Metals

II. Phase diagrams of alloys

J. McCord

(mostly taken from Gottstein)

Contents

some basic thermodynamics

Gibbs phase rule

Binary alloys
Monotectic phase diagram
Continuous miscibility isomorphous alloy systems
Eutectic phase diagram
Peritectic phase diagram
Intermediate and intermetallic phases

Ternary alloys
Multicomponent phase diagrams
2.2

Why alloying?

Purpose of alloying
Improve mechanical properties
Improve physical properties
Improve or impede chemical reactions (e.g. resistant to corrosion)
Reduce the overall material cost (simplify processing/reducing metal cost)

Steel & cast iron (Iron (Fe) & Carbon (C)

Brass (Copper (Cu) & Zinc (Zn))
Bronze (Copper (Cu) & Tin (Sn))
Sterling silver (92.5%Ag & 7.5%Cu)
2.3

Formation of alloys

Alloys from a large number of elements

Binary and ternary phase diagrams

Alloying
Starting from homogeneous liquid solution
Changes in state, i.e. from liquid to solid, and the equilibrium between
the various phases present are illustrated using a phase diagram
Defining microstructure after solidification

2.4

Thermodynamic considerations (brief)

Ideal configurational entropy
Entropy of mixing SM (ideal solution)

S M = k lnW
W: Number of configurations

S M = k ln

N!
N A ! NB !

= Nk (cB ln cB + c A ln c A )

= Nk [cB ln cB + (1 cB )ln(1 cB )]

ci =

Ni
(atomic concentrat ions)
N A + NB

N = NA + NB: Number of atoms

Entropy of mixing SM

S M / cB
A

cB

Fig. 2.1.
Entropy of mixing for ideal solution.
Note that for cB 0 and cB 1

approaches +/- infintiy. As a

result, it is impossible to produce
perfectly pure crystals.
2.5

Regular solution interaction of A-B

Free energy of mixing GM = HM - TSM
Enthalpy of mixing HM

A-B interaction is neglected in

calculating W

Pair interaction model

H M = NZc AcB

= AB

1
( AA + BB )
2

>0
Enthalpy of mixing HM

<0
A

ij interaction energy
Z coordination number

cB

Fig. 2.2. Enthalpy of mixing HM for regular

solutions.

2.6

Composition dependence of G = H - TS
>0
<0

G = H - TS

Fig. 2.3. Composition dependence of Gibbs free energy G and its component H and (-TS) at constant
temperature and pressure for (a) continuous miscibility ( < 0) and (b) miscibility gap at c1 < c < c2 ( > 0).
Here, further alloying would increase G. Therefore, it is favorable to form to separate phases with
concentrations c1 and c2. A positive value of means that the A-A and B-B attraction is larger than the A-B
attraction. Note the asymmetry of the diagrams despite the symmetry of SM and GM. This is due to HA HB.
Since S/c for the pure components it is not possible to obtain perfectly pure materials.
2.7

Chemical potential i

Diffusion of A and B atoms between phases until establishment of

equilibrium condition.

A = A

Equilibrium condition for 2 components and two phases:

B = B

G
i =
Ni

N j i ,T ,p

Ni = ciN : number
of atoms of i

Tangent construction (see also Fig. 2.3(b))

Assumption: n components & P phases
Gibbs phase rule for number of degrees of freedom1
f=n-P+2.

For p = const.:

f = n - P + 1.

Fig. 2.4. Tangent construction.

1 There

are (n 1)P concentration variables and the variables p and T. The equilibrium
conditions yield n(P 1) boundary conditions.
2.8

The Gibbs phase rule

f=n-P+2

f = number of degrees of freedom

or number of externally controlled variables (e.g. temperature, pressure,
composition)

n = number of components in the system

Smallest number of independent chemical constituents by means of which
the composition of every possible phase can be expressed

P = number of phases

2 = number of state variables

Temperature and pressure (usually incompressible at ordinary pressures,
pressure is considered fixed)

Gibbs phase rule can written as

f=n-P+1
2.9

Equilibrium Phase Diagrams

provide information for the control of the micro- or phase
structure of an alloy system.
are for predicting phase transformations and the
resulting microstructures.
represent the relationships between temperature and
the compositions and the quantities of phases at
equilibrium.
are maps of the equilibrium phases associated with
various combinations of temperature and composition.

2.10

Equilibrium phases in two component systems

liquidus line
L
L
L

L+S

solidus line

tie line

TM
L+S

S
liquidus line
S

f = degrees of freedom
n = number of components
P = number of phases

solidus line

f = n - P + 1.

Fig. 2.5. At a given pressure a one component system (a) has a certain melting point. In a binary
system, however, there is a melting range by liquidus and solidus lines. These can either fall (b) or rise
(c) with concentration. The tie line connects equilibrium concentration.
2.11

Monotectic phase diagram (Pb-Fe)

Complete miscibility gap in the solid and liquid phase.

Pb-melt + Fe-melt

GS 4.7
Pb-melt + Fe-crystal

Pb-crystal + Fe-crystal

Abb. 2.6. Monotectic phase diagram of lead iron PbFe.

2.12

Monotectic phase diagram (Cu-Pb)

Cu-solid + Pb-liquid

Abb. 2.7. The Copper-lead phase diagram.

2.13

Continuous miscibility

L
L
S

L
L

L
L+
L

Fig. 2.8. Composition dependence of Gibbs free energy of crystal or solid phase and melt L of a
binary alloy with continuous miscibility for different temperatures T. The composition ranges of the
occurring phases correspond to an isothermal section through the phase diagram.
2.14

Ni-Cu
Point y

Point x

Alloy of 20%Cu 80% Ni at T =

500C (solid)

Point y

Two-phase region (solid &

liquid) at T = 1200C

Composition not defined by

point y!

Fig. 2.9. The copper-nickel isomorphous

phase diagram
2.15

system composition

The Lever rule

No equilibration in solid phase

Tie line

c0 approached asymptotically
Strongly extended solidification
range
Formation of layered crystals

Weight fraction mL of melt and m of solid

Conservation of atom numbers
c0 = mL c 2 + m c1 ,
c0 c 2
c1 c 2
c c
mL = 1 0
c1 c 2
m =

m + mL = 1

m c0 c 2
=
mL c1 c0

Fig. 2.10. Illustration of the solidification of a

binary alloy. The microstructure of the three
states, liquid, semi-solid, and solid are
schematically illustrated.

Lever rule at T = T1
2.16

Continuous miscibility (II)

Fig. 2.11. Relationship of the free-energy curves that

lead to a maximum in the phase diagram.
2.17

Continuous miscibility (III)

Fig. 2.12. Relationship of the free-energy curves that

lead to a minimum in the phase diagram.
2.18

Cu-Au phase diagram

weight %Au

L+S

atomic %Au
Fig. 2.13. Cu-Au phase diagram with a minimum. In the solid state there
is a continuous solution.

2.19

Solid solutions
Substitutional or interstitial solid solution

Small solute atom

Interstitial solid solution

Substitution of the atoms in the solvent unit cell

Substitutional solid solution

Fig. 2.14. Different types of solid solution crystals. (a) Interstitial solid solution, (b) substitution solid
solution with random distribution, (c) ordered substitutional solid solution.

2.20

Interstitial solid solution

Metallic materials posses high atomic packing
factors, thereby the interstitial positions are
small.

The atomic diameter of an interstitial atom

smaller is than that of the host atoms.

Impurity atoms are ordinarily larger than the

interstitial sites.
Introduction of lattice strains on the adjacent
host atoms.

Interstitial solid solutions are often formed by

transition elements and metalloids.

2.21

Interstitials in the fcc and bcc lattice

fcc

bcc

Fig. 2.15. Interstitial in the fcc and bcc lattice. (a) Octahedral interstice in the fcc, (b) tetrahedral
interstice in fcc, (c) octahedral interstice in bcc. The open circles indicate the different but equivalent
interstitial positions.

Substitutional solid solution

Home-Rothery-Rules
1. Atomic size factor Difference in atomic radii between the two atom types
should not exceed 15%.
2. Valences The number of valence electrons should not be very different.
3. Electronegativity The difference of electronegativity (chemical affinity)
should be small. In case not, intermetallic compounds form instead of a
substitutional solid solution.

Crystal structure For appreciable solid solubility,

the crystal structures for metals of both atom types
must be the same (FCC, BCC, ...)

Melting point A metal of higher melting point

dissolves a metal of lower melting point to a
greater extent than vice versa.
2.23

Cu-Au phase diagram

weight %Au

Entropy contribution!!!
S

L+S

Fig. 2.16. Phase diagram of the system

CuAu that forms several solid state
ordered phases at low temperatures.
However, these turn to a disordered state
well below the melting point.
atomic %Au
2.24

Ordered solid solutions

bcc

fcc

Cu atoms

Cu atoms

Au atoms

Au atoms

Fig. 2.17. Ordered atom distributions of the AB-type can be realized in the (a) CsCl lattice (= B2
structure); (b) AB3 in the Cu3Au lattice (=L12 structure). Both are consistent with a bcc or fcc solid
solution crystal. A ordered face centered cubic solution of the AB type (c) loses its cubic structure.
2.25
Due to differences in the atomic radii a tetragonal crystal lattice is formed.

Long range order parameter s (sublattices)

s=

px
1 x

p: fraction of A-atoms in A-sublattices

x: fraction of A-atoms in the alloy

AB-alloy with bcc structure

s = 2p 1
Complete long range order

p = 1, s = 1

Complete statistical disorder

p = 0.5, s = 0

Wrong order

p = 0, s = 1

Order-disorder transition at elevated T:

mostly 2nd order transitions

Fig. 2.18. The bcc lattice consists of two cubic simple sublattices that are displaced along
the <111> -direction. With s = 1
each of the sublattices is
occupied by only one sort of
atoms.

2.26

Debye-Scherrer images of Cu3Au

T << Tc

T < Tc

T > Tc

Fig. 2.19. Occurrence of long-range ordered phases can be confirmed by superlattice lines in a DebyeScherrer-image. Note the distinct lines for T << Tc.

Short range order parameter

q qd
=
qm qd

q: fraction of B-atoms as next neighbors of A-atoms

qd: fraction of B-atoms as neighbors of A-atoms in
the disordered state
qm: fraction of B-atoms as neighbors of A-atoms in
the completely ordered state

No long range correlation needed

Short range order coefficients can be extended to more distant neighbors

0 1
Complete short range order

=1

No short range order

=0

Short-range order for < 0.

can be determined from the intensity of the diffuse scattering background. Derivations from ideal
crystal structure lead to diffuse x-ray scattering with intensity outside the Bragg-reflections.
2.28

Temperature dependence of order parameters

Temperature [K]
Fig. 2.20. Temperature dependence of the order parameters. Whereas the long range order
parameter s is zero above Tc, the short range order parameter exists also above Tc.

Antiphase boundaries (Cu3Au)

resistivity [10-6 cm]

(a)

(c)

quenched from 650 C

annealed at 200 C

atomic %Au

Abb. 2.21. Change of electrical resistivity with the

occurrence of superlattices. (b) Sketch of a long-range
ordered Cu3Au structure divided into domains. The
regions are separated by antiphase boundaries. (c)
Visualization of antiphase boundaries by TEM.

(b)

2.30

Formation of a solubility gap

Increasing energy of mixing GM > 0
L

L
L

L
L

Fig. 2.22. Schematic illustration of the evolution of the eutectic phase diagram resulting from a
widening of the miscibility gap in the solid state. This is equivalent to an increasing energy of mixing
GM > 0.
2.31

Eutectic system
S

S
S

L
L

L
L

L
L

L
L

L
S

Fig. 2.23. Composition dependence of Gibbs free energy of crystal or solid phase and melt L of a
binary alloy with a miscibility gap for different temperatures T. The composition ranges of the occurring
2.32
phases correspond to an isothermal section through the phase diagram.

Eutectic phase diagram

(solidification)

hypoeutectic

hypereutectic

Gibbs phase rule

f=n-P+1
Eutectic reaction
n = 2 (A, B) - components

P = 3 (L, , ) - phases
f = 0 (fixed point)
No degree of freedom
Simultaneous precipitation of and
(mostly fine-lamellar microstructure).
Invariant reaction L +

weight %B

Fig. 2.24. Schematic eutectic phase diagram illustrating

the development of the microstructure of a sub eutectic
alloy during solidification. At the eutectic composition cE
the alloy solidifies like a pure metal (no solidification
range).
2.33

Copper-Silver phase diagram

Fig. 2.25. The eutectic Cu-Ag phase diagram.

2.34

Example: PbSn lead-tin phase diagram

cE

Fig. 2.26. Schematic representations of the equilibrium microstructures for a leadtin alloy of composition
C4 cooled from the liquid-phase region.

Eutectic microstructure

Fig. 2.27. Example of an eutectically solidified microstructure (c = cE)

in the AlZn system (95.16 weight% Zn).

2.36

Peritectic phase diagram

Strongly different melting points

GM

Increasing energy of mixing

Peritectic phase diagram

>0

Fig. 2.28. Schematic illustration of the evolution of the peritectic phase diagram resulting from a
widening of the miscibility gap in the solid state accompanied by a strong difference of melting points
of the components A and B. The first is equivalent to an increasing energy of mixing GM > 0.
2.37

Example: Peritectic Fe-Ni phase diagram

Fig. 2.29. The FeNi phase diagram.

2.38

Phase diagram with an intermetallic phase

GM, < 0 Tendency to form high melting-point AxBy compounds

Fig. 2.30. Schematic illustration illustrating the formation of intermetallic phases due to a widening of
the miscibility gap in the solid state.

In the intermediate and intermetallic phase the crystal structure is different from
the structures of the components A and B.
2.39

Copper-Zinc phase diagram

Fig. 2.31. Copper zinc (brass) phase diagram.

2.40

Summary of
equilibrium phase
transformations
(binary alloys)

Abb. 2.32. Overview of different

type of phase transformations.

2.41

Multicomponent systems ternary systems

cA = 70 %
cB = 10 %
cC = 20 %

cA = 70 %
cC = 20 %

cB = 10 %
Fig. 2.33. Representation of the composition in a ternary system.
2.42

Multicomponent systems ternary systems

cA = 70 %
cB = 10 %
cC = 20 %

cA + cB + cC = 1

cA = 70 %
cC = 20 %

cB = 10 %
Fig. 2.34. Representation of the composition in a ternary system. From elementary
geometry the sum of the lengths of the arrows is 100%.

2.43

Eutectic ternary system

Fig. 2.35. (a) Perspective view of a ternary phase diagram. (b) Projection of liquidus plane on the
concentration valley including eutectic valleys and melt isotherms.
(e1, e2, e3: eutectic points of binary alloys; E: Eutectic point of ternary alloy).
2.44

Combining three
eutectic binaries

Eutectic valleys

Fig. 2.36. A ternary phase diagram

with three eutectic binaries between
A, B and C.

2.45

Isothermal sections

Fig. 2.37. Isothermal section for a ternary phase diagram. A few tie-lines are shown by dotted lines.
The lines represent two-phase equilibriums and are also called conodes. For a given point on the tielines, the fractions of the two phases are determined by the lever rule. Here the temperature is below
the A-B eutectic but above the eutectic temperature of the ternary A-C and B-C.

2.46

Isothermal sections

Fig. 2.38. Isothermal section for a ternary phase diagram. A few tie-lines are shown by dotted lines.
The lines represent two-phase equilibriums and are also called conodes. For a given point on the tielines, the fractions of the two phases are determined by the lever rule. Here the temperature is below
the binary eutectics but above the ternary eutectic temperature.

2.47

Isothermal sections

Fig. 2.39. Isothermal section for a ternary phase diagram. A few tie-lines are shown by dotted lines.
The lines represent two-phase equilibriums and are also called conodes. For a given point on the tielines, the fractions of the two phases are determined by the lever rule. Now the temperature is below
the ternary eutectic temperature.

2.48

Temperature-concentration sections

L
T
L+
L+
L+ +

L++

L++
+

++
AC

BC

Fig. 2.39. Temperature-concentration section for a ternary phase diagram together with the projection
of eutectic valleys, melt isotherms, and the non-variance plane.
2.49