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

1. Simple diffusion-dependent transformation: no

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

Phase 1 (e.g. liquid)

Nucleation of 2nd phase

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

1. Nucleation (homogeneous): What hinders nucleation? Surface energy ~ r2 E

r (size of nuclei) rc Net energy change = Internal energy ~ r3 2007, 2008 Moonsub Shim

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
surface free energy

Volume free energy change

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
rc

Sub-in to overall G equation

16 3 G = 3( Gv ) 2
*

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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 T T m
2

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
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LIQUID INSTABILITY at LOWER TEMPERTURES 2007, 2008 Moonsub Shim

MSE280

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

2007, 2008 Moonsub Shim

MSE280

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Kinetics of solid state reactions

Combining liquid instability and diffusion effects together: R t of Rate f Nucleation N l ti Contribution from liquid instability Nuclea ation rate Contribution from diffusion

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

G * n* exp kT

Q vd exp d kT

Net rate

Liquid instability 2007, 2008 Moonsub Shim

Diffusion Tm
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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.

2007, 2008 Moonsub Shim

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Kinetics of solid state reactions

2. Growth: nuclei increase in size All solid

All liquid By convention: This process can be described by:

rate

1 t1/ 2
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y = 1 exp(kt n )

Avrami eqn.

2007, 2008 Moonsub Shim k and n are time independent constants

MSE280

Kinetics of solid state reactions

Temperature dependence

Arrhenius behavior!

Q rate = A exp RT
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Growth rate

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Kinetics of solid state reactions

Combined nucleation and growth rate 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

Recall rates as fxn of T rat te T overall growth nucleation rate Flip x and y

Plot 1/rate on x-axis T

Since rate is defined as:

rate

1 t1/ 2

50% completion curve

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time MSE280

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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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MSE280

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 2007, 2008 Moonsub Shim

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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 Heating time

Spheroidite

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 at t 250oC f for 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 1 2

3 4

Essentially restart transformation process (for the remaining 50%). pearlite, 50% bainite
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5 Final composition = 50% 2007, 2008 Moonsub Shim MSE280

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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 2007, 2008 Moonsub Shim

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 ( ) slow cool

( + Fe 3 C layers + a proeutectoid phase)

moderate cool
( + Fe 3 C plates/needles)

rapid quench Martensite (BCT phase

diffusionless transformation)

Pearlite

Bainite

Martensite T Martensite bainite fine pearlite coarse pearlite spheroidite General Trends

reheat Ductil lity Tempered p Martensite

Streng gth

( + very fine Fe 3 C particles)

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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 33 bonding).
2007, 2008 Moonsub Shim MSE280

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)

vs.

PE (Mn = 106 g/mol)

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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 Cl
H2 H C C 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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