7.

Alloys & Strengthening

Lecture 10. Introduction & the equilibrium phase diagram

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Outline of lecture
1. Learning outcomes.

2. Why important.

3. Basic concepts

4. The equilibrium phase diagram

5. The lever rule and example question

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1. Learning outcomes
At the end of this lecture you should be able to do the following:

• Describe why alloys are used and define the following terms: alloy (binary,
ternary etc), component, phase, solvent, solute, solid solution, solid solubility
(complete and partial), phase diagram and eutectic.
• Explain the difference between an interstitial and a substitutional solid solution
and be able to give examples of each, and to identify the factors which must be
met to allow substitutional solid solutions to form.
• Sketch a simple equilibrium phase diagram and be able to label the liquidus,
solidus and solvus lines and also identify the phases present.
• Given a binary equilibrium phase diagram and the composition of the alloy, then
for a given temperature, be able to determine the phases present and the
composition and the mass fractions of these phases using the lever rule.
• Describe the microstructural changes which occur when cooling an alloy of given
composition from the liquid phase, and be able to sketch simple microstructures.

You will be able to answer Q1-3 on Tutorial Sheet 7.

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2. Why have alloys?

• To control the mechanical properties of a metal

– In particular, the balance between strength and ductility, by introducing

distortion into the lattice to control the movement of dislocations.

– This opens the possibility of heat treatment to control the size and form of a
dispersed second phase (more on this in lecture 11).

– To improve corrosion resistance, wear resistance and weldability

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3. Basic concepts
3.1 Important definitions (you need to learn these terms!) Full list is in your notes

• Alloy:
– Mixture of a metal with one or more other metals or non-metals (binary,
ternary etc.)
• Component:
– An element included in an alloy.
• Phase:
– A region of material having uniform physical and chemical characteristics.
• Solvent:
– The element or compound that is present in the greater concentration (host
atoms).
• Solute:
– The element or compound that is present in a minor concentration.
• Solid solution:
– A single phase region in which solute atoms have mixed with solvent atoms
to form a homogeneous composition.

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3.2 Alloying via substitution of atoms
• Solute atoms replace some solvent atoms.

• For this to occur, the atoms must be similar in all important respects:
→ Hume-Rothery rules. Atoms should:
– Be approximately the same size (within about 15%)
– Have the same preferred crystal structure
– Have the same number of valence electrons
– Have similar electronegativity.

Too great a departure from these rules mean

that there is too much lattice distortion, and
some other lower energy structure will form.

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3.3 Alloying via interstitial atoms
• This is where solute atoms (or ions) occupy the spaces between solvent atoms
(or ions).
• This requires that Dsolute < 0.6Dsolvent
• This means that only certain atoms can be solutes in common metals
– B, C, Cl, H, N, O, P, S. (but gases in metals cause problems!)
• Very important is C in Fe (see later).
• A limit to its solubility is reached when all the interstices are occupied.

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3.4 Phases

Phase: Region of material having uniform physical and chemical characteristics.

e.g. Water and ice→ same chemical but different physical properties,
thus 2 phases.

e.g. Fe3C in Fe→ both solid, but different chemically, thus 2 phases.

(a) (b)

30 mm 30 mm

Steel: Fe3C (dark) in a-Fe (light)

Water & ice
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3.5 Solid solution- complete solid solubility

Nickel atoms
Copper atoms

Heat atoms to above Tm, mix and cool. A solid solution forms

Single phase

→ complete solid solubility

Solid solution: A single phase region in which solute atoms have mixed with solvent atoms
to form a homogeneous composition.

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3.6 Limited (partial) solid solubility

• Take a simple example of a sugar and water solution.

Sucrose/Water Phase Diagram

10 0
Solubility
Question: What is the
Temperature (°C)

80 Limit L solubility limit at 20°C?

(liquid)
60 L + Answer: 65 wt% sugar.
40 (liquid solution S If Co < 65 wt% sugar: syrup
i.e., syrup) (solid If Co > 65 wt% sugar: syrup
20 sugar) + sugar.

0 20 40 60 80 100 Sugar
Water
Pure

Pure

Co =Composition (wt% sugar)

(Adapted from Callister p.254) 10

4. Equilibrium phase diagrams

4.1 Complete Solid Solubility: Cu-Ni system

(a) 100% Cu (c) 50% Cu, 50% Ni (b) 100% Ni

Temp Temp Temp 1453°C

(°C) (°C) (°C)
1084°C

Time Time Time

Freezing temperature is between pure Cu and pure Ni

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Equilibrium phase diagram for Cu-Ni system

Liquidus line
T(°C) Liquid (single phase region)
1453°C

1084°C
Liquid + Solid
(2 phase region)
Solidus line
Solid (single phase region)

0
0 Mass % Ni 100

Complete solid solubility

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4.2 Limited Solid Solubility
• If the solute is less soluble in solid than in liquid solvent, the freezing temperature
of the solution is lowered as the proportion of solute is increased.
• e.g. solution of NaCl in water freezes at a lower temperature than pure water.
• As an example, the Pb-Sn system is now analysed.

(a) 100% Pb (c) 50% Pb, 50% Sn (b) 100% Sn

Temperature (°C)

327C
250C 232C
183C

Time
Freezing temperature is reduced

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Equilibrium Phase Diagram for Pb-Sn alloy

a phase = solution of Sn in solid Pb b phase = solution of Pb in Sn

solidus
L Eutectic
Temperature (°C)

L+a
L+b
a b
183°C Isothermal solidus

a+b

0 50 100
Mass % Sn

We have: 3 single phase fields: (L), (solid a) and (solid b)

3 two-phase fields: (L+solid a), (L+solid b), and (solid a+solid b)
3 triple points, one of which is the Eutectic Point

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4.3 Microstructures formed during slow cooling of a 15%Sn 85% Pb alloy

L: Co wt% Sn 1-2. All liquid phase

T(°C)
400
1 2. First solid phase starts to
L precipitate. L↔L+a
L
300 2 a
L+a 2-3. Gradual solidification
a: Co wt% Sn
3
a
200
TE 4 3. Last remaining liquid phase
a solidifies. L+S ↔a
b
100
a+ b Pb-Sn 4. A second solid phase, b,
system starts to precipitate
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0 10 20 30 5. A two phase solid solution of
2 Co Co , wt% Sn a and b exists at room temp
(sol. limit at T room ) 18.3
(sol. limit at TE)
(b appears here as fine
inclusions in polycrystalline
a= solid soln of Sn in Pb, b= solid soln of Pb in Sn a phase)
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4.4 Microstructures formed during slow cooling of eutectic Pb-Sn alloy

Pb-Sn system Micrograph of Pb-Sn

eutectic
T(°C) microstructure
L: Co wt% Sn
300 L
L+ a
a 183°C L+b b
200
TE

160 mm
100
a+b Adapted from Fig. 9.14, Callister 7e.

0 20 40 60 80 100

C, wt% Sn
CE
61.9

(Adapted from Callister, p278-279)

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5. Amounts of each phase present in a two phase region

5.1 Equilibrium compositions of L and S phases

Temp
Liquid

Liquid + Solid
T

Solid

Composition

Composition of liquid Composition of solid

in equilib with L+S at in equilib with L+S at
temp T temp T
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5.2 The Lever Rule

Temp
Liquid
Liquid + Solid

Solid

Composition (% Ni)
0% xL X xS

To find the relative amounts of the two phases, in the two phase field.

Let the total mass of substance =M

Mass liquid phase = ML
Mass solid phase = MS
Mass of Nickel= MN
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M = ML + MS

MN X
For a composition with an arbitrary X% Ni 
M 100

 M L + M S )
X
Thus: MN 
100

x  x 
An independent mass balance for Ni gives: MN   L ML + S MS
 100   100 

X X x x
Eliminating MN: ML + MS  L ML + S MS
100 100 100 100

Rearranging:  X  xL ) M L  xS  X ) M S This is the Lever Rule

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The Lever Rule graphically

Temp
Liquid
Liquid + Solid
T

Solid

Composition (% Ni)
0% xL X xS

ML MS

 X  xL ) M L  xS  X ) M S
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For any 2 phase field

Temp
Liquid
Liquid + Solid
T

Solid

Composition (% Ni)
0% xL X xS

xs  X X  xL
ML  and M S 
xs  xL xs  xL
Note:
(i) MS+ML=1 (i.e. 100% as nothing else is present in the 2 phase region)
(ii) Liquid and solid phases could have been replaced by 2 solid phases, e.g. a and b.
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Example
A lead-tin alloy contains 40% by mass of tin.
(a) What phase(s) are present at 150°C?
(b) What are the compositions of these phases?
(c) What are the relative mass proportions of the phases present?

Pb-Sn system
Answer:
T(°C) (a) In two phase region: a and b
300 L (b) Composition of a:
- draw tie line to a/a+b phase
a L+ a
200 L+b b boundary
-read off composition
- about 10% Sn, 90% Pb

100 Composition of b:
a+b - draw tie line to b/a+b phase
boundary
0 20 40 60 80 100 -read off composition
- about 98% Sn, 2% Pb
wt% Sn
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Example continued…

Pb-Sn system Answer continued

T(°C) (c) Relative proportions of a and b?
300
L Use the lever rule

a L+ a
200 L+b b xb  X 0.98  0.4
Ma    0.66
150°C
xb  xa 0.98  0.1
100
a+b X  xa 0.4  0.1
Mb    0.34
xb  xa 0.98  0.1
0 20 40 60 80 100
wt% Sn
xa X xb i.e. 66% a, 34% b by mass

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