CONSTITUTION OF ALLOYS

Chapters 9&10 Reed Hill

ENGINEERING MATERIALS 1
Constitution of Alloys

1. Types of Alloys (solid solutions,

intermediate phase, interstitial phases);
2. Free energy of:
1. solid solutions;
2. Phase mixtures
3. Intermediate phases
3. Stable state of an alloy
4. Phase equilibrium and Gibbs phase rule
5. Nucleation and growth techniques
1. Volmer Weber and Becker Doring Theory;
2. Diffusion and interface controlled growth;

ENGINEERING MATERIALS 2
Type of alloys

 Solid solutions:
 Homogeneous mixtures in the solid state;
 Equivalent to liquids and gases forms;
 Proportions of components can vary
between fixed limits; and
 Mixtures do not separate naturally;
 Solvent: more abundant atomic form;
 Solute: less abundant;
 Usually crystalline.

ENGINEERING MATERIALS 3
Types of solid solutions
 Two distinct types:
 Substitutional :direct substitution in lattice;
 Interstitial: occupies interstices;

ENGINEERING MATERIALS 4
Intermediate Phases

 In alloys systems:
 Crystal structures or phases different
from those of elementary components;
 When they occur over a range of
compositions: solid solutions;
 When new crystal structures occur:
 With simple whole-number fixed ratios of
component atoms: intermetallic
compounds.

ENGINEERING MATERIALS 5
Intermediate Solutions and
Compounds: differences:
 Understood better by examples:
 Cu and Zn  brass
 # of structures with different compositions;
 Commercial importance:
 at a ratio of one Zn atom to Cu atom;
 Bcc crystal structure vis a vis Cu (fcc) and
Zn(cph);
 Bcc structure stable over range of
composition (47-50 Zn):
 it is a solid solution and not a compound!

ENGINEERING MATERIALS 6
Intermediate Solutions and
Compounds: differences2:

 Intermediate Compound example:

 C in Fe:
 Any amount greater one thousand of a
percent at RT results in a definite
intermetallic compound!
 Has fixed composition (6.67% C)
 Complex crystal structure (orthorhombic)
different from:
 Either iron (bcc)
 Or carbon (graphite)

ENGINEERING MATERIALS 7
Solubility of C in bcc Iron

 Any amount
greater one
thousand of a
percent at RT
results in a
definite
intermetallic
compound.

ENGINEERING MATERIALS 8
Interstitial Solid Solutions

 Solute atoms small in size;

 Conditions studied by Hume-Rothery and
others;
 Extensive interstitial solutions:
 Only if solute atom has an apparent diameter
smaller than 0.59 that of solvent;
 Interstitial atoms dissolve more easily in
transition series metals than others;
 Insolubility of C in non-transition series elements
allows the use of graphite crucible to melt them.

ENGINEERING MATERIALS 9
Interstitial Elements

 Only small atoms (r < 1Å) able to fit

 Nitrogen (0.71 Å)
 Oxygen (0.60 Å)
 Carbon (0.77 Å)
 Hydrogen (0.46 Å)
 Boron (0.97 Å)
 Mnemonic: NOCHB elements

ENGINEERING MATERIALS 10
Transition Metals

 Commercials transition metals are:

Iron Vanadium Tungsten
Titanium Chromium Thorium
Zirconium Manganese Uranium
Nickel Molybdenum
 Easy of solubility due to unusual electronic
structure:
 Possess incomplete electronic shells inside of the
outer or valence electron shells;
 Other metals have filled shells below valence
shells.
ENGINEERING MATERIALS 11
Solubility of Interstitial Atoms in
Transition Metals

 Depends on metal;
 Usually small
 Interstitial atoms diffuse easily through
solvent lattice:
 Thus influence properties more than
expected;
 Diffusion occurs not by vacancy
mechanism but by solute atoms jumping
from one interstitial site to another.

ENGINEERING MATERIALS 12
Solubility of carbon in the bcc
iron

Read chapter 9.4

Let go back to phases

ENGINEERING MATERIALS 13
Substitutional Solid solutions
and Hume-Rothery rules

ENGINEERING MATERIALS 14
Hume-Rothery Rules I

1. The atomic radii of the two elements

must differ by less than 15%.
 The closer the sizes of the atoms, the
more favorable is the formation of the
solid solutions;
2. The electrochemical nature of the
elements must be similar.
 If one is electropositive and the other
electronegative, compounds will form
rather than solid solutions;

ENGINEERING MATERIALS 15
Hume-Rothery Rules II

3. Other things being equal a metal of lower

valency tends to dissolve more of a metals
of higher valence than vice versa.
 If the solute metal has a different valence from
that of the solvent metal, the # of valency
electrons per atom, called the electron ratio will
be changed.
 Crystal structures are more sensitive to a
decrease in the electron ratio than an increase;
4. The crystal structures are the same;

ENGINEERING MATERIALS 16
Dislocations and solute atoms

 Please go through chapters:

 9.7 Dislocation Atmospheres
 9.8 Formation of a dislocation
atmosphere
 9.9 Evaluation of the interaction constant
 9.10 The drag of atmospheres on moving
dislocations

ENGINEERING MATERIALS 17
Home work

 Please work through problems

 9.1 Comparison of fcc interstitial
opening and bcc one
 9.5 prove of the value of the
interaction constant.
 9.7 Equilibrium # of C – atoms in a
cubic meter.

ENGINEERING MATERIALS 18
PHASES

Refer to Chapter 10 Reed-Hill

Abbaschian

ENGINEERING MATERIALS 19
Definitions

 Phase: macroscopically homogenous body of

matter
 Polymorphic (Allotropy)
 Alloys
 Binary Alloys (2 components)
 Ternary alloys (3 components)
 System
 Component

ENGINEERING MATERIALS 20
System and Component

 SYSTEM used in the sense employed in

thermodynamics;
 AN ISOLATED BODY OF MATTER
 The COMPONENTS of the system are often:
 The metallic elements that make up the system
 Pure Cu and Ni are one component systems
 Their alloys are two component system
 Pure chemical compounds can also be
components in metallic systems

ENGINEERING MATERIALS 21
Example of compound components

 A mixture of common salt (NaCl) and

water (H2O);
 Steels are also considered to be two
component systems consisting of:
 Iron (pure element) and
 Cementite (Fe3C), a compound

ENGINEERING MATERIALS 22
Gaseous and liquid phase

 In metallic systems, generally:

 only one gaseous phase;
 of little importance;
 In liquid state for most commercial
alloys;
 Liquid components form only one solution.

ENGINEERING MATERIALS 23
The Physical Nature of Phase
Mixtures

 Concept of:
 Continuous or matrix phase and
 Discontinuous or dispersed phase
 The structure of a two phase system can
also be so interconnected that both phases
are continuous.
 In metallic system a system of several
phases is also a mixture of several different
types of crystals.
 Effects of :
 Surface energy; electrical and magnetic fields
can be neglected.

ENGINEERING MATERIALS 24
Thermodynamics of solutions

 Phases in alloy systems are solutions;

 Either liquid, solid or gaseous
 Compounds can also be thought of as
solutions of very limited solubility.
 Free energy of a solution:
 Thermodynamic property of the solution;
 A variable dependent on the
thermodynamic state of the solution
(system)
ENGINEERING MATERIALS 25
One component system
(pure substance)

 Thermodynamic state :
 determined uniquely if any two of its
thermodynamic properties are known.
 Variables classified as properties:
 Temperature (T); Pressure (P);
 Volume (V); Enthalpy (H);
 Entropy (S) and Free energy (G)
 In one component system of given mass
and phase:
 If T and P are specified; V is fixed!
 G, H and other properties will have values that
are fixed and determinable.

ENGINEERING MATERIALS 26
Solutions: degrees of freedom

 Necessary to specify more than two

properties to define the state of a
solution;
 Usually :
 T and P as well as Composition of the solution.
 # of independent variables is one less than
the # of components;
 Consideration of the mole fractions in
ternary system proves this.

ENGINEERING MATERIALS 27
Solutions: Degrees of Freedom

 By definition of mole nA
NA 
fraction: n A  nB  nC
 NA+NB+NC=1
nB
 The value of any one of NB 
the mole fraction can n A  nB  nC
be computed once the
other two are known. nC
NC 
 There are only two n A  nB  nC
independent mole
fractions in a ternary
system.
ENGINEERING MATERIALS 28
Free Energy of a 3 component
system

 Metallurgical processes occur at const

T and P;
 State of solution  Composition
 Similarly other properties e.g. Free
Energy G
 In a 3 component system:G
 G = G(nA,nB, nC) (T & P constant)
G G G
dG  x dn A  x dnB  x dnC
n A nB nC
ENGINEERING MATERIALS 29
 Partial Molal free Energies
 In a 3 component system:
 A very small variation of component A while
the amounts of components B and C are
constant gives: dG G

dn A n A

 The partial derivates are the partial molal free

energies of the sol. designates by:
dG G dG G
GA   , GB   and
dn A n A dnB nB
dG G
GC  
dnC nC

ENGINEERING MATERIALS 30
 Partial Molal free Energies
 In a 3 component system:
 eqn G G G
dG  x dn A  x dnB  x dnC
 n A nB nC
 becomes:
 dG  G A dnA  GB dnB  GC dnC

 Integration gives the total free energy of a

three component system.

ENGINEERING MATERIALS 31
Molal free energies
 The relationship between the # of
moles of each component in a three-
component solution and the derivates
of the partial molal free energies is
the result of the integration of the
previous equation and gives:
n A dG A  nB dGB  nC dGC  0
 This will be used in explanation of
polyphase systems in equilibrium.

ENGINEERING MATERIALS 32
 Equilibrium between two Phases
 Binary system with  and  phase:
 Free energy of  phase: G  nA G A  nB GB
 That of  phase : G   n A G A  nB GB
 If a small dnA of component A is
transferred from  phase to  phase;
 Free energy of  phase will be decreased and
that phase will be increased;
 The total free energy change:
     
 dG  dG  dG  G A (  dn A )  G A ( dn A ) or dG  (G A  G A ) dn A

ENGINEERING MATERIALS 33
 Phases at equilibrium

 Because the two given phases are at

equilibrium:
 The state of the two phase system is at a
minimum with respect to its free energy
(total G of the 2 solutions).
 Therefore variation in G for any infinitesimal
change inside the system must be zero;
 Thus dG  (G A  G A )dn A  0
 Since dnA is not zero then :
G A  G A also GB  GB
ENGINEERING MATERIALS 34
The # of Phases in an Alloy system
 One Component system:
 Necessary: conditions determining the #
of phases in the system;
 For a one component system: e.g Iron
well known.

ENGINEERING MATERIALS 35
Causes for phase changes in one
component systems
 Solid state phase change:
 white tin to
 bct ( phase), commercial form, metallic
lustre;
 gray tin
 Gray in colour, diamond cubic structure, brittle
 Change occurs very slowly below 286.7
K
 Amenable to study properties over wide
temp range;

ENGINEERING MATERIALS 36
 Specific heat of Tin ( and )

 A plot of specific
Heat at constant
pressure of both
gray and white
forms of tin as
function of
temperature.

ENGINEERING MATERIALS 37
Computation of free energies for
Tin phases

 Gibbs free energy of a pure substance

is
 G = H-TS
 To evaluate the free energy of a
substance at some temperature T,
one needs to know both the enthalpy,
H and the entropy, S
 From these values the free energy
equations 10.18 in Reed-Hill have
been determined.
ENGINEERING MATERIALS 38
Equation 10.18 Reed-Hill
Abbaschian

 These can be T T
C p dT
G   H O   C p dT  T 
evaluated using 0 0
T
graphical T T
C p dT
calculus, using G   H O   C p dT  T 
T
the curves of fig 0 0

10.1.
 The results are in
the next figure.
(10.2 in Reed-
Hill)
ENGINEERING MATERIALS 39
Temp –G curves for two forms of
tin

Note Free energy of both phases decreases with

increasing temperature.

ENGINEERING MATERIALS 40
Curves for ΔG, ΔH, and –TΔS for the
solid phases of tin where ΔG=ΔH-TΔS

ENGINEERING MATERIALS 41
Tin Allotropic transformation:
Interpretation

 At low temps phase with smaller enthalpy is

stable:
 H = U + PV where U is the internal energy.
 Thus stable phase at low T is one with lower
U or with tighter binding of atoms;
 At High T : TΔS predominates;
 Phase with greater S becomes stable;
 Generally form with looser binding or greater
freedom of atom movement;
 In Tin diamond cubic lattice ( phase); lower
density;
 Atoms more restrained in vibratory motion than
in tetragonal or beta lattice.

ENGINEERING MATERIALS 42
Iron Allotropic transfomation

 Check this on page 310.

ENGINEERING MATERIALS 43
Two component systems

 More than one component 

solutions;
 Simplest :Binary systems;
 Least complex in this is a single solution
 Will therefore consider:
 Ideal solutions
 Nonideal solutions

ENGINEERING MATERIALS 44
Ideal Solutions

 Re: ideal solution definition:

 Two components A and B
 No preference for neighbours or interactions;
 No tendency to cluster or attract each other;
 Free energy is:
 sum of:
 G of NA moles of A atoms , plus
 G of NB moles of B atoms
 Less:
 G due to entropy of mixing of A atoms and B
atoms.

ENGINEERING MATERIALS 45
Free energy of ideal solution

 This is derived from:

G  G Ao N A  GBo N B  TS M
 Substituting term for entropy:
G  G Ao N A  GBo N B  RT ( N A ln N A  N B ln N B )
 Rearranging:
o o
G  N A (G  RT ln N A )  N B (G  RT ln N B )
A B

ENGINEERING MATERIALS 46
Partial Molal free energies of ideal
solution

G  N AG A  N B GB
 From:
o
G
 We get: A  G A  RT ln N A

GB  GBo  RT ln N B
 These can also be written as:
G A  G A  G Ao  RT ln N A
GB  GB  GBo  RT ln N B
 G A and GB represent increase in free G
when one mole of A or B is dissolved at
const. T in a very large quantity of solution.
ENGINEERING MATERIALS 47
Note on free energies for ideal
solutions

 Free energy changes are functions of

the compositions;
 Necessary to define them in terms of the
addition of a quantity of pure A or pure B
to a very large volume of solution in
order that the composition of the
solutions remains unchanged.

ENGINEERING MATERIALS 48
NONIDEAL SOLUTIONS

 General
 Most liquid and solid solutions are not ideal
 Not to be expected in solids that
 Any two atomic forms chosen in random will
show no preference either for their own or for
their opposites 
 larger or smaller free energy change ( G A , GB )
 than expected in ideal solution

ENGINEERING MATERIALS 49
Molal Free Change and non-ideal
solutions

 Ideal solution Molal free change given by

G A  RT ln N A
 For non-ideal solution a quantity “a”
known as activity is defined and molal
free change becomes:

G A  RT ln a A

G B  RT ln aB
ENGINEERING MATERIALS 50
Activity of Components

 Useful indicators of extent to which

solution is non-ideal.
 Functions of the composition of the
solution

ENGINEERING MATERIALS 51
 Example of positive deviation
Variation of Activity
between with concentration
ideal and non-ideal
solution

Curve aB => Activity of

component B
At composition
“x”, both activities
> corresponding
mole fractions,
Line NA => Atomic
Curve aA => Activity of
consider
fractions of component A only one
component A
Line NB => Atomic
component “B”
fractions of component B

ENGINEERING MATERIALS 52
Variation of Activity with concentration

NB = 0.70 while aB = 0.8

For ideal solution:

G  RT ln 0.70  0.356RT

At composition
“x”, both aA and aB
For the non-
ideal solution: > mole fractions
NA and NB,
G  RT ln 0.80  0.223RT
consider only one
component “B”

ENGINEERING MATERIALS 53
Variation of Activity with concentration
Extreme case:
• Two components
completely insoluble in
• The solution has a
each other;
smaller
• Activities would decrease
be
equal toin unity
free for
energy
all as a
ratiosresult of the
of A and B
formation of the
solution than if an
ideal solution had
formed.

•Attraction of atoms of the

same kind is greater than
the attraction between
dissimilar atoms
ENGINEERING MATERIALS 54
Variation of Activity with concentration
In this case: Unlike
atoms are more
strongly attracted to
each other than those
of the same kind.

Negative deviation of
activity curves from
the mole fraction lines.
ENGINEERING MATERIALS 55
Activity Coefficients

 Comparison of activities of
components to their respective atoms
fractions can indicate roughly the
nature of the interaction of the atoms
in solutions.
  Activity coefficients which are the
ratios of activities to their respective
atom fractions are convenient.

ENGINEERING MATERIALS 56
Activity coefficient: Binary solutions

 The activity coefficients of Binary

solutions A and B are defined as:

aA aB
A  and  B 
NA NB

ENGINEERING MATERIALS 57
Thermodynamic of diffusion
equalization

 In diffusion when a composition

gradient exists in a solid solution
diffusion usually occurs in such a way
as to produce a uniform composition
in the solid solution.
 The thermodynamic reasons will be
considered.

ENGINEERING MATERIALS 58
Energy of a mole of an ideal sol.

 If one has an ideal solution, the free

energy of a mole of the solution
should be given by:

G  N AGAo  N BGBo  RT ( N A ln N A  N B ln N B )
In the non-miscible Fe-Pb
Free energy of one system, these terms
total mole of the two would be all that are
components, if the required to specify the
two components are free energy of one total
not mixed or do not mole of Fe and Pb
mix ENGINEERING MATERIALS 59
Energy of a mole of an ideal sol.

 If one has an ideal solution, the free

energy of a mole of the solution
should be given by:

G  N AGAo  N BGBo  RT ( N A ln N A  N B ln N B )

• This is the contribution of the entropy of mixing

to the free energy of the solution
• Term  temp and becomes important as T 

ENGINEERING MATERIALS 60
Dependency of free energy on composition
Note: Curves
decreasing Free energy
with increasing curves of
temp. elements A and B,
completetly
soluble in each
other in the solid
state.

At 500K:
GAO =6,280J
GBO =8,370J

These are plotted

in the RH and LH
of the figure.
ENGINEERING MATERIALS 61
Dependency of free energy on composition
At 500K:
GAO =6,280J
GBO =8,370J

These are plotted

in the RH and LH
of the figure.

The dashed line

connecting these
points represents:
O O
N AG  N BG  6,280 N A  8,370 N B
A B

Or the free energy of the solution less

the entropy
ENGINEERING of mixing term.
MATERIALS 62
Data for Computing the Entropy of mixing Contribution to
the free energy of an ideal solution based on (table 10.2)

Atom Fraction (NALn(NA)+NBLn(NB)) G of mix G of Comp G of Sol

0 0 0 8370 8370
0.1 -0.325082973 -1351.37 8161 6809.63
0.2 -0.500402424 -2080.17 7952 5871.827
0.3 -0.610864302 -2539.36 7743 5203.637
0.4 -0.673011667 -2797.71 7534 4736.291
0.5 -0.693147181 -2881.41 7325 4443.587
0.6 -0.673011667 -2797.71 7116 4318.291
0.7 -0.610864302 -2539.36 6907 4367.637
0.8 -0.500402424 -2080.17 6698 4617.827
0.9 -0.325082973 -1351.37 6489 5137.63
1 0 0 6280 6280

ENGINEERING MATERIALS 63
Data for Computing the Entropy of mixing Contribution to
the free energy of an ideal solution (table 10.2)

ENGINEERING MATERIALS 64
 Hypothetical free energy of an ideal solution
10000

(NALn(NA)+NBLn(NB))
G of mix
8000 G of Comp
G of Sol

6000
Joules per Mole

4000

2000

0
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1

-2000

-4000
Atom Fractions

ENGINEERING MATERIALS 65
 2 components system with 2
phases

 Let us now take up the case of 2-

component systems that contain not
a single phase, but 2 phases.
 In either of the 2 phases, an equation
of the form:

 Must be satisfied

ENGINEERING MATERIALS 66
Restrictive Equations
This pair of
equations
 From the eqn: restricts the
This equationsvalues
will beof the
The phase superscripts of
Divide
the partial-molal
referred to as restrictive
eachfreeterm by: mole fractions
equations. In orderof to
the
energies are omitted,
 We get:
because assuming
understand howcomponents
restrictive in
equation work let us
theconsider
solution
equilibrium, the partial-
molal
Where: an example of alloy of copper
free energy of either and
and silver.
component
If the
is the same in
both phases
phases. are labelled “α” and “β”
 For the α phase:
 For the β phase:

ENGINEERING MATERIALS 67
Graphical determination of partial
molal free energies (10.7)

ENGINEERING MATERIALS 68
Two phases having compositions
Na and Nb (10.8)

ENGINEERING MATERIALS 69
Two phases in equlibrium

ENGINEERING MATERIALS 70
Table 10.3

ENGINEERING MATERIALS 71
A single component phase diagram

 Work on this

ENGINEERING MATERIALS 72