Phase Transformation

& Microstructure Evolution

Nokeun Park

Pyuck-Pa Choi

L02
1) Thermodynamics & Phase Diagrams
2) Diffusion
3) Crystal Interfaces & Microstructure
4) Solidification
5) Diffusional Transformations in Solids
6) Diffusionless Transformations

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Outline of Today´s Lecture

 Definition & Laws of Thermodynamics

 Thermodynamic State Functions
 Phase Transformation & Equilibrium
 Liquid to Solid Transformation

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Definition of Thermodynamics

Thermodynamics is a field of physics concerned with

heat & temperature & their relation to energy & work.

The behavior of these quantities is governed by the four

laws of thermodynamics, irrespective of the composition

or specific properties of the material or system.

www.wikipedia.org

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Thermodynamic Laws

 Thermodynamics is based on four laws which are universally valid.

0th law: If two systems are each in thermal equilibrium with a third, they are
also in thermal equilibrium with each other.

1st law: The internal energy of a closed system is constant.

2nd law: In a natural thermodynamic process, the sum of the entropies of the
interacting thermodynamic systems increases.

3rd law: At absolute zero temperature all processes cease & the entropy of
the system is zero.

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First Law of Thermodynamics
 The first law of thermodynamics postulates conservation of the internal energy of a
closed thermodynamic system.

 The internal energy 𝑈𝑈 of a closed system is the sum of potential & kinetic energy.

 An infinitesimal change of the internal energy of the system is given by:

𝛿𝛿𝑞𝑞: heat supplied to (> 0) or released (< 0) by the system

𝑑𝑑𝑑𝑑 = 𝛿𝛿𝑞𝑞 − 𝛿𝛿𝑤𝑤 (1.1)
𝛿𝛿𝑤𝑤: work done on (< 0) or done by (> 0) the system

⇒ 𝛿𝛿𝑞𝑞 = 𝑑𝑑𝑑𝑑 + 𝛿𝛿𝑤𝑤 = 𝑑𝑑𝑑𝑑 + 𝑃𝑃𝑃𝑃𝑃𝑃 (1.2)

 If heat is added to a system it can be

used for an increase in internal energy
&/or for mechanical work.

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Second Law of Thermodynamics
 The entropy 𝑆𝑆 is a measure of irreversibility of a change in thermodynamic state
(classical thermodynamics) & a measure of disorder (statistical mechanics).

 The second law of thermodynamics states that the total entropy of a closed
system increases over time or remains constant.

𝛿𝛿𝑞𝑞
𝑑𝑑𝑑𝑑 ≥ (1.3) 𝑇𝑇: absolute temperature (unit: K).
𝑇𝑇

𝛿𝛿𝑞𝑞𝑟𝑟𝑟𝑟𝑟𝑟
𝑑𝑑𝑑𝑑 = (1.4) (for reversible processes)
𝑇𝑇

(for more details, see Gaskell p. 37 – 59)

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Thermodynamic Properties

 Thermodynamic state functions describe the state of a system using state variables.
State functions do not depend on the path by which the system arrived at its
present state.

𝑈𝑈 (internal energy), 𝑆𝑆 (entropy)

𝐻𝐻 = 𝑈𝑈 + 𝑃𝑃𝑃𝑃 (enthalpy), 𝐹𝐹 = 𝑈𝑈 − 𝑇𝑇𝑇𝑇 (Helmholtz free energy)
𝐺𝐺 = 𝑈𝑈 + 𝑃𝑃𝑃𝑃 − 𝑇𝑇𝑇𝑇 = 𝐻𝐻 − 𝑇𝑇𝑇𝑇 (Gibbs free energy)

 Intensive variables (pressure 𝑃𝑃, temperature 𝑇𝑇,..) do not depend on system size.

 Extensive variables (volume 𝑉𝑉, number of particles 𝑛𝑛,..) depend on system size.

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Internal Energy

 Consider an one-component system (i. e. consisting of only one element or

compound of fixed stoichiometry).

 For a closed system undergoing a reversible process, the combination of

the first & second law of thermodynamics yields:

𝑑𝑑𝑑𝑑 = 𝑇𝑇𝑇𝑇𝑇𝑇 − 𝑃𝑃𝑃𝑃𝑃𝑃 (1.5)

 Above equation gives the relationship between the state function 𝑈𝑈 & the
independent variables 𝑆𝑆 & 𝑉𝑉.

 For a system at equilibrium with constant 𝑆𝑆 & 𝑉𝑉, the internal energy 𝑈𝑈 is at
minimum.

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Gibbs Free Energy
 Often, investigations of solids at constant temperature 𝑇𝑇 & pressure 𝑃𝑃 are of
relevance.

 For such systems one should consider the Gibbs free energy 𝐺𝐺:

𝐺𝐺 = 𝑈𝑈 + 𝑃𝑃𝑃𝑃 − 𝑇𝑇𝑇𝑇 = 𝐻𝐻 − 𝑇𝑇𝑇𝑇 (1.6)

𝐻𝐻 = 𝑈𝑈 + 𝑃𝑃𝑃𝑃 (1.7)

⇒ 𝑑𝑑𝐺𝐺 = 𝑑𝑑𝐻𝐻 − 𝑇𝑇𝑇𝑇𝑇𝑇 (1.8) for 𝑃𝑃, 𝑇𝑇 = 𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐.

 With the first & second law of thermodynamics it follows that 𝑑𝑑𝑑𝑑 = 0 & 𝐺𝐺 attains a
minimum for a closed system in equilibrium at constant pressure & temperature.

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Thermodynamic State Functions

 Recall following relationships for the thermodynamic state functions below:

𝑑𝑑𝑑𝑑 = 𝑇𝑇𝑇𝑇𝑇𝑇 − 𝑃𝑃𝑃𝑃𝑃𝑃

𝐻𝐻 = 𝑈𝑈 + 𝑃𝑃𝑃𝑃 ⇒ 𝑑𝑑𝑑𝑑 = 𝑑𝑑𝑑𝑑 + 𝑉𝑉𝑉𝑉𝑉𝑉 + 𝑃𝑃𝑃𝑃𝑃𝑃 = 𝑇𝑇𝑇𝑇𝑇𝑇 + 𝑉𝑉𝑉𝑉𝑉𝑉 (1.9)

𝐺𝐺 = 𝐻𝐻 − 𝑇𝑇𝑇𝑇 ⇒ 𝑑𝑑𝐺𝐺 = 𝑑𝑑𝑑𝑑 − 𝑆𝑆𝑆𝑆𝑆𝑆 − 𝑇𝑇𝑇𝑇𝑇𝑇 = −𝑆𝑆𝑆𝑆𝑆𝑆 + 𝑉𝑉𝑉𝑉𝑉𝑉 (1.10)

 Above equations are valid for closed systems of fixed size & composition, for
which the thermodynamic state can be described by two independent variables.

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Gibbs Free Energy
 A measure for the relative phase stability is the Gibbs free energy 𝐺𝐺.

𝐺𝐺 = 𝐻𝐻 − 𝑇𝑇𝑇𝑇 𝐻𝐻: enthalpy, 𝑇𝑇: temperature, 𝑆𝑆: entropy

Measure of the heat content of the system.

Measure of the disorder of the system.

 A spontaneous phase transformation from a state 1 to state 2 leads to a decrease

in 𝐺𝐺:
𝐺𝐺1 : Gibbs free energy of state 1
∆𝐺𝐺 = 𝐺𝐺2 − 𝐺𝐺1 < 0 (1.11)
𝐺𝐺2 : Gibbs free energy of state 2

 At thermodynamic equilibrium 𝐺𝐺 reaches an absolute minimum.

∆𝐺𝐺 = 𝐺𝐺2 − 𝐺𝐺1 = 0 (1.12)

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Specific Heat
 Consider a single component system.

 Changes in the thermodynamic state can be induced by varying temperature

at constant pressure.

 The specific heat is the heat absorbed to raise the temperature of the system
by 1K.
𝜕𝜕𝐻𝐻
𝐶𝐶𝑝𝑝 = (1.13) (Specific heat at constant pressure p)
𝜕𝜕𝑇𝑇 𝑝𝑝

 𝐶𝐶𝑝𝑝 can be experimentally determined & is available in the literature.

 If 𝐶𝐶𝑝𝑝 is known, thermodynamic state functions can be determined as functions

of temperature.

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𝐶𝐶𝑝𝑝 , 𝐻𝐻 & 𝑆𝑆 vs. Temperature
𝜕𝜕𝐻𝐻
𝐶𝐶𝑝𝑝 = (1.14)
𝜕𝜕𝑇𝑇 𝑝𝑝

 The enthalpy 𝐻𝐻 can be obtained from the

specific heat 𝐶𝐶𝑝𝑝 by integrating eq. (1.14)

 When considering phase transformations,

only relative changes in thermodynamic
state functions are relevant.

 Thus, 𝐻𝐻 can be defined relative to any

reference level. Usually 𝐻𝐻 = 0 at 298 K.

𝑇𝑇
⇒ 𝐻𝐻 = � 𝐶𝐶𝑝𝑝 𝑑𝑑𝑑𝑑 (1.15)
298 𝐾𝐾
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𝐶𝐶𝑝𝑝 , 𝐻𝐻 & 𝑆𝑆 vs. Temperature

 From classical thermodynamics:

𝐶𝐶𝑝𝑝 𝜕𝜕𝑆𝑆
= (1.16)
𝑇𝑇 𝜕𝜕𝑇𝑇 𝑝𝑝

 Defining 𝑆𝑆 = 0 at 0 K:

𝑇𝑇 𝐶𝐶
𝑝𝑝
⇒ 𝑆𝑆 = � 𝑑𝑑𝑑𝑑 (1.17)
0 𝑇𝑇

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𝐺𝐺 vs. Temperature

 For an one-component system with

fixed mass & composition:

𝑑𝑑𝑑𝑑 = −𝑆𝑆𝑆𝑆𝑆𝑆 + 𝑉𝑉𝑉𝑉𝑉𝑉

 At constant pressure (𝑑𝑑𝑑𝑑 = 0)

𝜕𝜕𝐺𝐺
= −𝑆𝑆 (1.18)
𝜕𝜕𝑇𝑇 𝑝𝑝 𝐺𝐺 = 𝐻𝐻 − 𝑇𝑇𝑆𝑆

⇒ 𝐺𝐺 decreases with 𝑇𝑇 at a slope given by −𝑆𝑆.

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Solid to Liquid Transformation
 Liquid has higher enthalpy than solid.

 Liquid has higher entropy than solid.

⇒ Gibbs Free Energy of liquid decreases
more rapidly with temperature.

 𝑇𝑇 < 𝑇𝑇𝑚𝑚 : Solid is more stable (𝐺𝐺𝑆𝑆 < 𝐺𝐺𝐿𝐿 ).

 𝑇𝑇 > 𝑇𝑇𝑚𝑚 : Liquid is more stable (𝐺𝐺𝐿𝐿 < 𝐺𝐺𝑆𝑆 ).

 At the melting temperature 𝑇𝑇𝑚𝑚 (𝑇𝑇 = 𝑇𝑇𝑚𝑚 ):

Solid & liquid are in equilibrium (𝐺𝐺𝐿𝐿 = 𝐺𝐺𝑆𝑆 ).

 At 𝑇𝑇 = 𝑇𝑇𝑚𝑚 , the latent heat 𝐿𝐿 is absorbed

(released) for transformation from solid to
liquid (liquid to solid).
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Latent of Heat of Fusion

https://www.youtube.com/watch?v=gDbo_vGOycU

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Driving Force for Solidification
 Undercooling a liquid metal below its melting temperature 𝑇𝑇𝑚𝑚 leads to
solidification with a decrease in Gibbs free energy ∆𝐺𝐺.

The Gibbs free energies of a liquid & solid at a temperature 𝑇𝑇 are:

𝐺𝐺 𝐿𝐿 = 𝐻𝐻 𝐿𝐿 − 𝑇𝑇𝑆𝑆 𝐿𝐿 (1.19)

𝐺𝐺 𝑆𝑆 = 𝐻𝐻 𝑆𝑆 − 𝑇𝑇𝑆𝑆 𝑆𝑆 (1.20)

The difference in 𝐺𝐺 between liquid & solid at 𝑇𝑇 is:

∆𝐺𝐺 = ∆𝐻𝐻 − 𝑇𝑇∆𝑆𝑆 (1.21)

where ∆𝐻𝐻 = 𝐻𝐻 𝐿𝐿 − 𝐻𝐻 𝑆𝑆 & ∆𝑆𝑆 = 𝑆𝑆 𝐿𝐿 − 𝑆𝑆 𝑆𝑆 (1.22)

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Driving Force for Solidification
 For 𝑇𝑇 = 𝑇𝑇𝑚𝑚 liquid & solid are in equilibrium:

⇒ ∆𝐺𝐺 = ∆𝐻𝐻 − 𝑇𝑇𝑚𝑚 ∆𝑆𝑆 = 0 (1.23)

∆𝐻𝐻 𝐿𝐿
⇒ ∆𝑆𝑆 = = (1.24)
𝑇𝑇𝑚𝑚 𝑇𝑇𝑚𝑚

∆𝑆𝑆: Entropy of fusion

𝐿𝐿: Latent heat of melting

 Combine eq. (1.21) & (1.24):

𝐿𝐿∆𝑇𝑇
⇒ ∆𝐺𝐺 ≈ (1.25) (for small ∆𝑇𝑇)
𝑇𝑇𝑚𝑚

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Summary
 Thermodynamics is a field of physics concerned with heat & temperature & their relation
to energy & work. It is based on four fundamental laws.

 The thermodynamic state of a material system can be expressed by thermodynamic state

functions/potentials.

 For solids, heat-treated at constant pressure & temperature, the thermodynamic state can
be most conveniently described by the Gibbs free energy 𝐺𝐺.

 Thermodynamic equilibrium of such a system is defined by an absolute minimum in Gibbs

Free Energy.

 Solidification occurs below the melting temperature 𝑇𝑇𝑚𝑚 because 𝐺𝐺𝑆𝑆 < 𝐺𝐺𝐿𝐿 .

 At 𝑇𝑇 = 𝑇𝑇𝑚𝑚 , the latent heat 𝐿𝐿 is used (released) for transformation from solid to liquid
(liquid to solid).

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