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Phase Transformation
Phase Transformation
Martensite - BCT
Austenite - FCC
Chapter 11
Phase
Transformations
Fe3C (cementite)- orthorhombic
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
No change in # of phases
No change in composition
Example: solidification of a pure metal, allotropic transformation,
recrystallization, grain growth
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 80-300°C).
• 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 (0.1-10ºC).
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 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 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 together-
similar 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
energy, GS). G = GS + GV
Transforming one phase into another takes time.
Fe Fe C
g Eutectoid 3
transformation (cementite)
(Austenite) +
C
a
FCC (ferrite) (BCC)
Homogeneous Nucleation & Energy Effects
Surface Free Energy- destabilizes
the nuclei (it takes energy to make
an interface)
GS 4r 2 g
g = surface tension
r* decreases as T increases
For typical T r* ~ 10 nm
Transformations & Undercooling
• Eutectoid transformation (Fe-Fe3C system): g a + Fe3C
• For transformation to occur, must 0.76 wt% C 6.7 wt% C
cool to below 727°C 0.022 wt% C
T(°C)
1600
d
1400 L
g g +L
1200 1148°C L+Fe3C
Fe3C (cementite)
(austenite)
1000
a g +Fe3C
Eutectoid:
ferrite 800 Equil. Cooling: Ttransf. = 727ºC
727°C
T a +Fe3C
600
Undercooling by Ttransf. < 727C
0.022
0.76
400
0 1 2 3 4 5 6 6.7
(Fe) C, wt% C
FRACTION OF TRANSFORMATION
• Fraction transformed depends on time.
100
T = 675°C
50
0
1 10 2 10 4 time (s)
T(°C)
Austenite (stable)
TE (727C)
700 Austenite
(unstable)
600 Pearlite
isothermal transformation at 675°C
500
400
time (s)
1 10 10 2 10 3 10 4 10 5
Eutectoid Transformation Rate ~ T
• Transformation of austenite to pearlite:
Diffusion of C
Austenite (g) cementite (Fe3C) during transformation
grain a Ferrite (a)
boundary a g a
g a
a g
a
pearlite g
growth a
a
direction
a
• For this transformation, 100
Carbon
diffusion
rate increases with ( T) 600°C
% pearlite
(T larger)
[Teutectoid – T ]. 50 650°C
675°C
(T smaller)
0
• Examples:
5
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
(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
d
1400 L
Fe3C (cementite)
g g +L
1200 L+Fe3C
(austenite)
1000
g +Fe3C
800
727°C
T a +Fe3C
600
0.022
0.76
400
1.13
0 1 2 3 4 5 6 6.7
(Fe)
C, wt%C
Martensite
T Martensite
Strength
Ductility
bainite
fine pearlite
coarse pearlite
spheroidite
General Trends
Coarse pearlite (high diffusion rate) and (b) fine pearlite
10
Pearlitic Steel partially transformed to Spheroidite
Martensite Formation
• Isothermal Transformation Diagram
800 Austenite (stable)
T(°C) A TE
P
600
400 A B
0%
200 M+A 50%
M+A 90%
M+A
10-1 10 103 105 time (s) Martensite needles
Austenite
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
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
4340 Steel
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-
pearlite transformation to longer
times;
Shift the pearlite and bainite noses nose
to longer times (decrease critical plain
cooling rate); carbon
Form a separate bainite nose; steel
Treatment (a)
Rapidly cool to 350 ˚C
Hold for 104 seconds
Quench to room temperature
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
time–temperature
treatments:
Alloy begins at 760˚C and
has been held long enough Austenite,
to achieve a complete and 100%
homogeneous austenitic
structure.
Treatment (b)
Rapidly cool to 250 ˚C
Hold for 100 seconds Martensite,
Quench to room temperature 100%
Example 11.2:
Iron-carbon alloy with Austenite,
eutectoid composition. 100%
Specify the nature of the Almost 50% Pearlite,
final microstructure (% 50% Austenite
bainite, martensite, pearlite
etc) for the alloy that is
subjected to the following
time–temperature
treatments:
Alloy begins at 760˚C and Bainite, 50%
has 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)
ferrite (soft) Cementite
(hard)
C0 < 0.76 wt% C C0 > 0.76 wt% C
Hypoeutectoid 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 a-ferrite. US Steel Corp.
4340 steel
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.
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 T0 and dissolve B phase.
Rapidly quench to T1
Nonequilibrium state (a phase
solid solution supersaturated with
B atoms; alloy is soft, weak-no
ppts).
Precipitation Heat Treatment – the 2nd stage
The supersaturated a solid
solution is usually heated to an
intermediate temperature T2
within the a+b region (diffusion
rates increase).
The b 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.
• Ex: Al-Cu system 700
T(°C) L CuAl2
• Procedure:
-- Pt A: solution heat treat
600 a+L a q+L
A
(get a solid solution) 500 q
-- Pt B: quench to room temp. C a+q
400
(retain a solid solution)
-- Pt C: reheat to nucleate 300
small q particles within 0 B 10 20 30 40 50
(Al) wt% Cu
a phase. composition range
available for precipitation hardening
Time
Pt B
Precipitation Heat Treatment – the 2nd stage
1
• Result: y ~
S
24
Several stages in the formation of the equilibrium
PPT (q) phase.
(a)supersaturated a solid solution;
(b)transition (q”) PPT phase;
(c) equilibrium q phase within the a matrix phase.
Influence of Precipitation Heat Treatment on
Tensile Strength (TS), %EL
• 2014 Al Alloy:
• TS peak with precipitation time. • %EL reaches minimum
• Increasing T accelerates with precipitation time.
process.
tensile strength (MPa)
30
%EL (2 in sample)
400
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.
Aluminum rivets