Chapter 4

Each element
- 3 different states: gas, liquid, solid
- at Tm - solid & liquid are in equilibrium
- at Tb - liquid & gas are in equilibrium
Tm & Tb
depend on pressure (p) but p has very
little effect on solid.

Fig 4.1

- on the lines in this diagram there are 2 phases in equilibrium with each other.
- at the triple point all 3 phases are in equilibrium with each other.
The border between the liquid and gas states of the substance is called the vapor pressure curve.
- For a given temp, it tells us the vapor pressure
- The vapor pressure ends at critical point

Critical point- The temp above which the gas cannot be liquidfied no matter how much pressure is applied.
(kinetic energy is too great for attractive forces to overcome, regardless of the applied pressure.)
- or beyond the critical point: liquid continuously transforms to gas.
At a given pressure there is a defined Tm and a defined Tb
1

Gibbs phase rule:

n no. of component
p no. of phase
f no. of degree of freedom
Eg. 1 component 1 phase:
f = 2
pressure and temp
At the triple point; n = 1, p = 3 :
f = 13+2 =0
means only specific values of temp and pressure that
3 phases are in equilibrium with each other.
Tm & Tb depend only little on pressure (for solid), therefore Gibbs phase rule can be modified
f = np+1
p constant
At melting temp:
f = 12 +1=0

For binary alloys:

2 components system
2 components system

n=2
p =1:
p =2:

= np+2

Other than temp, composition (in term of concentration, atomic percent)

can be introduced to the degree of freedom.
f = 2 1 + 1 = 2 (temp and concentration)
f = 2 2 + 1 = 1 (temp. or conc.)
- for a given conc., there is no defined Tm
- a finite range of melting temp where solid and
liquid are in equilibrium.

Different Types of Phase Diagrams

1. Complete solubility in liquid and solid (or binary system with complete miscibility) Fig. 4.3 Ag-Au
2. Diagram which solidus temp (or liquidus temp) decrease or increased on both sides Fig 4.4 and 4.5
- at the maximum or the minimum solidus & liquidus line intersect
- A diagram exhibit the maximum usually found in complex systems with intermetallic phases.
- melting temp increases or decreases reflects
strengthening or weakening of the atomic bonding forces.
tendency to decomposition or formation of intermetallic compounds in solid state.
in this case a miscibility gap will be formed.
A miscibility gap means there is a composition range over which the
components do not form solid solution but decompose to form a
mixture of 2 or more phases

3. Monotectic system
- miscibility gap occurs both in the solid and
liquid states. Fig 4.7 Fe-Pb
4. Complete solubility in the liquid state but limited
solubility in the solid state
- the solubility increase with increasing temp,
- if a miscibility gap exists only at temp below the solidus
temp, the melt solidifies as a solid solution and upon
cooling this solution decomposes into 2 phases. Fig 4.8
5. Complete solubility in liquid state and the max. temp of a
miscibility gap is higher than the solidus temp
- a point of intersection of the solidus temp with the solvus line of
the miscibility gap, the three phases (melt + 2 phases) are in
equilibrium.
(f = n p +1 = 2 3 + 1 = 0)
-There is solidification region has a cigar shape this phase
diagram is called peritectic phase diagram. Fig. 4.9
peritectic reaction:
L + 1 <==> 2 ( conc.= cp)
occur at Tp which is between melting temp of both components
- Occur when Tm of both components are very different.

6. A eutectic phase diagram

A miscibility gap intersect the solidus line. Fig. 4.6. & 4.11
cE - eutectic composition
L 1 + 2
TE - eutectic temperature

7. Phase diagrams with intermetallic compound

If the solidus line has a maximum, there is a tendency for intermetallic compound to form during
solidification from the melt, Fig 4.12.
- Intermetallic phases form from the melt during solidification can either be
- a finite range of composition as in the system Sb2Te3 Fig. 4.13 a
- the perfect stoichiometric composition, CaMg2, Fig. 4.13 b
- Intermetallic phases form from the solid state
- a finite solubility range of existence, -brass, Fig. 4.14
- a stoichiometric composition, NiBi3 ,Fig. 4.15

Thermodynamics of alloys
G = H TS
G = Gmin

(T, p = constant)
H - enthalpy
T - temp
S - entropy
p - pressure
S > 0 T up TS up
G down and Gmin at equilibrium
G of pure metal depending on temp. Fig 4.19
The free energy of crystal (Gc) & melt (Gm) change differently with temp
At melting temp: Gm = Gc liquid and solid in equilibrium
For pure element:
entropy = vibrational entropy + configuration entropy
(entropy of mixing)
S
= Sv + Sm
For alloys with 2 components A and B:
Total no. of atom N = no. of atom A + no. of atom B
N
= NA + NB
The atomic concentration of A: cA = NA/N
The atomic concentration of B: cB = NB/N = c
The entropy of mixing:
Sm = - N k {c lnc + (1 c) ln (1 c)}
c < 1, Sm > 0
-TS = -T(Sv + Sm) ~ -TSm
Fig. 4.20:
Sm curve is symmetry:

c = 0.5 slope = 0
c=0
slope = -
c=1

slope = +

S
=
c 0:1 c
lim

G = H TS
H does not change markedly with temp.
G(c) vary with -TS

Fig 4.21
T1 :

TA & TB:

T2 :

T3 :

GL < Gc for all component

only liquid exist in the system
Gc = GL for c = 0 and c = 1
melting temp of pure component
Gc & GL tangential line
both phases exist, cBS , cBL
Gc < GL for all composition
only solid () exist

Solid solutions
Primary solid solution or terminal solid solution
solid solution next to the pure component.
Intermediate solid solution phase with finite
composition range discrete from primary solid solution
Types of solid solutions Fig. 4.26
1. Interstitial solid solution - only H, B, C, N
2. Substitutional solid solution
-Interstitial site usually smaller than the size of the smallest atom
-Interstitial atom causes elastic distortion energy
-the size of interstitial atom elastic energy will rapidly increase decrease the solubility
-elastic distortion increase the free energy of the solid solution increase destabilizes the solid solution
Fig. 4.27 shows the determination of composition of the phases

10

Fe C system Fig. 4.28

-C are located in octahedral sites of bcc and fcc
- octahedral site in fcc:
roc t/ RFe = 0.41
- octahedral site in bcc: roc t/ RFe = 0.16
Rc / RFe = 0.61
- C atom is larger than the size of octahedral interstitial site
- the solubility of cmax = 2.08 wt%
cmax = 0.02 wt%
From Arrhenius law: temp dependence of terminal solid
solution
cmax = co e-Q/kT
Example:

Interstitial solid solution C in Fe

substitutional solid solution Zn in Cu

Fig. 4.30 shows an effect of temp on solubility of the alloying

elements.

Solid solutions are mostly substitutional solid

solution and some of them are completely
miscibility and some have a miscibility gap.

11

Hume Rothery rules

1. The difference of atomic radii should not exceed 15%
2. The difference of electronegativity should be small
3. The number of valence electrons should not be very
different.
Intermetallic compounds may be formed if this
rules is violated.

II The influence of the electronegativity

I The effect of the size

The different in electronegativity of the components

is high, the intermetallic compound is likely to form.

Ag-Au system completely solubility Fig. 4.3

Cu-Ag system large miscibility gap Fig. 4.6
the solubitity at room temp < 1%
aAu = 4.0786 A
aAg = 4.0863A
aCu = 3.6148 A
a - Ag & Au lattice parameter different 0.19%
b - Au & Cu lattice parameter different 12.8%
c- Ag & Cu lattice parameter different 13.0%
b) and c) have only minor different but lead to
complete change of solution behavior.
Therefore, only the size of the atoms cannot explain
this phenomena.

Bipolar of the bond increase with increasing

electronegativity.
Intermetallic compound limits the solubility of
terminal solid solution.

III The influence of the valence electron

Base metal :
small valence eAlloying element:
large no. of valence eSolubility is high
Base metal:
Alloying element:
Solubility is low

large no. of valence esmall no. of valence e12

IV Crystal structures
Single atom:
only one electron can occupy in on energy state.
Bring 2 atoms closer: e- in one atom needs to change its energy state or this energy state needs to split
into two levels.
N atoms together:
the energy state split into N energy level quasi continuous energy band.
In crystal: if the adjacent electronic state is a large energy different, the band gap is large. Therefore, the
energy of an additional electron can drastically increase at certain concentrations of valence
electrons. VEC valence electron concentration (no. of valence electrons per atom)
The critical electron density of this band gap depends on crystal structure; bcc has higher electron density in
the band gap than fcc.
If Zn (2 valence e-) added in Cu (1 valence e-) to form solid solution (fcc)
- no. of valence e- in the band gap drastically increase
- The critical valence electron concentration (VEC) of fcc is reached. fcc is not stable.
- bcc becomes more favorable (with increasing Zn atoms).
- Therefore the second phase will be formed and
stability of the second phase can be determined
by free energy diagram.
Fig. 4.31 shows the effect of VEC of the various alloys.
- Base metal: Cu
- alloying element: Zn(2), Ga(3), Ge ( 4), As (5 )
- Increasing valence e- the solubility decrease.

13

4.4 Intermetallic compounds

4.4.1 Overview
2 types of compounds
stoichiometeric compounds
non-stoichometric compounds
(composition range)
The existence and the composition range of
Intermetallic compounds can be determined by the free
energy curve, Fig 4.32, with respect to other phase in
the system. may not occur or at least not in the
most stable form.

4.4.2 Ordered solid solution

In binary alloy: If the bonding between unlike atoms is stronger than between the like atoms, each atom will
try to maximize the no. of unlike atoms as its next neighbors
A regular solution: an exchange energy , Ho
Ho =
HAB - (HAA + HBB)/2 << 0 ; Ho is largely negative
For stoichimetric compositions, strictly periodic arrangement
Composition: AB (ca = 0.5)
bcc lattice, Fig 4.33a
- consider 2 sublattices, each sublattice occupied by one type of atom. Each A atom
has only B neighbor.
- a perfectly ordered atomic arrangement extended across many unit cell long range order.
14

fcc lattice, Fig 4.33b

- consider 4 sublattice
1 sublattice can be occupied by A
In order to obtain
max.
unlike atoms
3 sublattices can by occupied by B
A:B = 25:75 AB3
- Therefore fcc cannot form AB structure
A:B =1:3
- In order to form AB structure, the atomic
arrangement in the crystal have to be as in
Fig 4.33c.
Fig. 4.33c
- AB type lattice
- The atomic arrangement have to be in layered
structure. This will break cubic symmetry
- A tetragonal structure (a = b c) will be formed
then the long range order will be found.

A:B =1:1

A:B =1:1

Note: the ordered and disorder structure are not equivalent even though they cannot be discriminated.
The ordered atomic distribution low entropy
Degree of ordered decreases with increasing temperature. If the exchange energy, Ho, is very small
disordered structure will be exist.
and at higher temperature disordered solid solution
Cu-Au : at T<390oC ordered structure formed
Tc : the critical temp is the temp that ordered state changes to disordered state.
Ni-Al system:

Ni3Al and NiAl are the ordered phases and remain ordered up to melting point

15

Degree of long range order: proposed by Bragg-William

The long range order parameter,

s =

p- x
1- x

p fraction of A-atoms in A sublattice

x fraction of A-atoms in the alloy
For an alloy of type AB: the solid solution has bcc structure.
s = (p-1/2)/ ( 1- ) = 2p-1
Perfect order:
s = 1, p = 1
Complete disordered:
s = 0 , p = 0.5
Perfect order but the atoms located at the wrong sublattice: s = -1
l s l - is used for now
Magnitude of s depends on Temp and Ho

G(s) = H TS

in equilibrium

dG/ds = 0

16

Methods to determines long range order parameter

(the order structure is also called superlattice)
1. X-ray diffraction, Fig. 4.37, X-ray patterns
Superlattices have larger lattice parameter, Fig. 4.38
2. The electrical resistivity, Fig. 4.39.
Resistivity increased by perturbation of periodic
arrangement. Superlattice has high ordered of solute
atoms low resistivity
The long range order parameter
The ordered structure transforms from disordered one
and initiate at different locations at the nucleus.
If the compounds have A and B components
Some ordered structure has
s = 1 : The interface between these 2 is called antiplane boundary
The other ordered structure has s = -1 :
The short range order parameter
q - fraction of B-atom as next neighbors of A
q qd
qd - fraction of B-atom as neighbor of A in disorder state
=
qm qd
qm- fraction of B-atom as next neighbor of A in completely ordered state
In case of long range order s = 1 then also = 1
For AB-alloy: qm = 1,
The value of varies between
0 1
depends on Temperature
(T), s(T) are function of Temperature, Fig 4.36.
1 (it doesnt go to zero. It remains > 1)
If
T<< Tc :
T Tc : (T) 0
17

Experimental methods to determine short range order

1.
X-ray and neutron scattering
2.
The electrical resistivity: resistivity increases with increasing degree of short range order
Disordered structure is obtained by quenched the alloy from high temperature
Short range ordered structure is obtained by tempered quenched alloy.
The lower the tempering temp, the higher degree of short range order. Fig. 4.42.
4.4.3 Compound Phases
Pure element non directional bond
Most alloys Ho 0
If the polarity of the atoms is very different, the ionic character of the bond become stronger.
The Zintl limit is located between group III A and IV A in the periodic table. Beyond this limit the ionic
character of bond dominates and form stoichiometric salt-like compound, the Zintl phases. Fig. 4.43
Fig. 4.44: Mg is alloyed with elements in group IV A (Si, Sn, Pb) and V A (Sb)
Mg + atom in group IV A VII A form stoichiometric compounds according to their valency (fig. 4.43)
Mg + atom in the other group form large variety of different phase where the valency is irrelevant.
The strength of the polarity
Electronegativity of anion (-) decreases the ionic bonding character decreases.
Electropositivity of cation (+) decreases the ionic bonding character decreases.
The melting temp. of the Zintl phases can imply their stability, Fig 4.44.
The electronegativity of the elements in the periodic table decrease from left to right in any period and from
top to bottom in any group.
The electropositivity of the elements increases from right to left and from top to bottom.
Fig. 4.44a - Si, high
period 2 Mg high electropositivity melting temp
18
Sn,
EN melting temp
period 3 Zn
Pb low
low

19

4.4.4 Phases with High Packing Density

If the bonds have a strong metallic character, the high packing density of atomic arrangement is obtained.
The high packing density crystal structure can only be obtained for
- specific compositions
- specific sizes of the component atoms
For example: Laves phases :
Composition AB2 Fig. 4.46, size A:B = 1.225
eg. The specific crystal structure with high packing density of MgCu2 in Fig. 4.46,
MgCu2 : 1 unit cell contains 24 atoms. Mg at diamond lattice and Cu at tetrahedral interstitial sites.
close packing plane is on (110). RMg /RCu = 1.225 , the high packing density is obtained if
both the Cu atoms and the Mg atoms are in contact. Packing density = 71%
Laves phase occurs in many lattice systems. The ratio of the atomic radii = 1.225 and its can divert from
this value but not exceed 10%, table 4.3.

20

If the alloying element is so small that it can fit in the interstitial sites of the other component, the
requirement is r/R = 0.59. For example:
- AB type compound if all octahedral interstitial sites of fcc are occupied, NaCl lattice.
- This phases have a very sharply defined upper solubility limit since all interstitial sites are occupied,
no more alloying elements can be dissolved, Fig 4.47. This phase is called Hgg phase high
stability. Fig. 4.47a Hgg phase TaC has high melting temperature ~ 3988 o C.
- Crystal structure of the Hgg phase is not necessary the same lattice of the pure component.
eg. Ta is bcc, TaC is fcc which C atoms occupy in octahedral interstitial of fcc, Fig 4.47b.
(Ta2C is Hgg phase with hexagonal structure, Fig. 4.47.)
- Hgg phase AB4 : interstitial sites in the center of fcc are occupied.

21

4.4.5 Electronic phases (Hume-Rothery-phase, Electron compound)

- Binary alloys : non-equal valency
The alloys of Cu, Ag, Au with B sub-group metals shows that their equilibrium diagrams have many
similarity. Their crystal structures change in the same sequence, ,,,. Each phase does not occur
at the same composition (by weight or by atomic %) but it does occur at the same electron
concentration. Electron compound.
( solid solution is not controlled by e/a (electrons/atom) ratio but the others do.)
For Cu-Zn: found at e/a ratio of 3/2 disordered bcc or ordered CsCl-type as .
For Cu-Al: is found at Cu3Al, 3 valence e- of Al and 1 valence e- from each Cu. e/a = 6/4=3/2.
For Cu-Sn: is found at Cu5Sn, e/a = 9/6
phase, Cu5Zn8, has a complex cubic (52 atoms per unit cell), e/a = 21/13.
phase, CuZn3, has a cph structure. e/a = 7/4.
The stability of the phases can be explained by VEC (valence electron concentration)
VEC = CA.NVA + (1-CA).NVB

CA - the fraction of A-atoms

NVA and NVB- the no. of valence e- of A and B

VEC - depends on compositions

- if higher valency alloying element is added
a certain value of VEC is obtained the structure becomes unstable
- if continue adding this alloying element, critical value of VEC is reached then another crystal
structure becomes stable. Table 4.4.
22

The model to explain the stability of the phases

When an alloying element is added in the metal, the valence e- of the alloying element also added in the
structure. The VEC increases. With increasing VEC the added electrons have to assume progressively
high energy states. For free electrons in a solid the energy is given by
E ~ (nx2 + ny2 + nz2)

nx , ny , nz are the principle quantum numbers.

n = (nx , ny , nz)
All states of the same energy can be found on a sphere with radius:
l r l = (nx2 + ny2 + nz2)1/2
A smaller energy A smaller sphere
The highest energy Fermi energy Fermi sphere
In crystals only specific energy ranges are allowed. Vector n has a defined space as a cube
called Brillouin zones
At the boundaries of Brillouin zones, the electron energy changes discontinuously.
Assuming: the Brillouin zone has a shape of cube.
If the Fermi sphere smaller than the cube,
- additional e- can be easily be accepted Fermi sphere grows
If the Fermi sphere touches the cube of Brillouin zone,
- the remaining sites for new electrons decrease rapidly.
- the addition electrons have to assume state of much higher energy in the next Brillouin zone.
- Fig. 4.48 and 4.49.
Size of the Brillouin zone depends on crystal structure.
- the more e- can be accommodated in a lower Brillouin zone, the lower the total energy of the crystal,
23
the more stable the phase.

24