Physical metallurgy principles

Reza Abbaschian,
Lara Abbsdvjisn,
Robert E. Reed-Hill
Really Weird Author Ranking?!
September 13, 2014

The original book (1st and 2nd edition) was written solely by Prof. Robert Reed-Hill.
As to the 3rd edition, it is improved, including fracture mechanics, solidification, TEM
etc, so it is still good one.
The 3rd edition is written by Professor Robert Reed-Hill (1st author) and the Reza
Abbaschian (2nd author), and is also a good book.

However, as to the 4th edition, it is disappointing since it is almost identical to 3rd

edition- major change is the removal of 2 chapters and technically it cannot be even
regarded as a new edition.

By then, the original author, Professor Reed-Hill has passed away (~2001). However,
the 2nd author of 3rd edition, Reza Abbaschian was listed as 1st author. Despite to
very little change of 4th edition, there is a 3rd author Lara Abbaschian coming in, and
ranked as 2nd author. Thus, the original author Professor Reed-Hill is moved to the
place of 3rd author. The 2nd author Ms. Abbaschian, based on the front page of the
book, is from an affiliation of business, other than academic institution.

https://www.amazon.com/Physical-Metallurgy-Principles-SI-Version/dp/0495438510
Chapter 1: The Structure of Metals
Chapter 2: Characterization Techniques
Chapter 3: Crystal Binding
Chapter 4: Introduction to Dislocations
Chapter 5: Dislocations and Plastic Deformation
Chapter 6: Elements of Grain Boundaries
Chapter 7: Vacancies
Chapter 8: Annealing
Chapter 9: Solid Solutions

Chapter 10: Phases

Chapter 11: Binary Phase Diagrams
Chapter 11: Binary Phase Diagrams
Chapter 12: Diffusion in Substitutional Solid Solutions
Chapter 13: Interstitial Diffusion
Chapter 14: Solidification of Metals
Chapter 15: Nucleation and Growth Kinetics
Chapter 16: Precipitation Hardening
Chapter 17: Deformation Twinning and Martensite
Reactions
Chapter 18: The Iron-Carbon Alloy System
Chapter 19: The Hardening of Steel
Chapter 20: Selected Nonferrous Alloy Systems
Chapter 21: Failure of Metals
Physical metallurgy principles

Ch10 Phases
 Contents
• Definitions
• Thermodynamics of solutions
• Equilibrium between two phases
• Phases number
• Phases rule
• Two-component systems
• Ternary systems
 Phases
• A phase is defined as a macroscopically homogeneous body of
matter.
Ex. Three forms of copper—solid, liquid, and gas—constitutes a
separate and distinct phases.
• Each crystal structure defines a separate phase, so that
polymorphic metals can exist in more than one solid phases.
Ex. Fe
 definitions
• Binary alloys: two component systems, are mixtures of
two metallic elements. Ex. Cu-Zn
• Ternary alloys: three component systems, mixtures of
three metallic elements. Ex. Ag-Ni-Zn
• System: as used in the sense usually employed in
thermodynamics, or physical chemistry, is an isolated
body of matter.
• Component: often the metallic elements that make up
the system.
component

system

Binary alloys Ternary alloys

• Ex. Pure copper or pure nickel are by themselves one-
component systems, while alloys formed by mixing are two
component systems.

• Steels are normally considered to be two-component systems

consisting of iron and iron carbide(Fe3C), a compound.

• Terminal solid solution: phases based on the crystal structures

of the components.
Ex. Binary alloys of copper and silver.
(copper acts as the solvent, with silver the solute; another in
which silver is the solvent and copper the solute)

• Intermediate phases: crystal structures different from those of

either component may form at certain ratios of the two
components. They do not have a fixed composition (ratio of the
components) and appear over a range of compositions.
Ex. Intermediate solid solution: Brass (copper(53-50%)-zinc(47-
50%)), intermetallic compound: iron-carbide, Fe3C.
• In a system, continuous (matrix) phase:the phase that
surrounds the other phase ; discontinuous (dispersed) phase:
the phase that is surrounded.

• The phases in alloy systems are usually solutions — either liquid,

solid or gaseous.
• The free energy of a solution is a thermodynamic property of
the solution, or a variable that depends on the thermodynamic
state of the solution.
G = H(U) + PV – TS
• Variables: temperature(T), pressure(P), volume(V), enthalpy(H),
entropy(S), and the free energy(G).

• In a one-component system of a given mass and phase, if the

two variables temperature and pressure are specified, the
volume of the system will have a definite fixed value. At the
same time, its free energy, enthalpy, and other properties will
also have values that are fixed and determinable.
Ex. In a three-component system, the mole fraction are:
nA nB nC
NA  NB  NC 
n A  nB  nC n A  nB  nC n A  nB  nC
NA ,NB ,NC :are the mole fractions; nA,nB,nC :are the actual number
of moles of the A, B, and C components.
By definition of the mole fraction, then:
N A  N B  NC  1
• There are only two independent mole fractions in a ternary
system.
• Most metallurgical processes occur at constant temp. and
pressure, the state of a solution can be considered to be a
function of its composition. Such as free energy can be
considered a function of only the composition variables. So, the
total free energy (G) of a solution is :
G  G(n A , nB , nC ) (temp. and pressure constant)
• By partial differentiation, the differential of the free energy of a
single solution of three components at constant pressure and
temperature is: G G G
dG   dn A   dnB   dnC
n A n B nC
• Where the partial derivatives, such as G n A , represent the
change in the free energy when only one of the components is
varied by an infinitesimal amount.
• For a very small variation of component A, while the amounts of
the components B and C in the solution are maintained constant,
we have dG G

dn A n A
• The partial derivatives are the partial mole free energies of the
solution and are designed by the symbols G A , GB , GC

dG  G A dnA  GB dnB  GC dnC

• The total free energy of a solution composed can be obtained by

integrating the upper equation. The partial-molar free energies are
functions of only the composition of the solution (at constant
temperature and pressure), they will also be constant during the
formation of the solution.
G  n AGA  nBGB  nC GC
• Let us differentiate upper equation completely to obtain

dG  n A dG A  G A dnA  nB dGB  GB dnB  nC dGC  GC dnC

• But we have already seen that the derivative of the free energy
is
dG  G A dnA  GB dnB  GC dnC

n A dG A  n B dGB  nC dGC  0
..... for three- componentsolution
and, n A dG A  n B dGB  nC dGC  n D dGD  0
..... for four components

• The significance of these relationships in explaining the

phenomena of polyphase systems in equilibrium.
Equilibrium between two phases

• A binary (two-component) system with two phases in equilibrium

will now be considered.
• Total energy: a phase Ga  naA G Aa  naB GBa

b b b b b
b phase G  n A G A  nB GB
* A small quantity (dnA) of component A: a phase  transferred to
 b phase

dnA Binary system dG  dGa  dG b  GaA (dn )  G bA (dn )

A A
A, B A, B b a
 dG  (G A  G A )dnA
a b
A, B

A, B A, B A, B
• Because we assumed the two phases are at
equilibrium. The variation in the free energy for any
infinitesimal change inside the system  the shift of
a small amount of component A from one phase to
the other must be zero.
b a
dG  (G A  G A )dn A  0
a b
G A  G A
a b
same manner GB  GB
for M componentsand  phase in equilibriu m
a b  
G A  G A  G A  .....  G A
a b  
G B  G B  G B  .....  G B
a b  
G C  G C  G C  .....  G C

a b  
G M  G M  G M  .....  G M
Number of phases in an alloy system
• One-component systems
ex. white tin  gray tin
b phase a phase
body-centered diamond cubic
tetragonal large volume expansion (27%)
upper 286.2K below 286.2K
• Gibbs free energy of a pure substance is : G = H – TS
• In a reversible process at constant pressure, the heat exchanged
between the system and its surrounding equals the enthalpy
change of the system.


q  dH  C p dT
q : a small transfer of heat into or out of the system
dH : accompanying enthalpychange of the system
C p : the specific heat at a constant pressure

T
 H  H0  C
0
p dT

Simlarly, a reversible process for entropy

dq C p dT T C p dT T C p dT
dS 
T

T
 S  S0  0 T
 
0 T
(0K  S 0  0)
• The free energy of both the
white and gray tin:

T T C ap dT
Ga  H 0a  
0
C ap dT  T 
0 T
T T C pb dT
G b  H 0b  
0
C pb dT  T  0 T
286.2K  G  0 (gray and white tin are coexists)
below 286.2K  gray tin has the lowest free energy
 gray tin is the most stable phase
above 286.2K  white tin has the lowest free energy
 white tin is the most stable phase
T  G  (TS term is importancein the free energy equation)
 the closest packing structure
More closely bound phase

More open structure  the

greatest entropy of vibration

High-T stable phase is BCC;

Low-T phase has a close-packed
structure (FCC, HCP)
Ex. Li, Na, Ca, Ti….
G  H  TS
T T
 
b b a
H  H 0  C p dT  H 0  C ap dT
0 0
T C pb dT T C ap dT
and TS  T  T0 0 T
T 
at the temperature of transformation (286.2K)
H  TS  G  0
Two-component systems
-- single phase binary systems
• Ideal solutions: no tendency for either A atoms or for B atoms to
cluster together or for opposite types of atoms to attract each other.

free energy of mixing N A moles of A atoms and N B moles of B atoms

G  G A0 N A  GB0 N B  TS M
G A0 : free energy per mole of pure A
GB0 : free energy per mole of pure B
T : the absolute temperature
S M : the entropyof mixing

G  G A0 N A  GB0 N B  RT ( N A ln N A  N B ln N B )
G  N A (G A0  RT ln N A )  N B (GB0  RT ln N B )
if G A  G A0  RT ln N A
GB  GB0  RT ln N B
G A  G A  G A0  RT ln N A
GB  GB  GB0  RT ln N B
G A andGB : the quantities of the increase in free energy when one mole (A or B)
is dissolved at constant temperature in a very large quantity of the solution.
• Nonideal solutions: in most liquid and solid solutions, no preference
either for their own or for their opposites.
G A  RT ln a A
G B  RT ln a B
• aA is the activity of component A:
indicate the extent to which a solution Ideal solution :
departs from an ideal solution. Gi  RT ln 0.70  0.356RT
nonideal solution :
Gn  RT ln 0.80  0.223RT
positive deviation :
a A  N A and a B  N B
Gi  Gn
attractionbetween same atoms
 attractionbetween dissimilar atoms
if a A and a B  1  two components
were completelyinsoluble

Positive deviation Negative deviation negative deviation :

a A  N A and a B  N B
Gi  Gn
attractionbetween same atoms
 attractionbetween dissimilar atoms
• Activity coefficients: the ratios of the activities to their
respective atom fractions.
aA aB
A  and  B 
NA NB

• The free energy of a mole of ideal solution should given by:

G  N AG A0  N B GB0  RT ( N A ln N A  N B ln N B )
N AG A0  N B GB0 : free energy of one totalmole of the two
components(not mixed)
RT ( N A ln N A  N B ln N B ) : the contribution of the entropy
of mixing to the free energy of the solution,
and directly proportional to the temperature

• The homogeneous solid solution has the lower free energy and
represents the stable state.
G  N AG A0  N B GB0  RT ( N A ln N A  N B ln N B )

At 500K temperature
 Two-component
systems b
a
-- two phases binary systems A, B A, B
• Two-component (A, B) systems containing two
phases (a, b)
n A d G A  nB d G B  0  N A d G A  N B d G B  0
a phase : N aA dG A  N aB dGB  0 0.86dG Ag  0.14dGCu  0

b phase : N Ab dG A  N Bb dGB  0 0.05dG Ag  0.95dGCu  0

• Restrictive equations: restricts the values of 0.86dG Ag  0.14dGCu

the mole fractions of the components in the 
solutions. 0.05dG Ag  0.95dGCu

0.86 0.14
 so, dG Ag  dGCu  0
• Ex. 0.05 0.95

a phase b phase Which means that at a constant temperature

N Ag  0.86 N Ag  0.05 and a constant pressure there can be no
N Cu  0.14 N Cu  0.95 change in the partial-molal free energies
when the two phases are in equilibrium.
 Graphical determinations of partial-molal free
energies

G  G B  N A (G A  G B )
G  N AG A  (1  N A )G B
(1  N A )  N B
G  N AG A  N B G B
•At constant pressure and temp.
the compositions of the phases are
fixed.
•The partial-molal free energies of
each component be the same in
both phases at equilibrium.

G Aa  G Ab
GBa  GBb
Two-components systems with three phases in equilibrium
• In two-component systems, three
phases in equilibrium occur only under
constant temp., pressure, and
compositions.
• Ex. Three-phase reaction: Cu-Ag alloy
phase diagrams
 Phase rule
P+F=C+2

A single-component phase diagram

Ternary phase
diagram

The vertical axis is temperature

27%A – 46%B – 27%C