Thermodynamics: Thermochemical Properties

10/7/20
Lecture 4
Thermodynamics
Mechanical and Materials Engineering

Phase Transform ation and Kinetics in M aterials M M E427/527 © 2015 Portland State University, All rights reserved.
Portland State University
1
Thermochemical Properties
• Materials respond to
– Thermal stimuli (temperature)
– Chemical stimuli (composition or environment)
– Electromagnetic stimuli (electric or magnetic fields)
– Mechanical stimuli (mechanical forces)
• Consider the first two together

– Responses to thermal or chemical stimuli define
thermochemical properties

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The thermochemical properties of materials govern two

kinds of behavior:
Internal reactions that occur within the material and

determine its microstructure
Environmental interactions that alter the chemistry of the

material or its environment

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Thermodynamics: what material wants to do

Thermodynamics governs whether a given process is possible and fixes
the magnitude of the forces that drive it.
Kinetics: what it can do, and how quickly

Kinetics determines how quickly the process can happen, given the
thermodynamic driving force. In many cases, kinetic constraints are
used to prevent thermodynamically favorable processes from happening
at all.

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Materials are made to have useful microstructures by

combining thermodynamics and kinetics in a constructive
way.
The material is brought into a condition, in which the

microstructure that is wanted is both thermodynamically
possible and kinetically achievable.
The conditions are then altered, usually by cooling, to

prevent further microstructural changes.

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Thermodynamics
Properties
Condition of Equilibrium
Equilibrium phase diagrams
Kinetics
Continuous: heat and mass diffusion
Structural phase Transitions/Transformation
Environmental interactions
Wetting and Corrosion

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Thermodynamics
• The conditions of equilibrium and stability

– Equilibrium ⇒ no desire for change
– Deviation from equilibrium ⇒ driving force for change
– Beyond limits of stability ⇒ must change
• Internal equilibrium
– T, P, {µ} are constant
– Deviation drives heat and mass diffusion
• Global equilibrium
– Thermodynamic potential is minimum
– Deviation drives structural phase transformations

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First Law of Thermodynamics
• Defines internal energy, E

• Energy is conserved
dE = dW + dQ
dW = work done (chemical + mechanical +electromagnetic)
dQ = heat transferred (thermal work)
– Energy transferred to one material is taken from another

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Second Law of Thermodynamics
• Defines entropy: S (time)

• Entropy is associated with
– Evolutionary time (most fundamental)
– Heat
• When a system is isolated, S can only increase

– Any system is isolated when its surroundings are included
⇒Time runs forward

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The Conditions of Equilibrium
X
metastable
unstable
stable
S S
stable
unstable
metastable
• The entropy of an isolated system can only increase

⇒ A stable state must have a maximal value of the entropy
• Conditions of equilibrium:
– Local: S is not increased by infinitesimal changes
– Global: maximum with respect to all possible changes
• Conditions of stability
– S is not increased by small, finite changes
– Stable vs. metastable equilibrium

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A body of material that is homogeneous in its composition and structure is called a

phase.
The thermodynamic state of a homogeneous phase of a simple material is fixed by

its energy, its volume and its chemical content, that is, by the variables E, V, and {N}.
Entropy = S(E,V,{N})

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The Necessary Conditions of Equilibrium
metastable
unstable
stable
S
• For an isolated system in equilibrium, there must be no small change of

state that increases its entropy:
δS(E,V,{N}) ≤ 0 (for every possible change)
• Any part of it is in equilibrium with respect to internal changes

– That is, any subvolume is in equilibrium when regarded as an isolated system
– The inequality is always a necessary condition for equilibrium

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Internal Equilibrium: Thermal
The picture can't be

displayed.
1 T2
h
e
p
i
• Let two small volumes exchange c energy at constant total
energy,volume and composition: t
δ E δu E ⎡1 1⎤
(δ S)E,V , N ≤ 0 = 1 + r 2 = δ E1 ⎢ − ⎥
T1 Te2 ⎣ T1 T2 ⎦
• Equilibrium requires: c
a
n
T1 = T2 (temperature
't is constant)
b
e Mechanical and Materials Engineering
d 13
13 i
s
p
l
a
y
e
d
.
Internal Equilibrium: Mechanical
The picture can't be

displayed.
1 T2
h
e
p
i
• Two small volumes in thermal cequilibrium exchange volume at
constant composition: t
u
P1 rP δV
(δ S)E,V , N ≤ 0 = δV1 + e2 δV2 = 1 [ P1 − P2 ]
T T T
c
• Equilibrium requires: a
n
P1 = P2 (pressure
't is constant)
b Mechanical and Materials Engineering
e
Phase Transform ation and Kinetics in M aterials M M E427/527
© 2015 Portland State University, All rights reserved.
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Internal Equilibrium: Chemical
The picture
can't
1 be2
displayed.
• Two small volumes in thermal and mechanical equilibrium exchange one

component:
µ1 µ δ N1
(δ S)E,V , N ≤ 0 = −
T
δ N1 − 2 δ N 2 =
T T
[ µ2 − µ1 ]
• Equilibrium requires:
µ1 = µ2 (chemical potential is constant)
– For every component

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Necessary Conditions for Internal

Equilibrium
• Thermal equilibrium:
– Temperature is constant (T)
• Mechanical equilibrium (for a fluid):

– Pressure is constant (P)
• Chemical equilibrium:
– Chemical potential of each component is constant (µk)
– Disclaimer: the conditions of mechanical and chemical equilibrium change slightly in electrical or strong
gravitational fields, but we won’t care much

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Equilibrium When the System is not Isolated:

Thermodynamic Potentials
• Consider three cases:
• Material interacts thermally with environment:

– Equilibrium requires that the “Helmholtz free energy” be a minimum
F = E – TS = F(T,V,{N})
• Material interacts thermally and mechanically with environment:
– Equilibrium requires that the “Gibbs free energy” be minimum
G = E - TS + PV = G(T,P,{N})
• Material interacts thermally and chemically with environment

– Equilibrium requires that the “work function” be minimum
Ω = E − TS − ∑ µk N k = Ω(T, P,{µ})
k

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Summary: Thermodynamic Potentials and

Conditions of Equilibrium
• Isolated system: E, V, {N} controlled

– Entropy, S(E,V{N}) = maximum
• Thermal contact: T, V, {N} controlled

– Helmholtz free energy, F(T,V,{N}) = E-TS = minimum
• Thermomechanical contact: T, P, {N} controlled

– Gibbs free energy, G(T,P,{N}) = E-TS+PV = minimum
• Open contact: T, V, {µ} controlled

– Work function, Ω(T,V,{µ}) = - PV = minimum
– Or, equivalently, pressure, P(T,{µ}) = maximum

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Application: Equilibrium Phase in a

One-Component System
• Preferred phase has lowest free energy
– G~F
α – F = E-TS
β • At low T
– Phase with lowest E
G – β preferred since Eβ < Eα
• At high T
β α
– Phase with highest S
αβ – α preferred since Sα > Sβ
T • Since (∂G/∂T)P = (∂F/∂T)V = - S
T

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Equilibrium Phase Diagrams
• Changing T, P or x may change the “phase” of a solid

– Phase = state of aggregation
– Gas, liquid, solid (in a particular crystal structure)
• Phase diagrams:
– Maps showing equilibrium phases as a function of T, x (sometimes P)
– We shall consider equilibrium phases in
• One component systems
• Two component systems
– As a function of (T,x), not P
– Consider
• How to read any binary phase diagram
• How to understand a few simple phase diagrams

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One-Component Phase Diagram:

First-Order Phase Transformations
• Phases are distinct “states of aggregation”
– Differ by symmetry
– Gas, liquid, solid (particular crystal structure)
• Preferred phase minimizes free energy

– F = E-TS
- As T↓, gas→liquid→solid(low ΘD )
➝solid(high ΘD )
• Energy dominates at low T (Eβ < Eα)
• Entropy dominates at high T (Sα > Sβ)
– Transformations at well-defined temperatures
• Metastability
– Phase transformation requires structural change
– Phase retained beyond Tαβ if slow kinetics

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Mutations
ferromagnetism order ferroelectricity
• One phase simply become another at a particular Tc

– Symmetry of phase change must permit morphing
– Disordered high-temperature phase spontaneously orders
• Examples:
– Ferromagnetism: alignment of magnetic moments
– Chemical order: A and B separate to different lattice sites (some are first-order)
– Ferroelectricity: ion is displaced to asymmetric position, creating dipole

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Phases in a Two-Component System

• The Gibbs free energy per atom:
G
g= = g(T,P, x)
N
dg = −sdT + vdP + ( µ2 − µ1 )dx
⎛ ∂g⎞
⎜⎝ ⎟ = µ (x) = µ 2 (x) − µ1 (x)
∂x⎠T
• Stability requires:
⎛ ∂ 2g ⎞
⎜ 2⎟ ≥0 ⇒ g(x) is concave up
⎝ ∂x ⎠T

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Phases in a Two-Component System:

The Common Tangent Rule
• Binary System at (T,P)

– Phases α and β
– Free energy curves cross as shown
• Possible states:
– Pure α: g(x) = gα(x)
– Pure β: g(x) = gβ(x)
– Two-phase mixture:
g(x) = fαgα(xα) + fβgβ(xβ)
• Common tangent rule:

– Draw common tangent to gα(x) and gβ(x)
– Tangent touches at xα and xβ
– Then:
• If x < xα, α preferred
• If x > xβ, β preferred
• If xα <x< xβ, two-phase mixture preferred

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Phases in a Two-Component System
γ • Binary System at (T,P)

– Phases α, β and γ
– Free energy curves cross as shown
• Top figure:
– Phase γ does not appear
– Regions of α, β and α + β appear
– The least free energy is along lower curve
– Note within two-phase region
• α has fixed composition xα
• β has fixed composition xβ
• Bottom figure:
– Phase γ appears at intermediate x
– α and γ separated by α + γ region
– γ and β separated by γ + β region

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Binary Phase Diagrams
L TB
L+α
T
TA
å
A B
x
• Equilibrium phase diagrams are maps

– Show phases present at given (T,x)
– Binary phase diagrams also give compositions, phase fractions
• We will learn
– The “solid solution” phase diagram (above left)
– The “eutectic” phase diagram (above right)
– How to read any binary phase diagram
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Binary Phase Diagrams;

Three Pieces of Information for Given (T,x)
1. Phases present
• From phase field
2. Compositions of phases
• Only needed for two-phase fields
• xα and xβ from intersection of
isothermal line with boundaries
3. Phase fractions
• From the “lever rule”
xβ − x
fα =
x β − xα
x − xα
f β = 1− f α =
x β − xα

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Complex Diagrams:
Read in the Same Way
1. Phases from
phase field
Al-Cu Phase Diagram
2. Compositions
from isotherm
3. Fractions from
lever rule

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The Solid Solution Diagram
L TB
L+α
T
TA
å
A B
x
• To form a solid solution at all compositions

– Pure A and pure B must have the same crystal structure
– A and B must have chemical affinity
• The (α+L) region appears near the melting points

– Generated as the L and α curves pass through one another
– Often (but not always) between TA and TB

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Solidifying a Solid Solution
• Let the solution have the composition shown

• First solid to form is very rich in B
• As T decreases:
– Fraction of α increases
– Composition of α (xα) evolves toward x
• Final α has the average composition of the solution (xα = x)

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Application:
Purification (Zone Melting)
• To purify an impure (AB) liquid to pure B

– Cool until first solid forms (rich in B)
– Extract, re-melt and repeat (richer in B)
– Repeat as often as needed to create as pure B as desired
• “Zone melting”: A continuous process that accomplishes this

– Was the “enabling technology” for the transistor
– Very pure starting materials are necessary to create doped semiconductors

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The Simple Eutectic Phase Diagram
• Eutectic diagram:
– Simplest diagram when α and β have different structures
– Named for “eutectic reaction”: L → α + β at TE
• Source:
– As T rises, L free energy curve cuts through α,β common tangent
– Note TE is the lowest melting point

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Eutectic Diagram:
Characteristic Equilibrium Microstructure at x1
• Let L at composition x1 be cooled slowly

• L freezes gradually as T drops into α region
– Likely into polygranular microstructure shown
• On further cooling β precipitates from α
– Likely into microstructure shown
– β precipitates on grain boundaries and/or in grain interiors

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Eutectic Diagram:

• Solidification occurs sharply at TE
– Eutectic reaction: L → α + β
• Microstructure resembles that shown (the eutectic microstructure)
– α and β grow as plates side-by-side to maintain composition at interface
– Overall microstructure is grain-like eutectic “colonies”
– This transformation mechanism is the easiest kinetic path

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Eutectic Diagram:

• Solidification occurs in two steps:
– L solidifies gradually to α as it cools through L+α region
– At TE, the remaining liquid solidifies by the eutectic reaction: L → α + β
• Microstructure resembles that shown (the “off-eutectic” microstructure)
– Islands of “pro-eutectic” α composition at interface
– Surrounded by eutectic colonies

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“Eutectoid” Reactions
• The “eutectoid” is a eutectic between

solid phases:
– γ → α+β
– γ is a solid
• The classic example is the Fe-C diagram

shown at left
– Pure Fe:
• L→δ(bcc) → γ (fcc) → α(bcc)
– Eutectic (“cast iron”)
• L → γ+Fe3C
– Eutectoid:
• γ → α+Fe3C
• The most important reaction in steel

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Lamellar eutectic
Sn-43Bi In-3Ag
• Examples of the lamellar eutectic microstructure
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Divorced Eutectic
Sn-37Pb Sn-43Bi
• Ultrafine-grained divorced eutectic by rapid solidification

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Asymmetric eutectic: Sn-Ag
• Asymmetric eutectic
– Eutectic well away from 50A-50B
• Eutectic very rich in A

– At TE, L solidifies to A-rich microstructure
– Colonies cannot form
– Microstructure = A + B precipitates
• Ex: Sn-Ag
– Important to “Pb-free”solders
Sn-rich eutectic

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Asymmetric Eutectic
Ag3Sn
Ag3Sn
needles
Sn-4Ag-0.5Cu
• Sn-rich grains with discrete Ag3Sn islands and needles
• Sn-Ag and Sn-Ag-X “near eutectics” have this microstructure

– Used in “Pb-free solders” for microelectronics

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10/7/20

Mechanical and Materials Engineering

• Consider the first two together

Mechanical and Materials Engineering

The thermochemical properties of materials govern two

Internal reactions that occur within the material and

Environmental interactions that alter the chemistry of the

Mechanical and Materials Engineering

Thermodynamics: what material wants to do

Kinetics: what it can do, and how quickly

Mechanical and Materials Engineering

Materials are made to have useful microstructures by

The material is brought into a condition, in which the

The conditions are then altered, usually by cooling, to

Mechanical and Materials Engineering

Mechanical and Materials Engineering

• The conditions of equilibrium and stability

Mechanical and Materials Engineering

First Law of Thermodynamics

• Defines internal energy, E

Mechanical and Materials Engineering

Second Law of Thermodynamics

• Defines entropy: S (time)

• When a system is isolated, S can only increase

Mechanical and Materials Engineering

The Conditions of Equilibrium

• The entropy of an isolated system can only increase

Mechanical and Materials Engineering

A body of material that is homogeneous in its composition and structure is called a

The thermodynamic state of a homogeneous phase of a simple material is fixed by

Mechanical and Materials Engineering

The Necessary Conditions of Equilibrium

• For an isolated system in equilibrium, there must be no small change of

δS(E,V,{N}) ≤ 0 (for every possible change)

• Any part of it is in equilibrium with respect to internal changes

Mechanical and Materials Engineering

Internal Equilibrium: Thermal

The picture can't be

The picture can't be

Internal Equilibrium: Chemical

• Two small volumes in thermal and mechanical equilibrium exchange one

Mechanical and Materials Engineering

Necessary Conditions for Internal

• Mechanical equilibrium (for a fluid):

Mechanical and Materials Engineering

Equilibrium When the System is not Isolated:

• Material interacts thermally with environment:

• Material interacts thermally and chemically with environment

Mechanical and Materials Engineering

Summary: Thermodynamic Potentials and

• Isolated system: E, V, {N} controlled

• Thermal contact: T, V, {N} controlled

• Thermomechanical contact: T, P, {N} controlled

• Open contact: T, V, {µ} controlled

Mechanical and Materials Engineering

Application: Equilibrium Phase in a

Mechanical and Materials Engineering

Equilibrium Phase Diagrams