FerriteBCC

MartensiteBCT

AusteniteFCC

Chapter 11

Fe3C(cementite)orthorhombic

Phase
Transformations

Phase Transformations
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

More complicated diffusion-dependent

No change in # of phases
No change in composition
Example: solidification of a pure metal, allotropic transformation,
recrystallization, grain growth

Change in # of phases
Change in composition
Example: eutectoid reaction

Diffusionless

Example: metastable phase - martensite

Phase Transformations

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.
Homogeneous nucleation - nuclei form uniformly throughout
the parent phase; requires considerable supercooling
(typically 80-300C).
Heterogeneous nucleation - form at structural
inhomogeneities (container surfaces, impurities, grain
boundaries, dislocations) in liquid phase much easier since
stable nucleating surface is already present; requires
slight supercooling (0.1-10C).

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 supercooling (or
undercooling.
The driving force to nucleate increases as T
increases
Small supercooling slow nucleation rate - few
nuclei - large crystals
Large supercooling rapid nucleation rate many nuclei - small crystals

Nucleation and Growth

Rate is a result of nucleation and growth of crystals.
100
% Pearlite

Nucleation rate increases w/ T

50 Nucleation
regime

Growth
regime

t50

Growth rate increases w/ T

log (time)

Examples:

pearlite
colony

T just below TE

Nucleation rate low

Growth rate high

T moderately belowTE
Nucleation rate med
Growth rate med.

T way below TE
Nucleation rate high
Growth rate low

Nucleation of a spherical solid particle in a liquid

The change in free energy G (a function of the
internal energy and enthalpy of the system) must
be negative for a transformation to occur.

Liquid

Assume that nuclei of the solid phase form in the

interior of the liquid as atoms cluster togethersimilar to the packing in the solid phase.

Also, each nucleus is spherical and has a radius r.

Free energy changes as a result of a

transformation: 1) the difference between the solid
and liquid phases (volume free energy, GV); and
2) the solid-liquid phase boundary (surface free
G=GS+GV
energy, GS).

Transforming one phase into another takes time.

Fe

(Austenite)

FCC

Fe C

3
Eutectoid
transformation (cementite)

(ferrite)

(BCC)

Homogeneous Nucleation & Energy Effects

Surface Free Energy- destabilizes
the nuclei (it takes energy to make
an interface)
GS 4r 2
= surface tension

GT = Total Free Energy

= GS + GV
Volume (Bulk) Free Energy
stabilizes the nuclei (releases energy)
4
GV r 3 G

volume free energy

unit volume

r* = critical nucleus: for r < r* nuclei shrink; for r >r* nuclei grow (to reduce energy)

Solidification
2Tm
r*
Hf T

r* = critical radius
= surface free energy
Tm = melting temperature
Hf = latent heat of solidification (fusion)
T = Tm - T = supercooling

Note:Hf and are weakly dependent on T

r*

decreases asT increases

For typicalT

r* ~10nm

Transformations & Undercooling

+ Fe3C
Eutectoid transformation (Fe-Fe3C system):
0.76 wt% C
6.7 wt% C
For transformation to occur,
0.022 wt% C

must cool to below 727C

T(C)
1600

+L

1200
(austenite)
1000

+Fe3C

Eutectoid:

Equil. Cooling: Ttransf. = 727C

727C
T
+Fe C

800

400
0
(Fe)

Undercooling by Ttransf. < 727C

0.76

600
0.022

ferrite

L+Fe3C

1148C

Fe3C (cementite)

1400

6.7

C, wt% C

Fraction transformed, y

Rate of Phase Transformation

transformation
complete

Fixed T

0.5

t0.5

maximum rate reached now

amount
unconverted decreases so rate
slows
rate increases as surface area
increases
& nuclei grow
Fraction

log t

Avrami equation => y = 1- exp (-kt n)

fraction
transformed

By convention

transformed
depends on
time

time

rate = 1 / t0.5

Avrami relationship - the rate is defined as the inverse of the time to complete half of the
transformation. This describes most solid-state transformations that involve diffusion.12

Temperature Dependence of
Transformation Rate
135C 119C

10

113C 102C

88C

102

43C

104
Adapted from Fig. 10.11,
Callister 7e. (Fig. 10.11
adapted from B.F. Decker and
D. Harker, "Recrystallization in
Rolled Copper", Trans AIME,
188, 1950, p. 888.)

In general, rate increases as T

r = 1/t0.5 = A e -Q/RT

R = gas constant
T = temperature (K)
A = preexponential rate factor
Q = activation energy

Arrhenius expression

r is often small so equilibrium is not possible.

Generation of Isothermal Transformation Diagrams

Consider:

% transformed

The Fe-Fe3C system, for Co = 0.76 wt% C

A transformation temperature of 675C.
100

T = 675C

50
0

10 2

T(C)

Austenite (stable)

10 4

time (s)
TE (727C)

Austenite
(unstable)

600

Pearlite
isothermal transformation at 675C

500
400

%
100
te
50%pearli
0%

700

10

10 2 10 3 10 4 10 5

time (s)

Eutectoid Transformation Rate ~ T

Transformation of austenite to pearlite:

For this transformation,

rate increases with ( T)

[Teutectoid T ].

cementite (Fe3C)
Ferrite ()

pearlite
growth
direction

100
% pearlite

Austenite ()
grain
boundary

Diffusion of C
during transformation

600C
(T larger)

50

Carbon
diffusion

650C
675C
(T smaller)

Coarse pearlite formed at higher temperatures relatively soft

Fine pearlite

formed at lower temperatures relativelyhard

Isothermal Transformation Diagrams

2 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
(727C).
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 > 727C
Rapidly cool to 625C and hold isothermally.

Austenite-to-Pearlite

Transformations Involving
Noneutectoid Compositions
Consider C0 = 1.13 wt% C
T(C)

1400
1200

+L

L+Fe3C

(austenite)

1000

+Fe3C

800
0.76

400
0
(Fe)

1.13

0.022

600

727C

+Fe3C
2

Fe3C (cementite)

1600

6.7

C, wt%C

Hypereutectoid composition proeutectoid cementite

Transformations Involving
Noneutectoid Compositions
Consider C0 = 1.13 wt% C
T(C)

T(C)

900

A
+

1200

C
A

+L

L+Fe3C

(austenite)

1000

+Fe3C

800
600

500
1

10

102

103

time (s)

Adapted from Fig. 11.16,

Callister & Rethwisch 3e.

104

400
0
(Fe)

0.76

600

TE (727C)

1.13

700

1400

0.022

800

727C

+Fe3C
2

Adapted from Fig. 10.28,

Callister & Rethwisch 3e.

Fe3C (cementite)

1600

6.7

C, wt%C

Hypereutectoid composition proeutectoid cementite

19

Martensite
T Martensite
bainite
fine pearlite
coarse pearlite
spheroidite
General Trends

Ductility

Strength

Possible Transformations

Coarse pearlite (high diffusion rate) and (b) fine pearlite

- Smaller T:
colonies are
larger

- Larger T:
colonies are
smaller

Bainite: Non-Equil Transformation Products

elongated Fe3C particles in -ferrite matrix
diffusion controlled
lathes (strips) with long rods of Fe3C

Martensite

800

Austenite (stable)

T(C)

400

TE

600

100% pearlite

Cementite

B100% bainite

Ferrite

10

103

%
100

10-1

50%

0%

200

105

time (s)

Bainite Microstructure
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 (considered
semi-stable below 150C).

Spheroidite: Nonequilibrium Transformation

Fe3C particles within an -ferrite matrix
diffusion dependent
heat bainite or pearlite at temperature just below eutectoid for long times
driving force reduction of -ferrite/Fe3C interfacial area

800

Austenite (stable)

T(C)

600

400

TE
100% spheroidite

Spheroidite

100% spheroidite

200
10-1

10

103

105 time

(s)
10

Pearlitic Steel partially transformed to Spheroidite

Martensite Formation
Isothermal Transformation Diagram
800

Austenite (stable)

T(C)

600
400

200
10-1

B
5
0% 0%

10
0%

M+A
M+A
M+A

10

TE

103

0%
50%
90%

105

time (s)

single phase
body centered tetragonal (BCT) crystal structure
BCT if C0 > 0.15 wt% C
Diffusionless transformation
BCT few slip planes hard, brittle
% transformation depends only on T of rapid cooling

Martensite needles
Austenite

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.

Isothermal Transformation Diagram

Iron-carbon alloy
with eutectoid
composition.

A: Austenite

P: Pearlite

B: Bainite

M: Martensite

Effect of Adding
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-topearlite transformation to longer
times;
Shift the pearlite and bainite noses
to longer times (decrease critical
cooling rate);
Form a separate bainite nose;

Plain carbon steel: primary

alloying element is carbon.

4340 Steel

nose

plain
carbon
steel

Example 11.2:
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
timetemperature
treatments:
Alloy begins at 760C and
has been held long enough
to achieve a complete and
homogeneous austenitic
structure.
Treatment (a)
Rapidly cool to 350C
Hold for 104 seconds
Quench to room temperature

Bainite,
100%

Example 11.2:
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
timetemperature
treatments:
Alloy begins at 760C and
has been held long enough
to achieve a complete and
homogeneous austenitic
structure.
Treatment (b)
Rapidly cool to 250C
Hold for 100 seconds
Quench to room temperature

Austenite,
100%

Martensite,
100%

Example 11.2:
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
timetemperature
treatments:
Alloy begins at 760C and
has been held long enough
to achieve a complete and
homogeneous austenitic
structure.
Treatment (c)
Rapidly cool to 650C
Hold for 20 seconds
Rapidly cool to 400C
Hold for 103 seconds
Quench to room temperature

Austenite,
100%
Almost 50% Pearlite,
50% Austenite

Bainite, 50%

Final:
50% Bainite,
50% Pearlite

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 (dashed 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.

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)
ferrite (soft)
C0 < 0.76 wt% C
Hypoeutectoid

Pearlite (med)
Cementite
(hard)
C0 > 0.76 wt% C
Hypereutectoid

Mechanical Properties: Fe-C System

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 -ferrite. US Steel Corp.
4340steel

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) that
has been rapidly quenched to form 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.
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 (MN).
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 ( phase solid

solution supersaturated with B
atoms; alloy is soft, weak-no ppts).

Precipitation Heat Treatment

The supersaturated solid

solution is usually heated to an
intermediate temperature T2
within the region (diffusion
rates increase).
The 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.

Solution Heat Treatment

Heat treatable aluminum alloys gain strength from
subjecting the material to a sequence of processing steps
called solution heat treatment, quenching, and aging.
The primary goal is to create sub-micron sized particles in
the aluminum matrix, called precipitates that in turn
influence the material properties.
While simple in concept, the process variations required
(depending on alloy, product form, desired final property
combinations, etc.) make it sufficiently complex that heat
treating has become a professional specialty.
The first step in the heat treatment process is solution heat
treatment. The objective of this process step is to place the
elements into solution that will eventually be called upon for
precipitation hardening.
Developing solution heat treatment times and temperatures
has typically involved extensive trial and error, partially due
to the lack of accurate process models.

Aging-microstructure
The supersaturated solid solution is
unstable and if, left alone, the excess
will precipitate out of the phase. This
process is called aging.
Types of aging:
Natural aging process occurs at room
temperature
Artificial aging If solution heat treated,
requires heating to speed up the
precipitation

Overaging
After solution heat treatment the material is ductile,
since no precipitation has occurred. Therefore, it may
be worked easily.
After a time the solute material precipitates and
hardening develops.
As the composition reaches its saturated normal state,
the material reaches its maximum hardness.
The precipitates, however, continue to grow. The fine
precipitates disappear. They have grown larger, and as
a result the tensile strength of the material decreases.
This is called overaging.

Precipitation Heat Treatment

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.
Guinier-Preston (GP) zones - Tiny clusters
of atoms that precipitate from the matrix in
the early stages of the age-hardening
process.

Hardness vs. Time

The hardness and tensile strength vary
during aging and overaging.

Influence of Precipitation Heat Treatment on

Tensile Strength (TS), %EL

2014 Al Alloy:

400
300
200
100

204C

fe
pre wer
ov cip lar
era ita ge
ge tes
d

ma
pre ny s
cip ma
ita ll
ag tes
ed

no
so n-eq
lid uil
so .
lut
ion

tensile strength (MPa)

Increasing T accelerates
process.

%EL reaches minimum

with precipitation time.

149C

1min
1h 1day 1mo 1yr
precipitation heat treat time

%EL (2 in sample)

TS peak with precipitation time.

30
20
10
0

204C

149C

1min
1h 1day 1mo 1yr
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.

Aluminum rivets

Alloys that experience significant

precipitation hardening at room
temp, 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.

Several stages in the formation of the equilibrium

PPT () phase.
(a) supersaturated solid solution;
(b) transition () PPT phase;
(c) equilibrium phase within the matrix phase.

Precipitation Hardening
Particles impede dislocation motion.
700
Ex: Al-Cu system
T(C)
Procedure:
600
+L
-- Pt A: solution heat treat
(get solid solution)
-- Pt B: quench to room temp.
(retain solid solution)
-- Pt C: reheat to nucleate
small particles within
phase.

500

+L

400

300
0 B 10

(Al)

C
20

30

40

50

wt% Cu

composition range
available for precipitation hardening

Temp.
Pt A (solution heat treat)
Pt C (precipitate

Pt B

CuAl2

At room temperature the stable state

of an aluminum-copper alloy is an
aluminum-rich solid solution () and
an intermetallic phase with a
tetragonal crystal structure having
nominal composition CuAl2 ().

Time

PRECIPITATION STRENGTHENING
Hard precipitates are difficult to shear.
Ex: Ceramics in metals (SiC in Iron or Aluminum).
precipitate
Large shear stress needed
to move dislocation toward
precipitate and shear it.

Side View

Top View

Unslipped part of slip plane

Dislocation
advances but
precipitates act as
pinning sites with
spacing S.

Slipped part of slip plane

1
Result: y ~
S
24

Aging
Aging either at room or moderately elevated
temperature after the quenching process is used to
produce the desired final product property
combinations.
The underlying metallurgical phenomenon in the
aging process is precipitation hardening. Due to the
small size of the precipitate particles, early
understanding was hampered by the lack of
sufficiently powerful microscopes to actually see them.
With the availability of the transmission electron
microscope (TEM) with nanometer-scale resolution,
researchers were able to actually image many
precipitate phases and build on this knowledge to
develop improved aluminum alloy products.

Aluminum

Aluminum is light weight,

but engineers want to
improve the strength for
high performance
applications in
automobiles and
aerospace.
To improve strength,
they use precipitation
hardening.

Age-hardening heat treatment phase diagram

Quenching
Quenching is the second
step in the process.
Its purpose is to retain the
dissolved alloying elements
in solution for subsequent
precipitation hardening.
Generally the more rapid the
quench the better, from a
properties standpoint, but
this must be balanced
against the concerns of part
distortion and residual stress
if the quench is non-uniform.

Changes in Microstructure due to quenching