11/3/2008

MSE 280: Introduction to Engineering Materials

Phase Transformations
Reading:
g Callister Ch. 11

Time and temperature dependence of phase

transformations.
Engineering non-equilibrium structures.
Differences in mechanical properties between
equilibrium and non
non-equilibrium
equilibrium structures
(steel).
Phase transformations in polymers.
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Phase transformation

Takes time (transformation rates: kinetics).

Involves movement/rearrangement of atoms.
Usually involves changes in microstructure.

1. Simple diffusion-dependent transformation: no

change in number or compositions of phases present (e.g.
solidification of pure elemental metals, allotropic transformation,
recrystallization, grain growth).

2. Diffusion-dependent transformation: transformation

with alteration in phase composition and
and, often
often, with changes in
number of phases present (e.g. eutectoid reaction).

3. Diffusionless transformation: e.g. rapid T quenching to

trap metastable phases.
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Kinetics of solid state reactions

Nucleation of 2nd phase

Phase 1 (e.g. liquid)

1. Nucleation (homogeneous): What hinders nucleation?

Surface energy ~ r2
E

r (size of nuclei)
rc
Net energy change =
Internal energy ~ r3

Growth
Initially the surface
energy dominates
but eventually bulk
energy takes over.
Need nuclei larger
than critical radius
before growth
occurs!

4 3
r Gv + 4r 2
3
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Kinetics of solid state reactions

Critical nucleus size (rc) and the activation energy (G*)
Net energy
gy = G =

4 3
r Gv + 4r 2
3

Volume
free energy
change

surface
free energy

Take the derivative and set equal to zero to find max.

d (G ) 4
= ( Gv )(3r 2 ) + 4 ( 2r ) = 0
dr
3

rc =

2
Gv

Sub-in to overall G equation

16 3
G =
3( Gv ) 2

rc

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Kinetics of solid state reactions

In terms of heat of fusion Hf (i.e. energy release upon solidification):

Gv =

H f (Tm T )
Tm

Tells us how Gv changes

g with temperature
p
T1 > T2

With this definition, we then have:

rc =

2
H f

Tm

Tm T

16 3 Tm

G =
2
3H f Tm T

As T decreases both rc
and G* become smaller

Number of stable nuclei:

G *

n* exp
kT

LIQUID INSTABILITY at LOWER TEMPERTURES

2007, 2008 Moonsub Shim

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Kinetics of solid state reactions

We also need to consider diffusion:
Faster diffusion leads to more collisions between atoms.
More collisions means higher probability of atoms sticking to each other.
Recall diffusion

Q
D = Do exp d
kT

Then, the frequency of atoms sticking together is directly related to diffusion:

Frequency of attachment:

Q
vd exp d
kT

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Kinetics of solid state reactions

Combining liquid instability and diffusion effects together:

G *
dN
Q
= Kn * vd = K ' exp
exp d
dt
kT
kT

G *

n* exp
kT

Liquid instability

Q
vd exp d
kT

Contribution
from liquid
instability
Nuclea
ation rate

R t off Nucleation
Rate
N l ti

Contribution
from
diffusion

Net rate

Diffusion

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Tm

T
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Example problem: critical radius

and activation energy for nucleation
A) If pure liquid gold is cooled to 230oC below its melting
point, calculate the critical radius and the activation
energy.

B) Calculate the number of atoms per nucleus of this

critical size. Au is FCC with a = 0.413nm.

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Kinetics of solid state reactions

2. Growth: nuclei increase in size
All solid

All liquid
By convention:

rate

This process can be described by:

y = 1 exp(kt n )

Avrami eqn.

1
t1/ 2
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k and n are time independent constants

MSE280

Kinetics of solid state reactions

Arrhenius behavior!

Q
rate = A exp

RT

Growth rate

Temperature dependence

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Kinetics of solid state reactions

rate

Combined nucleation and growth rate

Overall rate of
transformation

growth

nucleation

T
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Isothermal transformation
Initial rapid T change then allow transformation to occur at constant T
Eutectoid reaction
(0.76wt%C)
(0 76wt%C)

cool
heat

(0.022wt%C)
(0 022wt%C) + Fe3C (6
(6.70wt%C)
70wt%C)

Pearlite

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Pearlite

T vs. t
transformation
plot (TTT plot)

Where does the line shape

(e.g. 50% completion curve)
come from?

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TTT plot and relation to rates

ratte

Recall rates as fxn of T

T
overall

growth

Flip x and y

nucleation

Since rate is defined as:

rate

Plot 1/rate on x-axis

rate

t1/ 2
50% completion curve
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Pearlite
Initial rapid
T quench

Constant T during
transformation

Do the microstructures change when we quench to different T?

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Pearlite
Recall limited diffusion in solids leading to layered structure

Fill in the blank

coarse pearlite structure.
Initial rapid quench to higher T will lead to ________
Initial rapid quench to lower T will lead to _________
pearlite structure.
fine
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Bainite & Martensite

Coarse pearlite
Fine pearlite
Bainite

Bainite: needles or plates consisting

of cementite and ferrite (much finer
than fine pearlite).
M t
Martensite:
it Formed
F
d when
h quenched
h d
rapid enough to prevent C diffusion.
Body-centered tetragonal.
Bainite
Martensite

Martensite

BCT structure of martensite

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Spheroidite
Forms when pearlite or bainite structures are heated (below
eutectoid T) for an extended period of time.

Pearlite

Partially transformed

Spheroidite

Heating time

Why do spherical shapes dominate at the end?

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Example problem
1. What is the microstructure
of steel that has been:
(i) instantaneously
quenched to 560oC
(ii) held for 2s then
(iii) Instantaneously
quenched to 250oC?
2. What happens if the
resulting structure is held
att 250oC ffor 1d
1day?
?
3. What happens if the
structure from part 1 is
quenched directly to RT?

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Example problem
Specify final microstructure(s)
present and approximate
percentage of each for
f ll i processing
following
i condition
diti
beginning at 760oC.
1. Rapid cool to 650oC.
2. Hold 20s.
3. Rapid cool to 400oC.
4. Hold for 103s.
5. Quench to RT.
2 ~50% transformation to p
pearlite.
4

3
4

Essentially restart
transformation process (for
the remaining 50%).

5 Final composition = 50%

pearlite, 50% bainite

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TTT diagrams at different compositions

Eutectoid composition

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Hypereutectoid composition
e.g. 1.13wt%C

+ Fe3C

+ Fe3C

1.13wt%C
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Example
Starting with austenite
having 1.13 wt%C in
composition, what cooling
path will produce 6
6.2%
2%
mass fraction proeutectoid
cementite, 46.9 % mass
fraction coarse pearlite,
46.9% mass fraction
Bainite?

TTT diagram for 1.13wt%C Fe-C alloy

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1.13

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Continuous Cooling Transformation

Recall % transformed vs. time

Transformation at constant T (T1)

Complete transformation
occurs faster due lower final
T.
Nucleation to growth transition is
slower since it is not cooled
instantaneously initially.
What happens when T is varied as transformation occurs?
(e.g. continuously cool from To to T2 at a constant rate)
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Continuous Cooling Transformation

Recall how we arrived at TTT
diagram for isothermal
cooling
g
What happens when T varies
during transformation?

Looks like the curves

are shifted down and
t the
to
th right.
i ht

675oC
(isothermal)

Constant
cooling rate
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CCT diagrams

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Microstructures from continuous cooling

Note: usually no Bainite is formed in continuous cooling

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Mechanical behavior of plain carbon steel

Fine pearlite

Strength increases and ductility decreases with C content.

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How do processing conditions change

mechanical properties?
coarse pearlite
Fine pearlite
Bainite

Extended
heating
g
Spheroidite

Fast quench: higher strength, lower ductility.

Slow quench: lower strength, higher ductility.
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Austenite ( )
moderate
cool

slow
cool
Pearlite

Bainite
( + Fe 3 C plates/needles)

Martensite
T Martensite
bainite
fine pearlite
coarse pearlite
spheroidite

Martensite
(BCT phase
diffusionless
transformation)

reheat
Ductillity

Strenggth

( + Fe 3 C layers + a
proeutectoid phase)

rapid
quench

Tempered
p
Martensite
( + very fine
Fe 3 C particles)

General Trends
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Phase transformation in polymers

y
Crystallization.
Melting.
Glass transition.

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Crystallization
Many polymer crystallization processes are similar
kinetics as discussed earlier in phase transformations
((Avrami equation).
q
)
Some differences:
Nucleation and growth
Random entangled chains become ordered and aligned.

Usually 100% crystallization is not achievable.

Crystallization can be induced by strain.

P l
Polypropylene
l
Normalized!

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Melting
Melting occurs over a range of temperature
Melting temperature (Tm) depends on:
1. History of the specimen (e.g. how
it was crystallized).
2. Heating rate: faster heating rate
leads to higher Tm.
3. Chemical composition
Bulky side groups lead to
higher Tm (hindered rotation
and flexibility).
Polar side groups lead to higher
Tm (stronger secondary
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Melting continued
Melting temperature depends on:
4. Molecular Weight: at relatively
low MW, Tm increases with MW.
5. Degree of branching: more
branching leads to lower Tm.

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Melting Temperature: example problems

For each polymer pair, determine which will have higher melting temperature.
1. Branched polyethylene

vs.

Linear polyethylene

2. Polyethylene (n = 5000)

vs.

PMMA (n = 5000)

3. Polystyrene (Mn = 80,000g/mol) vs.

Polystyrene (Mn = 800g/mol)

4. PE (Mn = 107 g/mol)

PE (Mn = 106 g/mol)

vs.

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Glass Transition
Transition from rubbery to rigid state.
Abrupt changes in:
Stiffness.
Viscosity.
Vi
it
Coefficient of thermal expansion
Glass transition temperature (Tg) depends on:
1. Chemical composition
Bulky groups increase Tg.
Polar groups increase Tg.
2 Molecular weight: higher MW higher Tg.
2.
3. Degree of branching: higher density of
branching higher Tg (entangled branches
restrict chain motion).
4. Crosslinking increases Tg due to chain
motion restriction.
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Glass transition: example problems

For each polymer pair, determine which will have higher
glass transition temperature.
g
p
H2
H C
C

H2
H C
C

Cl

CH3

a) poly(vinyl chloride)

vs.

polypropylene

b) polystyrene

vs.

polypropylene

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Concepts to remember
Kinetics of solid state reaction:
nucleation (surface vs volume energies) and growth.
Avrami equation.
Rates.

Isothermal transformation.
TTT plots and relation to reaction rates.
Microstructures of Fe-C systems at different cooling
conditions:
Fine and coarse pearlite, bainite, spheroidite and martensite.

CCT diagrams.
Processing effects on mechanical properties.
Phase transformation in polymers (consider similarities
and differences with metals).
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