Development of Microstructure and Alteration of

Mechanical Properties

Martensite - BCT

Ferrite - BCC

Austenite - FCC
Fe3C (cementite)- orthorhombic
Chapter Outline:
 Homogeneous Nucleation & Energy Effects
Surface Free Energy- destabilizes
the nuclei (it takes energy to make
an interface)
DGS  4r 2 
 = surface tension

DGT = Total Free Energy

= DGS + DGV

Volume (Bulk) Free Energy –

stabilizes the nuclei (releases energy)
4
DGV  r 3DG
3
volume free energy
DG 
unit volume
r* = critical nucleus: for r < r* nuclei shrink; for r >r* nuclei grow (to reduce energy)
 Nucleation of a spherical solid particle in a liquid

 The change in free energy DG (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, DGV); and
2) the solid-liquid phase boundary (surface free
energy, DGS). DG = DGS + DGV

 Transforming one phase into another takes time.

Fe Fe C
 Eutectoid 3
transformation (cementite)
(Austenite) +
C
a
FCC (ferrite) (BCC)
 Nucleation and Growth
• Rate is a result of nucleation and growth of crystals.
with
with

Where, T = time temperature

• Rate is depends on temperature. Example :

TE is eutectoid temperature
 Solidification
r* = critical radius
 2Tm  = surface free energy
r* 
DHf DT Tm = melting temperature
DHf = latent heat of solidification (fusion)
DT = Tm - T = supercooling

Note: DHf and  are weakly dependent on DT

 r* decreases as DT increases

For typical DT r* ~ 10 nm
 Transformations & Undercooling ( Fast cooling)
• Eutectoid transformation (Fe-Fe3C system):   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
  +L
1200 1148°C L+Fe3C

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

0.76

400
0 1 2 3 4 5 6 6.7
(Fe) C, wt% C
 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 surface area increases
t0.5 & nuclei grow

log t

Fraction transformed depends on time

For comparison among different

temperatures or materials - standard
A = a temperature dependent constant
Q = an activation energy for the
particular reaction
k = time dependent constant for
particular reaction
R = the gas constant

135C 119C 113C 102C 88C 43C

1 10 102 104
Fast cooling

Fast heating
 Eutectoid Transformation Rate ~ DT
• Transformation of austenite to pearlite:
Diffusion of C
Austenite () cementite (Fe3C) during transformation
grain a Ferrite (a)
boundary a  a
 a
a 
a
pearlite 
growth a
a
direction
• For this transformation, 100 a
Carbon
rate increases with ( DT) % pearlite 600°C diffusion

[Teutectoid – T ]. (DT larger)

650°C
50
675°C
(DT smaller)
0

Coarse pearlite  formed at higher temperatures – relatively soft

( carbon diffusion rate is high – can diffuse long distance)
Fine pearlite  formed at lower temperatures – relatively hard
( carbon diffusion rate is low – diffuse only short distance)
 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.

The thickness of the

ferrite and cementite
layers in pearlite
is ~ 8:1.

The absolute layer

thickness depends on
the temperature of the
transformation.

The higher the

temperature, the thicker
Austenite-to-Pearlite the layers --- bcz high
carbon diffusion rate
Coarse pearlite (high diffusion rate) and (b) fine pearlite

- Smaller DT: - Larger DT:

colonies are colonies are
larger smaller
 Transformations Involving
Noneutectoid Compositions
Consider C0 = 1.13 wt% C
T(°C)
1600
d
1400 L

Fe3C (cementite)
  +L
1200 L+Fe3C
(austenite)
1000
 +Fe3C
800
727°C
DT a +Fe3C
600
0.022
0.76

400
1.13

0 1 2 3 4 5 6 6.7
(Fe)
C, wt%C

Proeutectoid cementite will coexist with pearlite.

Proeutectoid phase curve must be added
 2. Above N line : pearlite will form
(540°C - 727°C)

1. Rate of transformation is max at N

3. Below N line : bainite will form

(215°C - 540°C)
 Pearlitic Steel partially
transformed to Spheroidite
 Austenite (white region)

Martensite
(dark needle
like structure)

 BCT  few slip planes  hard,

brittle
 % transformation depends only on T
of rapid cooling
 Complete Isothermal Transformation Diagram

Iron-carbon alloy
with eutectoid
composition.

 A: Austenite
 P: Pearlite
 B: Bainite
 M: Martensite
 F: Proeutectoid ferrite
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 to longer
times (decrease critical cooling rate);
 Form a separate bainite nose;
nose
 4340 steel: Chemical compositions:
plain
carbon
steel

 Plain carbon steel: primary alloying

element is carbon.
Example 1.1:
 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 following
time–temperature Bainite,
treatments: 100%
 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 1.2:
 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 1.3:
 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 (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.
 Example:

 Moderately rapid and slow

cooling curves are
superimposed on a
continuous cooling
transformation diagram of a
eutectoid iron-carbon alloy.
 The transformation starts All austenite
after a time period completely
transformed into
corresponding to the Pearlite So,
intersection of the cooling Bainite will not
form
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
 Proeutectoid ferrite line

 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.

F: Proeutectoid ferrite
 Mechanical Properties
• Hardness
• Brinell, Rockwell
• Yield Strength
• Tensile Strength
• Ductility
• % Elongation
• Effect of Carbon Content
The possible microstructures in iron-carbon alloys

1. Fine pearlite

2. Coarse pearlite
Ferrite + Cementite
3. Spheroidite
Cementite much harder and brittle than ferrite
4. Bainite

5. Martensite
 Mechanical Properties: Influence of Carbon Content

Pearlite (med) Pearlite (med)

Proeutectoid: ferrite (soft) Proeutectoid: Cementite
(hard)
C0 < 0.76 wt% C C0 > 0.76 wt% C
Hypoeutectoid Hypereutectoid

Cementite is
harder and more
brittle than ferrite

Increasing
cementite
fraction therefore
makes harder,
less ductile
material.
Mechanical Properties: Influence Microstructures

- Larger DT:- Smaller DT:

Fine pearlite is harder and stronger than coarse pearlite: colonies arecolonies are
smaller larger

Strong and rigid cementite will district the deformation of softer ferrite at the
boundaries. Cementite reinforce ferrite effect

Greater boundary area in fine pearlite strong reinforcement

 Spheroidite

 Spheroidite less stronger and harder than pearlite

 But ductility is higher than pearlite

Due to
 Less cementite-ferrite boundary in spheroidite compared to pearlite
 Low cementite reinforcement effect and less impedance to dislocation
motion.

Spheroidized steels are ductile and tough

 Bainite
 Bainite stronger and harder than pearlite

Due to
 Due to finer structure than pearlite
 High cementite reinforcement effect ------ restrict dislocation motion.

Bainite steels are strong but less ductile

 Martensite
 Martensite is the strongest, hardest and most brittle microstructure in steels

Due to
 NOT due to finer structure….
 But because of the effectiveness of the interstitial carbon atoms in hindering
dislocation motion ------ solid solution effect.
 AND relatively few slip system in BCT

Strong and hard but brittle

---- for BCT
 Effect of tempering temperature and time

 Higher temperature -----> accelerate carbon diffusion ----->increase cementite particle

size --------> softening
 Longer tempering time -----> growth and coalescence of cementite particles ----> low
hardness.
Hardness and Strength
increase

Ductility
In Summary: Microstructure and strength, ductility relation

Martensite
T Martensite
Strength

Ductility
bainite
fine pearlite
coarse pearlite
spheroidite
General Trends
Example problem: Relation between microstructure and hardness

Relation between hardness and tensile strength

Tensile strength (MPa) = 3.45 X HB
Thermal processing / heat treatments
of metals
Purpose : To alter mechanical properties

Processes (Heat treatments)

1. Annealing
 Process annealing
 Stress relief
 Normalizing
 Full annealing
 Spheroidizing

2. Hardening ( 2 stage heat treatment)

 Solution heat treatment

 Precepition hardening
- Reduce strain and stress
- Altering microstructure
------> refer to continuous cooling diagram
- Softening
- Hardening
WHY HARDNESS CHANGES W/POSITION
• The cooling rate varies with position.

Chapter 11-
 Water  Faster
 Severity
Oil (warping,
Air craking)

4140 steel

Plain carbon steel

Effect of alloying elements

Effect of size ( diameter)
 PRECIPITATION HARDENING
Precipitation strengthening mechanism

• Hard precipitates are difficult to shear.

Ex: Ceramics in metals (SiC in Iron or Aluminum).
 Lattice distortions

Impede dislocation motion

Increase hardness and

strength
 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 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.
 Example of
Precipitation
Hardening :
in Al-Cu system

Phase transition
during precipitation
heat treatment
 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
due to overaging (continued Small solute-enriched regions in a solid
particle growth). 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:

• 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 on
strength and ductility during
precipitation hardening

 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.
 Strengthening process is accelerated
as temperature is increased.
 Ductility is reduced instead of
increment in strength
 Natural Aging

Ex: 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.
 Example of Precipitation Hardening :
Al-Cu system
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

 The heat treatment process
• Particles impede dislocation motion.
• Ex: Al-Cu system 700
• Procedure: T(°C) L CuAl2
600 a a+L
-- Pt A: solution heat treat q+L
A
(get a solid solution) 500 q
-- Pt B: quench to room temp. a+q
400 C
(retain a solid solution)
-- Pt C: reheat to nucleate 300
small q particles within 0 10 20 30 40 50
(Al) B
a phase. composition range
wt% Cu
available for precipitation hardening

Temp. At room temperature the stable state

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

Time
Pt B
 The mechanism

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.
 SUMMARY OF
PRECIPITATION HARDENING
 1st step - Solution Heat Treatment

• The first step in the precipitation hardening 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.
 2nd step - 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

 3rd step - 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.
 Aging-microstructure

• The supersaturated solid solution is unstable and if, left alone, the
excess q will precipitate out of the a 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.