07-Sep-2021

The Importance of Alloying and the Role of

Phase Diagrams in Engineering
The structure-property induced changes include:
1. increases yield strength and tensile strength which …
2. allows weight to be reduced
3. increase hardness to better resist wear
4. raises the melting point
5. Raises maximum use temperature of the solvent for
elevated-temperature service
6. lowers the melting point of the solvent/solute to facilitate
casting or allow brazing or soldering
7. enhances the corrosion resistance of the solvent, often
significantly
8. improves fabricability through improved machinability,
castability, formability, or weldability.
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The Importance of Alloying and the Role of

Phase Diagrams in Engineering
Important issues:
1. Which materials to mix into an alloy?
2. How much to mix (composition)? Up to solubility limit

Solubility studies, empirical rules and Phase

diagrams help.

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Solubility Limits
1. Usually there is a limit to how much of a given solute
will dissolve in a particular solvent at any temperature.

2. The reason for there being limit to solubility in the solid

state of crystalline materials is the extent to which the
internal energy (enthalpy) of the crystal increases from
strain in the lattice relative to the extent to which the
crystal is made more disordered (i.e., the entropy is
increased).

3. In solids, there is a limit to how much strain will be

tolerated, while in liquid solutions, strain is not the
limiting factor. Gases have unlimited solubility.

4. What are solubility limits? Experimentally determined,

but there are some prediction rules: we study one. 492

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Hume-Rothery's Rules
A set of empirical rules (developed from
observations) that rationalize the solubility limits
for substitutional solid solutions in metals,
including, in descending order of importance:
1. The greater the difference in size between solute and
solvent atoms, the lower the solid-state solubility,
with:
a.Complete solid solubility for a size difference of <8%
b.No solid solubility for a size difference of >15%
c. Almost proportional partial solubility for a size difference of 8-
15%.
Remember
numbers in 493
rule 1!

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 07-Sep-2021

Hume-Rothery's Rules
2. The greater the difference in the electronegativity
(Pauling's EN index) between solute and solvent, the
lower the solid-state solubility.
3. The greater the difference in valence number (i.e.,
number of valence electrons) between solute and
solvent, the lower the solid-state solubility (with some
additional details available on the Internet).
• Important consequence of rule-1a:
4. Complete solid-solubility can only occur if the solute
and solvent both have the same equilibrium crystal
structure. (These are called isomorphous alloys)
Remember
underlined 494
phrases

494

The Importance of Alloying and the Role of

Phase Diagrams in Engineering
Important issues:
1. Which materials to mix into an alloy?
2. How much to mix (composition)?

Solubility studies, empirical rules and Phase

diagrams help.

495

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 07-Sep-2021

The Importance of Alloying and the Role of

Phase Diagrams in Engineering
1. Alloy phase diagrams serve as "maps" of the
various physical and chemical forms the
material can take as a function of composition
and temperature under equilibrium conditions.
2. Phase diagrams portray
1. melting points
2. melting ranges
3. solubility limits, and
4. Phase transformations (sometimes called
phase reactions).
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1-Component P-T Phase Diagrams

Figure 12.1 497

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Recall 2-component liq-liq phase diagrams:

Pxy and Txy diagrams

For metals/solids, pressure has negligible effect, so

temperature is the main degree of freedom.
498
So Txy important.
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Phase diagrams for solid mixtures

•Cu-Ni

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Liquidus/Solidus Temperatures
1. The liquidus temperature is the temperature above which a
material is completely liquid.
2. The solidus temperature is the temperature below which the alloy
is 100% solid.
3. The freezing range of the alloy is the temperature difference
between the liquidus and solidus where the two phases exists, ie.,
the liquid and solid.
The cooling curve
for an isomorphous
alloy during
solidification. The
changes in slope of
the cooling curve
indicate the liquidus
and solidus
temperatures.

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Recall the Gibb’s phase rule

• Degrees of freedom (dof) = F = C - Π + 2 – r
C: number of components or species
Π: number of phases
r: number of reactions in equilibrium

• The dof correspond to: T, P, xji in j=1,…,Π phases for

i=1,…,C-1 components.

• Example: single component (C=1), no reaction (r=0):

• F= 1 – Π + 2 – 0 = 3 – Π
So dof for:
• One phase: 2 (can change T, P both, and within limits)
• Two phases: 1 (can change T or P but not both)
• Three phases: 0 (occurs at a fixed T, P known as triple point) 501

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Recall the Gibb’s phase rule

• Degrees of freedom (dof) = F = C - Π + 2 – r
C: number of components or species
Important note for solids and
Π: number of phases
liquids where vapour is not
r: number of reactions in equilibrium
involved: such systems are
• insensitive
The dof correspondto
to: pressure P, so
T, P, xji in j=1,…,Π dofforis
phases
i=1,…,C-1 components.
reduced by 1, giving:
• F =component
Example: single C - Π +(C=1), 2 – no r -1 or (r=0):
reaction
F=C-Π+1–r
• F= 1 – Π + 2 – 0 = 3 – Π
So dof for:
• One phase: 2
• Two phases: 1
• Three phases: 0 502

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Phase diagrams

• Cu-Ni

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Phase diagrams
• Cu-Ni

Amount of liquid = Amount of solid=

Liq = S/(R+S) Solid = R/(R+S)
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Solidification of a Solid-Solution Alloy

Under equilibrium or slow conditions

The change in structure

and composition of a Cu-
40% Ni alloy during
equilibrium solidification
showing that the liquid
contains 40% Ni and the
first solid contains Cu-52%
Ni. At 1250 C, solidification
has advanced and the
phase diagram tells us that
the liquid contains 32% Ni
and the solid contains 45%
Ni, which continues until
just below the solidus, all
of the solid contains 40%
Ni, which is achieved
through diffusion.

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Nonequilibrium Solidification and Segregation

Under nonequilibrium or fast conditions
When cooling is
too fast for atoms
to diffuse and
produce equilibrium
conditions,
nonequilibrium
concentrations are
produced. The
first solid formed
contains 52% Ni
and the last solid
only 25% Ni with
the last liquid
containing only
17% Ni. The
average
composition of Ni
is 40% but it is not
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uniform.

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Non - isomorphous phase diagrams

1. Recall isomorphous comes from having
complete miscibility for all concentrations
2. Only a few systems are isomorphous
3. Usually systems show complex phase
diagrams, e.g., eutetic, and more complex
4. These arise from having many crystalline
phases, and from insolubility
5. Equilibrium exists between liquid (melt)
and the various solid phases, and in-
between the various solid phases 507

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Other, More Complicated Phase

Diagrams

Figure 12.8 508

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Simple Eutectic Binary Alloy Systems

• For binary systems in
which the solute and
solvent differ in size
by 8-15%, giving rise
to partial solid-
solubility, or for
systems in which
there is no solid
solubility, a simple
eutectic reaction
occurs.

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Simple Eutectic Binary Alloy Systems

• For binary systems in
which the solute and
solvent differ in size
by 8-15%, giving rise
to partial solid-
solubility, or for
systems in which
there is no solid
solubility, a simple
eutectic reaction
occurs.

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