Lecture 20

Phase Diagrams/Phase
Transformation

ChE 31000

04/26/21 Lecture 20 Slide 1 Intro to Materials Science ChE 31000

The Iron-Iron Carbide Phase Diagram

BCC
Eutectic
Nonmagnetic

FCC

Eutectoid

Magnetic

BCC
Intermediate compound
0.022
iron-rich portion
04/26/21 Lecture 20 Slide 2 Intro to Materials Science ChE 31000

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 Ferrite & Austenite

(Copyright 1971 by United States Steel Corporation.)

04/26/21 Lecture 20 Slide 3 Intro to Materials Science ChE 31000

Ferrous Alloys
• Iron: < 0.008 wt% C

• Steel: 0.008 - 2.14 wt% C; normally <1.0 wt%.

• Cast irons: 2.14 - 6.70 wt% C; normally < 4.5 wt%.

04/26/21 Lecture 20 Slide 4 Intro to Materials Science ChE 31000

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 Develop Microstructure in Fe-C Alloys
A eutectoid steel showing the pearlite

Eutectoid

Pearlite

(From Metals Handbook, Vol. 9, 9th edition,

Thickness ~ 8:1 Metallography and Microstructures, 1985.
Reproduced by permission of ASM International,
Materials Park, OH.)

Pearlite has properties intermediate

between those of the soft, ductile
0.76 ferrite and the hard, brittle cementite
04/26/21 Lecture 20 Slide 5 Intro to Materials Science ChE 31000

Formation of pearlite from austenite

Carbon atoms need diffuse only
minimal distances with the formation
of pearlite structures.

04/26/21 Lecture 20 Slide 6 Intro to Materials Science ChE 31000

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 Hypoeutectoid Alloys
The fraction of proeutectoid α?

The fraction of pearlite?

The fraction of total α?

T U X 𝑈 𝑋
𝑊
𝑇 𝑈 𝑋

The fraction of total Fe3C?

𝑇
𝑊
𝑇 𝑈 𝑋

0.76
0.022
04/26/21 Lecture 20 Slide 7 Intro to Materials Science ChE 31000

Hypoeutectoid Alloys

(Photomicrograph courtesy of Republic Steel Corporation.)

04/26/21 Lecture 20 Slide 8 Intro to Materials Science ChE 31000

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 Hypereutectoid Alloys
The fraction of pearlite Wp?

The fraction of proeutectoid

cementite WFe3C?

x
T V

0.76

04/26/21 Lecture 20 Slide 9 Intro to Materials Science ChE 31000

Hypereutectoid Alloys

04/26/21 Lecture 20 Slide 10 Intro to Materials Science ChE 31000

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 Instant Freeze Water

https://youtu.be/JEWQRJ49CPo
04/26/21 Lecture 20 Slide 11 Intro to Materials Science ChE 31000

Instant Freeze Water

https://youtu.be/zVAL5I-WtAQ
04/26/21 Lecture 20 Slide 12 Intro to Materials Science ChE 31000

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 Phase Transformations
• Diffusion-dependent with no change in phase
composition or number of phases present (e.g. melting,
solidification of pure metal, allotropic transformations,
recrystallization, etc.)
• Diffusion-dependent with changes in phase
compositions and/or number of phases (e.g. eutectic or
eutectoid transformations)
• Diffusionless phase transformation - by cooperative
small displacements of all atoms in structure, e.g.
martensitic transformation

04/26/21 Lecture 20 Slide 13 Intro to Materials Science ChE 31000

Kinetics of Phase Transformations

• Nucleation of the new phase(s) - formation of stable small
particles (nuclei) of the new phase(s). Nuclei are often
formed at grain boundaries and other defects.
• Growth of the new phase(s) at the expense of the original
phase(s).

04/26/21 Lecture 20 Slide 14 Intro to Materials Science ChE 31000

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 Nucleation
• Homogeneous – nuclei of the new phase form uniformly
throughout the parent phase.
• Heterogeneous – nuclei form preferentially at structural
inhomogeneities, such as container surfaces, insoluble
impurities, grain boundaries, dislocations, and so on.

04/26/21 Lecture 20 Slide 15 Intro to Materials Science ChE 31000

Gibbs Free Energy

G = H – TS, where H is the enthalpy and S is the entropy

H = U + PV, where U is the internal energy

A transformation occurs spontaneously only when G has

a negative value.

Equilibrium is trade-off between minimization of

enthalpy and maximization of entropy

04/26/21 Lecture 20 Slide 16 Intro to Materials Science ChE 31000

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 Homogeneous Nucleation

Critical
nucleus radius
Critical free
energy change

04/26/21 Lecture 20 Slide 17 Intro to Materials Science ChE 31000

Homogeneous Nucleation

where ΔHf is the latent heat of fusion.

04/26/21 Lecture 20 Slide 18 Intro to Materials Science ChE 31000

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 Homogeneous Nucleation
• The number of stable nuclei n*
(having radii greater than r*) is a
function of temperature:

• The diffusion effect is related to the

frequency at which atoms from the
liquid attach themselves to the solid
nucleus:

04/26/21 Lecture 20 Slide 19 Intro to Materials Science ChE 31000

Homogeneous Nucleation
• The nucleation rate: proportional to the product of
n* and vd :

Supercooling ΔT (or undercooling)

04/26/21 Lecture 20 Slide 20 Intro to Materials Science ChE 31000

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 Heterogeneous Nucleation

Surface free
energy is
reduced.

04/26/21 Lecture 20 Slide 21 Intro to Materials Science ChE 31000

Heterogeneous Nucleation
• The critical radius r* for
heterogeneous nucleation
is the same as for
homogeneous nucleation.
• The activation energy
barrier for heterogeneous
nucleation is smaller than
the homogeneous barrier.

04/26/21 Lecture 20 Slide 22 Intro to Materials Science ChE 31000

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 Growth
• Once a stable nucleus of the new phase exceeding
the critical size r* is formed, it starts to grow.
• The growth rate:

At a specific temperature, the overall

transformation rate is equal to some
product of 𝑁 and 𝐺 .
high T (close to Tm): low nucleation and
high growth rates_coarse microstructure
with large grains
low T (strong undercooling): high
nucleation and low growth rates_fine
structure with small grains

04/26/21 Lecture 20 Slide 23 Intro to Materials Science ChE 31000

Rate of phase transformations

• Time to 50% reaction completion, t0.5

04/26/21 Lecture 20 Slide 24 Intro to Materials Science ChE 31000

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 Kinetics of phase transformations
• The time dependence of solid-
state phase transformations at
a fixed temperature is often
described in terms of the time
dependence of the fraction of
transformation (y):

Percent recrystallization
as a function of time and
at constant temperature
for pure copper.

04/26/21 Lecture 20 Slide 25 Intro to Materials Science ChE 31000

Microstructural and Property Changes

in Iron–Carbon Alloys

04/26/21 Lecture 20 Slide 26 Intro to Materials Science ChE 31000

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Isothermal transformation (TTT) diagrams

04/26/21 Lecture 20 Slide 27 Intro to Materials Science ChE 31000

PEARLITE MORPHOLOGY
Two cases:
• Ttransf just below TE • Ttransf well below TE
--Larger T: diffusion is faster --Smaller T: diffusion is slower
--Pearlite is coarser. --Pearlite is finer.
10m

- Smaller T: - Larger T:

colonies are colonies are
larger smaller

04/26/21 Lecture 20 Slide 28 Intro to Materials Science ChE 31000

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 Martensite
• Martensite:
--(FCC) to Martensite (BCT)
(involves single atom jumps)
x

60 m
Fe atom potential
x x
sites x x C atom sites
x

• Isothermal Transf. Diagram

800 Austenite (stable) Martentite needles
T(°C) A TE Austenite
P
600
S

B
400 A
10
•  to M transformation..
0% -- is rapid!
0%
50

0% -- % transf. depends on T only.

%

200 M+A 50%

M+A 90%
M+A
10-1 10 103 105 time (s)
04/26/21 Lecture 20 Slide 29 Intro to Materials Science ChE 31000

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