify the nature of the final
microstructure (% bainite,
martensite, pearlite etc) for the
alloy that is subjected to the Bainite,
following time–temperature 100%
treatments:
 Alloy begins at 760˚C and has
been held long enough to
achieve a complete and
homogeneous austenitic
structure.

Treatment (a)
 Rapidly cool to 350 ˚C
 Hold for 104 seconds
 Quench to room temperature
Example 2:
 Iron-carbon alloy with
eutectoid composition.
 Specify the nature of the final
microstructure (% bainite,
martensite, pearlite etc) for the
alloy that is subjected to the
following time–temperature
treatments:
 Alloy begins at 760˚C and has
been held long enough to Austenite,
achieve a complete and 100%
homogeneous austenitic
structure.

Treatment (b)
 Rapidly cool to 250 ˚C
 Hold for 100 seconds Martensite,
 Quench to room 100%
temperature
Example 3: Austenite,
 Iron-carbon alloy with 100%
eutectoid composition. Almost 50% Pearlite,
 Specify the nature of the final 50% Austenite
microstructure (% bainite,
martensite, pearlite etc) for the
alloy that is subjected to the
following time–temperature
treatments:
 Alloy begins at 760˚C and has Bainite, 50%
been held long enough to
achieve a complete and
homogeneous austenitic
structure.

Treatment (c)
 Rapidly cool to 650˚C Final:
 Hold for 20 seconds 50% Bainite,
 Rapidly cool to 400˚C 50% Pearlite
 Hold for 103 seconds
 Quench to room
temperature
 Continuous Cooling Transformation Diagrams
 Isothermal heat treatments are not the
most practical due to rapidly cooling
and constant maintenance at an
elevated temperature.
 Most heat treatments for steels involve
the continuous cooling of a specimen
to room temperature.
 TTT diagram (dotted curve) is modified
for a CCT diagram (solid curve).
 For continuous cooling, the time
required for a reaction to begin and
end is delayed.
 The isothermal curves are shifted to
longer times and lower temperatures.
 Moderately rapid and slow cooling
curves are superimposed on a
continuous cooling transformation
diagram of a eutectoid iron-carbon
alloy.
 The transformation starts after a
time period corresponding to the
intersection of the cooling curve
with the beginning reaction curve
and ends upon crossing the
completion transformation curve.
 Normally bainite does not form
when an alloy is continuously
cooled to room temperature;
austenite transforms to pearlite
before bainite has become possible.
 The austenite-pearlite region (A---
B) terminates just below the nose.
Continued cooling (below Mstart)
of austenite will form martensite.
 For continuous cooling of a
steel alloy there exists a critical
quenching rate that represents
the minimum rate of
quenching that will produce a
totally martensitic structure.
 This curve will just miss the
nose where pearlite
transformation begins

Continuous cooling diagram
for a 4340 steel alloy and
several cooling curves
superimposed.

This demonstrates the
dependence of the final
microstructure on the
transformations that occur
during cooling.

Alloying elements used to
modify the critical cooling
rate for martensite are
chromium, nickel,
molybdenum, manganese,
silicon and tungsten.
Mechanical Properties
Hardness
Brinell, Rockwell
Yield Strength
Tensile Strength
Ductility
% Elongation
Effect of Carbon Content
 Mechanical Properties: Influence of Carbon Content
Pearlite (med)
Pearlite (med) Cementite
ferrite (soft) (hard)
C0 > 0.76 wt% C
C0 < 0.76 wt% C
Hypoeutectoid Hypereutectoid
Mechanical Properties: Fe-C System
Example: P10.37
For a eutectoid steel, describe isothermal
heat treatments that would be required to
yield specimens having the following Brinell
Hardnesses:
1. 180 HB
2. 220 HB
3. 500 HB
 Tempered Martensite
 Martensite is hard but also very brittle so that it can not be used in
most of the applications.
 Any internal stress that has been introduced during quenching has a
weakening effect.
 The ductility and toughness of the material can be enhanced by heat
treatment called tempering. This also helps to release any internal
stress.

 Tempering is performed by heating martensite to a T below eutectoid

temperature (250°C-650°C) and keeping at that T for specified period
of time.
 The formation of tempered martensite is by diffusion.
 Tempered Martensite
 Tempered martensite is less brittle than martensite; tempered at 594 °C.
 Tempering reduces internal stresses caused by quenching.
 The small particles are cementite; the matrix is α-ferrite. US Steel Corp.

4340 steel
 Tempered Martensite
 Tempered martensite may be nearly as hard and strong as martensite,
but with substantially enhanced ductility and toughness.
 The hardness and strength may be due to large area of phase
boundary per unit volume of the material.
 The phase boundary acts like a barrier for dislocations. The
continuous ferrite phase in tempered martensite adds ductility and
toughness to the material.
 The size of the cementite particles is important factor determining
the mechanical behavior.
 As the cementite particle size increases, material becomes softer
and weaker. The temperature of tempering determines the
cementite particle size. Since martensite-tempered martensite
transformation involves diffusion, Increasing T will accelerate the
diffusion and rate of cementite particle growth and rate of
softening as a result.
Hardness as a function of carbon
concentration for steels
 Rockwell C and Brinell Hardness

Hardness versus tempering time for a water-quenched eutectoid plain carbon steel (1080); room
temperature.
Example: P10.25
Briefly describe the simplest continuous cooling
heat treatment procedure that would be used in
converting a 4340 steel from microstructure to
another.
1. (Martensite + Ferrite + Bainite) to (Martensite +
Ferrite + pearlite + Bainite)
2. (Martensite + Ferrite + Bainite) to (spheroidite)
3. (Martensite + Ferrite + Bainite) to (tempered
Martensite)
Precipitation Hardening
The strength and hardness of some metal alloys
may be improved by the formation of extremely
small, uniformly dispersed particles (precipitates)
of a second phase within the original phase matrix.
Other alloys that can be precipitation hardened or
age hardened:
 Copper-Beryllium (Cu-Be)
 Copper-Tin (Cu-Sn)
 Magnesium-Aluminum (Mg-Al)
 Aluminum-Copper (Al-Cu)
 High-strength Aluminum alloys
 Phase Diagram for Precipitation Hardened Alloy
Criteria:
Maximum solubility of 1 component in

the other (M);

Solubility limit that rapidly decreases

with decrease in temperature (M→N).

Process:
Solution Heat Treatment – first heat

treatment where all solute atoms are

dissolved to form a single-phase solid
solution.
Heat to T and dissolve B phase.
0

Rapidly quench to T1
Nonequilibrium state (α phase solid
solution supersaturated with B atoms;
alloy is soft, weak-no ppts).
 Precipitation Heat Treatment – the 2nd stage

The supersaturated α solid
solution is usually heated to an
intermediate temperature T2
within the α+β region (diffusion
rates increase).
 The β precipitates (PPT) begin
to form as finely dispersed
particles. This process is referred
to as aging.
 After aging at T2, the alloy is
cooled to room temperature.

Strength and hardness of the
alloy depend on the ppt
temperature (T2) and the aging
time at this temperature.
Precipitation Hardening
• Particles impede dislocation motion.
700
• Ex: Al-Cu system
T(°C) L CuAl2
• Procedure: 600
-- Pt A: solution heat treat
α+L α θ+L
A
(get α solid solution) 500 θ
-- Pt B: quench to room temp. C α+θ
400
(retain α solid solution)
-- Pt C: reheat to nucleate 300
small θ particles within 0 B 10 20 30 40 50
(Al) wt% Cu
α phase. composition range
available for precipitation hardening

Temp. At room temperature the stable state

Pt A (solution heat treat) of an aluminum-copper alloy is an
aluminum-rich solid solution (α) and
an intermetallic phase with a
tetragonal crystal structure having
Pt C (precipitate θ) nominal composition CuAl2 (θ).

Time
Pt B
 Precipitation Heat Treatment – the 2nd stage

PPT behavior is represented in
the diagram:

With increasing time, the
hardness increases, reaching a
maximum (peak), then
decreasing in strength.

The reduction in strength and
hardness after long periods is
overaging (continued particle
growth). Small solute-enriched regions in a solid
solution where the lattice is identical or
somewhat perturbed from that of the
solid solution are called Guinier-
Preston zones.
PRECIPITATION STRENGTHENING
• Hard precipitates are difficult to shear.
Ex: Ceramics in metals (SiC in Iron or Aluminum).
precipitate
Large shear stress needed
Side View to move dislocation toward
precipitate and shear it.

Unslipped part of slip plane Dislocation

Top View
“advances” but
precipitates act as
“pinning” sites with
S spacing S.
Slipped part of slip plane

1
• Result: σ y ~
S
24
Several stages in the formation of the equilibrium PPT (θ)
phase.
(a)supersaturated α solid solution;
(b)transition (θ”) PPT phase;
(c)equilibrium θ phase within the α matrix phase.
 Influence of Precipitation Heat Treatment on Tensile
Strength (TS), %EL
• 2014 Al Alloy:
• TS peak with precipitation time.
• Increasing T accelerates • %EL reaches minimum
process. with precipitation time.
ita ll
cip ma
“ag tes
”
ed
ion

pre ny s
so .

era ita ge
lid uil
lut

“ov cip lar

ge tes
so n-eq

30
ma
tensile strength (MPa)

%EL (2 in sample)
pre wer

d”
no

400 fe
20
300
149°C 10
200 204°C 149°C
204°C
100 0
1min 1h 1day 1mo 1yr 1min 1h 1day 1mo 1yr
precipitation heat treat time precipitation heat treat time
 Effects of Temperature


Characteristics of a 2014 aluminum
alloy (0.9 wt% Si, 4.4 wt% Cu, 0.8
wt% Mn, 0.5 wt% Mg) at 4
different aging temperatures.

Alloys that experience significant
precipitation hardening at room
temp and after short periods must
be quenched to and stored under
refrigerated conditions.
 Several aluminum alloys that are
used for rivets exhibit this
behavior. They are driven while
still soft, then allowed to age
harden at the normal room
temperature.