Chapter 10: Phase Transformations and

Microstructure in Fe-C Alloys

ISSUES TO ADDRESS...
• Transforming one phase into another takes time.

Fe Fe C
3
 Eutectoid
transformation (cementite)
(Austenite) +
C

FCC (BCC)
(ferrite)

• How does the rate of transformation depend on

time and Temperature?
• How can we slow down the transformation so that
we can engineer non-equilibrium structures?
• Are the mechanical properties of non-equilibrium
structures better? 1
IRON-CARBON (Fe-C) PHASE DIAGRAM

2
 Phase Transformations
• Phase Transformation: An alteration (change) in the number
and/or character of the phases.
• Phase transformation takes place in going from a liquid to solid
phase and from one solid phase to another. It is present in the
development of microstructure of any single or two phase alloys
(discussed in the previous chapter).
• Solid state reactions (transformation of one solid phase to
another) takes long time to complete
• Reason: The transformed new phase has composition and/or
crystal structure different from the parent one  some atomic
rearrangement via diffusion are required  which is slow in
solid sate
• Most of the transformation processes involves Diffusion
3
 Diffusion
• Phenomenon of material transport by atomic motion
• A necessary process for any transfer of mass within a solid. Also
necessary for transfer of mass form a liquid, a gas or from
another solid to a solid
• Mainly occurs by vacancy or interstitial mechanisms.
• Diffusion is a time dependent with diffusion rate increasing with
temperature
Initially After some time

4
Equilibrium and Non-equilibrium Phases
• Transformations can lead to EQUILIBRIUM Phases dictated by the
Phase Diagram (Chapter 9), or NON-EQUILIBRIUM or
METSTABLE Phases because of insufficient time given for
transformation
• Equilibrium:
– A system is at equilibrium when its energy is at its lowest value.
The phase diagram shows the stable equilibrium phases.
• Metastable:
– The processes required to change a system to a more stable state
(e.g. diffusion) may be extremely slow. A non-equilibrium or
metastable state may persist.

5
 Phase Transformations
Nucleation
– nuclei (seeds) act as template to grow crystals
– for nucleus to form rate of addition of atoms to
nucleus must be faster than rate of loss
– once nucleated, grow until reach equilibrium
Driving force to nucleate increases as we increase T
– supercooling (eutectic, eutectoid)
– superheating (peritectic)
Small supercooling  few nuclei - large crystals
Large supercooling  rapid nucleation - many nuclei,
small crystals

6
6
Solidification: Nucleation Processes

• Homogeneous nucleation
– nuclei form in the bulk of liquid metal
– requires supercooling (typically 80-300°C max)
• Heterogeneous nucleation
– much easier since stable “nucleus” is already
present
• Could be wall of mold or impurities in the liquid
phase
– allows solidification with only 0.1-10ºC
supercooling

7
7
 Homogeneous Nucleation & Energy Effects
Surface Free Energy- destabilizes
the nuclei (it takes energy to make
an interface)
GS  4r 2 
 = surface tension

GT = Total Free Energy

= GS + GV

Volume (Bulk) Free Energy –

stabilizes the nuclei (releases energy)
4
GV  r 3 G
3
volume free energy
G 
unit volume
r* = critical nucleus: nuclei < r* shrink; nuclei>r* grow (to reduce energy)
Adapted from Fig.10.2(b), Callister 7e. 8
8
 Solidification
r* = critical radius
 2Tm  = surface free energy
r* 
HS T Tm = melting temperature
HS = latent heat of solidification
T = Tm - T = supercooling

Note: HS = strong function of T

 = weak function of T

 r* decreases as T increases

For typical T r* ca. 100Å

9
9
10
 Rate of Phase Transformations

Kinetics - measure approach to equilibrium vs. time

• Hold temperature constant & measure conversion vs.
time

How is conversion measured?

X-ray diffraction – have to do many samples
electrical conductivity – follow one sample
sound waves – one sample

11
11
 Kinetics of Solid-State Transformations
• Phase transformation involves:
– Nucleation: Formation of very small particles or nuclei of the new phase.
Favorable locations for the formation of nuclei are grain boundaries.
– Growth: Nuclei increases in size until the equilibrium fraction given by
lever rule is attained.
• The time dependence of phase transformation rate (Kinetics of Phase
Transformation) is measured by the fraction of reaction that has occurred as a
function of time, at a constant temperature
• A S-shaped curve is obtained, when fraction of transformed material vs. log of
time is plotted at a fixed temperature

• T fixed
• Nucleation and growth stages are shown
• The rate of transformation strongly
depends on temperatures

12
 Rate of Phase Transformation
Fraction transformed, y
All out of material - done
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 Adapted from

Fig. 10.10,
Callister 7e.
Avrami rate equation => y = 1- exp (-ktn)
fraction time
transformed
– k & n fit for specific sample

By convention r = 1 / t0.5
13
13
 Kinetics of Solid-State Transformations
• The Figure below shows the effect of temperature on the Fraction
of Transformation vs. log t time plot (for recrystallization of
Copper)

• Rate of transformation often small: Equilibrium not possible!

– The phases predicted by phase diagram are not achieved
• Some time under-cooling or over-heating is required for the
transformation to take place
14
 Rate of Phase Transformations
Adapted from Fig.
10.11, Callister 7e.
(Fig. 10.11 adapted
135C 119C 113C 102C 88C 43C from B.F. Decker and
D. Harker,
"Recrystallization in
Rolled Copper", Trans
AIME, 188, 1950, p.
888.)
1 10 102 104

• In general, rate increases as T 

r = 1/t0.5 = A e -Q/RT
– R = gas constant Arrhenius
– T = temperature (K) expression
– A = preexponential factor
– Q = activation energy
• r often small: equilibrium not possible! 15
15
 Isothermal Transformation Diagrams or
T-T-T Time-Temperature-Transformation Plots
• A more convenient way to express the effect time and
temperature on the transformation is isothermal
transformation diagrams or T-T-T plots
• T-T-T Plots:
– Vertical axis  Temperature; and horizontal axis  Log time
– Two solid curves plotted:
• For time required at each temperature for the initiation or
start of transformation
• For time required for the complete conversion or
conclusion of transformation
– A dashed line correspond to 50% of transformation
completion is also plotted
• The plot is made from series of S-shaped plots at different
temperatures
16
 • Consider Fe-C system at
Eutectoid Co = 0.76 wt%C
T=675°C • Supercooling is required for
transformation to take place
(start and finish line parallel
near the eutectoid T=727°C)
Only Austenite present
• To the left of left line (0%
Pearlite) only Austenite is
present and to the right of
right line (100% Pearlite) only
Pearlite is present
• Rate r=1/t0.5 increases with
decrease in temperature
• The plot only useful for
Eutectoid composition,
different plots are required for
other compositions
isothermal transformation at 675°C
• Transformation at T = 675C° is
17
shown
 Microstructure and Property Changes in
Iron-Caron Alloys
• Let us apply the basic kinetic principles of solid-state phase transformation to
Iron-Carbon alloys
• We will see that metastable structures (intermediate between initial and final
equilibrium states) can be formed and sometimes these metastable structures
are desirable
• The main reason for the formation of the metastable phases is that for the
formation of equilibrium structures extremely slow and unrealistic cooling
rate are required.
• We will explore the relation between heat treatment, the development of
microstructure and mechanical properties.
• Following microstructures will be discussed:
1. Pearlite
2. Bainite
3. Spherodite
4. Martensite

18
 1. Pearlite:
   + Fe 3 C
• Pearlite is product of Eutectoid
0.77wt%C 6.7wt%C
Transformation: 0.022wt%C

T(°C) • Pearlite can be formed at

1600 727ºC but require
unrealistically slow cooling
1400 L
+L • It can be formed at more
1200  L+Fe3C realistic cooling rate by
austenite undercooling below 727ºC
1000
 +Fe 3C
Eutectoid:
ferrite 800 Equil. cooling: Ttransf. = 727ºC Fe 3C
727°C
T +Fe 3C
600
cementite
Undercooling by T: Ttransf. < 727ºC
0.022

0.77

6.7
400
0 1 2 3 4 5 6
(Fe) Co, wt% C
19
Example: Cooling history or heat
treatment cycle for Pearlite formation
• Eutectoid composition, Co = 0.76 wt%C
• Begin at T > 727°C
• Rapidly cool to 625°C and hold isothermally.

3.5 s 15 s 20
EUTECTOID TRANSFORMATION RATE ~ T
• Growth of pearlite from austenite:

• Reaction rate
increases with
T (the degree
undercooling)

21
 NUCLEATION AND GROWTH
• Reaction rate is a result of nucleation and growth
of crystals.
100 Nucleation rate increases with T
% Pearlite Growth
regime Growth rate increases with T
50 Nucleation
regime

0 t50 log (time)

• Examples:
pearlite
 colony  

T just below TE T moderately below TE T much below TE

Nucleation rate low Nucleation rate med . Nucleation rate high
Growth rate high Growth rate med. Growth rate low

22
 PEARLITE MORPHOLOGY
Two cases:
• Ttransformation just below TE • Ttransf well below TE
--Larger T: diffusion is faster --Smaller T: diffusion is slower
--Thick layers of  and Fe3C phases --Thin layers of  and Fe3C phases
--Pearlite is coarser. --Pearlite is finer.

- Smaller T: - Larger T:

colonies are colonies are
larger smaller

23
• For composition other than Eutectoid composition an
additional curve for pro-eutectoid transformation must
also be included on the isothermal transformation
diagram:

24
 Transformations with
Proeutectoid Materials
CO = 1.13 wt%
T(°C) C T(°C)
900 1600
d
A 1400 L

Fe3C (cementite)
800
A TE (727°C)  +L
+ 1200  L+Fe3C
700 A C (austenite)
P 1000
A
+ P   +Fe3C
600
800
727°C
T  +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) Co , wt%C
Adapted from Fig. 10.16, Adapted from Fig. 9.24,
Callister 7e. Callister 7e.

Hypereutectoid composition – proeutectoid

cementite 25 25
NON-EQUIL TRANSFORMATION PRODUCTS for Fe-C:
2. Bainite:

• Bainitie is in the form of needles and

plates consisting of (like Pearlite) Austenite
Ferrite and Cementite phases Pearlite
• T-T-T curves just extension of
pearlitic transformation curves
• At point N (nose); the transformation Bainitie
rate is highest:
– Pearlite forms above N (540-727°C)
– Bainite forms below N (215-540 °C)

26
• Bainite:
-- lathes (strips) with long
rods of Fe3C
--diffusion controlled
Fe3C
• Isothermal Transf. Diagram
(cementite)
 (ferrite)

5 m
(Adapted from Fig. 10.8, Callister, 6e. (Fig.
10.8 from Metals Handbook, 8th ed.,
Vol. 8, Metallography, Structures, and
Phase Diagrams, American Society for
Metals, Materials Park, OH, 1973.)

27
3. Spheroidite:
• Spheroidite microstructure forms 
when Pearlite or Bainite is heated (ferrite)
and left at temperature below
eutectoid for a sufficiently long Fe3C
period of time (cementite)

• E.g: 700°C for 18-24 hours

• Fe3C phase forms sphere-like
60 m
particles embedded in continuous 
phase matrix (unlike layered
structure of Pearlite)
Summary:
-- crystals with spherical Fe3C
--diffusion dependent.
--heat bainite or pearlite for long times
-- Driving Force is reduction in
interfacial area between phases
28
4. Martensite:
• Martensite is formed when Austenite is rapidly cooled (or quenched)
to a relatively low temperature
• Martensite is a non-equilibrium SINGLE PHASE structure and is a
result of diffusion-less transformation of Austenite  The martensitic
transformation occurs when the quenching rate is rapid enough to
prevent carbon diffusion  Otherwise Ferrite and Cementite will form
• The transformations to Pearlite, Bainite, and Martrensite are
competitive and may be taking place simultaneously (all of them can
coexist)
• In martensitic transformation FCC Austenite experience a polymorphic
transformation to a body-centered-tetragonal (BCT) martensite (an
elongated BCC structure)
• Martesnite although a non-equilibrium structure can exist indefinitely
at room temperature, however, it will transform by diffusion if the
temperature is increased
29
 Martensite (continued)
• Martensitic transformation does not
involve diffusion, so it occurs very
quickly
• Figure shows a general isothermal
transformation diagram for a plain-
carbon steel
• Since martenistic transformation is
time independent (does not involve
time) it appear as straight line in the
Figure
• The beginning of the
transformation is represented by
horizontal line M (start). Two
other horizontal dashed lines M
(50%) and M (90%) indicate %age
of phase transformation
• The temperature of theses lines
vary with alloy composition
30
 Martensite (continued)
• Martensite:
--(FCC) to Martensite (BCT)
(involves single atom jumps)
x
Fe atom potential

60 m
x x
sites x x C atom sites
x

• Isothermal Transf. Diagram

Martentite needles
Austenite

•  to M transformation..
-- is rapid!
-- % transf. depends on T only
(not on time)

31
 Martensite Formation

 (FCC) slow cooling (BCC) + Fe3C

quenc
h tempering
M (BCT)

M = martensite is body centered tetragonal (BCT)

Diffusionless transformation BCT if C > 0.15 wt%
BCT  few slip planes  hard, brittle

32
32
 Phase Transformations of Alloys
Effect of adding other elements
Change transition temp.

Cr, Ni, Mo, Si, Mn

retard    + Fe3C
transformation

Adapted from Fig. 10.23, Callister 7e.

33
33
Cooling Curve
plot temp vs. time

Adapted from
Fig. 10.25,
Callister 7e.

34
34
 Summary of Microstructures
• Pearlite:
– Pearlite is a layered structure of Ferrite and Cementite Phases
• Bainite:
– Bainitie is in the form of needles or plates consisting of Ferrite and
Cementite phases
• Spherodite:
– Fe3C phase forms sphere-like particles embedded in continuous -
phase matrix
• Martensite:
– A Single Phase
– BCT Structure formed by diffusion-less transformation

35
Example 10.1: Specify the final microstructure for the
given thermal or heat treatment history

Co=Eutectoid Composition

36
Example 10.1: Specify the final microstructure for the
given thermal or heat treatment history

Result: 100% Bainite

37
COOLING EX 10.1: Fe-C SYSTEM (2)

Result: 100% Martensite

38
COOLING EX 10.1: Fe-C SYSTEM (3)

Result: 50% Pearlite and

50% Bainite
39
 Dynamic Phase Transformations
On the isothermal transformation diagram for 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

40
40
 Example Problem for Co = 0.45 wt%
a) 42% proeutectoid ferrite and 58% coarse pearlite

first make ferrite 800

A
A+
T (°C)
then pearlite
A+P
600 P
B
A+B
course pearlite A
400 50%
 higher T M (start)
M (50%)
M (90%)
200

Adapted from
Fig. 10.29,
Callister 5e. 0
0.1 10 103 105
time (s)
41
41
 Example Problem for Co = 0.45 wt%
b) 50% fine pearlite and 50% bainite

first make pearlite 800

A
A+
T (°C)
then bainite
A+P
600 P
B
A+B
fine pearlite A
50%
 lower T
400
M (start)
M (50%)
M (90%)
200

Adapted from
Fig. 10.29,
Callister 5e. 0
0.1 10 103 105
time (s)
42
42
 Example Problem for Co = 0.45 wt%
c) 100 % martensite – quench = rapid cool
d) 50 %
800 A+
martensite A
T (°C)
and 50 % A+P
600 P
austenite B
A+B
A
400 50%
M (start)
M (50%)
M (90%) d)
200

Adapted from
Fig. 10.29, c
Callister 5e. 0
0.1 ) 10 103 105
time (s)
43
43
 Mechanical Behavior of Iron-Carbon Alloys
• We have discussed the effect of Processing or Heat Treatment
on the Microstructure
• We will now discuss the relationship between Microstructure
and Mechanical Properties
• Microstructure discussed included:
– Fine and Coarse Pearlite
– Spherodite
– Bainite
– Martensite
• Except Martensite two phases, i.e., Ferrite and Cementite are
present in the different microstructures
• CEMENTITE IS MUCH HARDER BUT MORE BRITTLE
THAN FERRITE
44
1. Pearlite Mechanical Properties:
• Increasing the fraction of Fe3C (cementite) in a steel alloy while holding other
micro-structural elements constant results in a harder and stronger material
• The Yield Strength, Tensile Strength and Hardness increase with increasing
weight percent carbon, while the Ductility (in terms of %Elongation and
%Area Reduction) and Toughness (or impact energy) decreases
• The layer thickness of the ferrite and cementite phase also effect mechanical
properties

Fine Pearlite is Harder and Stronger than Coarse Pearlite

(but less ductile)
• Reason:
– With fine Pearlite greater phase boundary area per unit volume exist between
Ferrite and Cementite
– Strong and rigid cementite phase restricts the deformation of the softer ferrite
phase in regions adjacent to the phase boundary, and the phase boundaries also
resist the dislocation motion
45
Mechanical Properties of Pearlite

46
Mechanical Properties of Pearlite

47
2. Spherodite Mechanical Properties:
• Spherodite has less strength and hardness than Pearlite, however, it
has high ductility (Spherodite steel are the softest and weakest steels)
• Reason: The spherical cementite phase in spherodite has less Phase Boundary
Area leading to less reinforcement effect and less resistance to dislocation motion

48
3. Bainite Mechanical Properties:
• Because Bainitic steels have a finer structure (i.e. smaller -
Ferrite and Fe3C particles), they are generally stronger and harder
than Pearlitic Steels; They exhibit a desirable combination of
strength and ductility

49
4. Martensite Mechanical Properties:
• Martensite is the hardest and strongest microstructure for a
given steel alloy
• Also the most brittle exhibiting negligible ductility
• High strength, hardness and brittleness of martensite is due to
carbon trapped in solid-solution; not due to the microstructure as
was the case in other Pearlitic Steels  Interstitial carbon atoms
hinder dislocation motion
• Austenite is slightly denser than Martensite, therefore, during
phase transformation, there is a net volume increase
• Large pieces that are rapidly quenched may crack as a result of
internal stresses due to non-homogeneous cooling

50
Martensite Mechanical Properties (continued):

• Fine Pearlite vs Martensite:

• Hardness: fine pearlite << martensite.

51
 Tempered Martensite
• As quenched pure martensite is very hard and brittle  cannot be used
for most applications
• Tempering: A heat treatment to improve the ductility and toughness
of martensite and relieve internal stresses produced during quenching
• Procedure: Accomplished by heating a martensitic steel to a
temperature below the eutectoid for a specified time period. Normally
tempering is carried out at temperatures between 250-650C
• Following reaction takes place by DIFFSUION (Allowing carbon to
leave the martensite and form fine precipitates of iron carbide):
martensite (BCT, single phase)  tempered martensite (+Fe3C phases)
• Tempered martensite has microstructure very similar to spherodite
(spherical cementite particles) but the cementite particle size is much
smaller
• Smaller the size of particles more phase boundary area more
strengthening effect
• Higher the tempering temperature larger the particles size lesser the
52
strength
 TEMPERING MARTENSITE
• reduces brittleness of martensite,
• reduces internal stress caused by quenching.

53
Quenched and Tempered Steel

900ºC
Temperature

Temper
200ºC

Quench
(Fast Cool)

Time

54
 Quenched and Tempered Steel

Normalised/Pearlitic Steel Quenched & Tempered Steel

55
 Alloying of Steels
• Alloying slows the diffusion
controlled phase transformations in
steel
– E.g. Cr, Mo
• This allows martensite to be Temperature
obtained for slower cooling rates,
which minimises distortion and 1% transformed
allows larger components to be (plain carbon steel)
treated.
1% transformed
(alloy steel)

Ms
Effect of
Alloying
Time
56
SUMMARY: PROCESSING OPTIONS

57
 Home Work # 5
ME 207: Engineering Metallurgy

Attempt Text (Callister 6th edition) Problems:

10.9, 10.10, 10.11, 10.14, and 10.15

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