ENGINEERING MATERIALS

(ME-221)

Instructor: Dr. Rafiq Ahmad

Lecture 05: Phase Diagram

“Because without materials, there is no engineering.”

 Components and Phases

• Components:
The elements or compounds that are mixed initially (Al and Cu).
• Phases:
A phase is a homogenous, physically distinct and mechanically
separable portion of the material with a given chemical
composition and structure (a and b).

Aluminum-
Copper
Alloy

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 Phase Equilibria: Solubility Limit

• Solution – solid, liquid, or gas solutions, single phase

• Mixture – more than one phase

Sugar/Water Phase Diagram

• Solubility Limit:
Maximum concentration for 100
Solubility
which only a single phase L
80 Limit

Temperature (°C)
solution exists. (liquid)
60 L +
Question: What is the
(liquid solution S
solubility limit for sugar in 40
water at 20°C? i.e., syrup) (solid
20 sugar)
Answer: 65 wt% sugar.
At 20°C, if C < 65 wt% sugar: syrup 0 20 40 6065 80 100
At 20°C, if C > 65 wt% sugar: syrup + sugar
Water

C = Composition (wt% sugar)

Sugar
 Equilibrium

• A system is at equilibrium if its free energy is at a

minimum, given a specified combination of temperature,
pressure and composition.
• The (macroscopic) characteristics of the system do not
change with time — the system is stable.
• A change in T, P or C for the system will result in an
increase in the free energy and possible changes to
another state whereby the free energy is lowered.

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One Component Phase Diagram

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 Phase Diagrams

• Indicate phases as a function of Temp, Comp and Pressure.

• Focus on:
- binary systems: 2 components.
- independent variables: T and C (P = 1 atm is almost always used).
T(°C)
1600 • 2 phases:
L (liquid)
1500 L (liquid) a (FCC solid solution)

1400 • 3 different phase fields:

Cu-Ni L
system 1300 L+a
1200 a a
(FCC solid
1100
solution)
1000
0 20 40 60 80 100 wt% Ni 6
 Effect of Temperature & Composition (Co)

• Changing T can change # of phases: path A to B.

• Changing Co can change # of phases: path B to D.
T(°C)
1600

1500 L (liquid)

1400
B D
1300
Cu-Ni
system 1200 a
(FCC solid solution)
1100 A

1000 wt% Ni
0 20 40 60 80 100
Cu 7
 Determination of phase(s) present

• Rule 1: If we know T and Co, then we know:

--how many phases and which phases are present.

• Examples:

Cu-Ni
phase
diagram

Melting points: Cu =
1085°C, Ni = 1453 °C

Solidus - Temperature where alloy is completely solid. Above this line, liquefaction begins.
Liquidus - Temperature where alloy is completely liquid. Below this line, solidification
begins. 8
 Phase Diagrams: composition of phases

• Rule 2: If we know T and Co, then we know:

--the composition of each phase.
Cu-Ni
• Examples: system

At TA = 1320°C:
Only Liquid (L) present
CL = C0 ( = 35 wt% Ni)
At TD = 1190°C:
Only Solid (a) present
Ca = C0 ( = 35 wt% Ni)
At TB = 1250°C:
Both a and L present
CL = C liquidus ( = 32 wt% Ni)
Ca = C solidus ( = 43 wt% Ni)
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 Phase Diagrams: weight fractions of phases

• Rule 3: If we know T and Co, then we know:

--the amount of each phase (given in wt%).
• Examples:
Cu-Ni system

SS
W  43  35
WLL R S 
43  32
 73wt %
R S
RR
W 
Waa R S = 27wt %
R S 10
 Ex: Equilibrium Cooling of a Cu-Ni Alloy

T(°C) L (liquid) L: 35wt%Ni

• Phase diagram:
Cu-Ni
Cu-Ni system. system
130 0 A
• Consider L: 35 wt% Ni
a: 46 wt% Ni B
microstuctural 35 46
changes that 32 C 43
accompany the D
24 36 L: 32 wt% Ni
cooling of a
a: 43 wt% Ni
C0 = 35 wt% Ni alloy 120 0 E
L: 24 wt% Ni
a: 36 wt% Ni
a
(solid)

110 0
20 30 35 40 50
C0 wt% Ni
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• Development of
microstructure during
the non-equilibrium
solidification of a 35
wt% Ni-65 wt% Cu
alloy outcome:
• Segregation-
nonuniform
distribution of
elements within
grains.
• Weaker grain
boundaries if alloy
is reheated.
 Cored vs Equilibrium Phases

• Ca changes as it solidifies.
• Cu-Ni case: First a to solidify has Ca = 46wt%Ni.
Last a to solidify has Ca = 35wt%Ni.
• Fast rate of cooling: • Slow rate of cooling:
Cored structure Equilibrium structure

• Coring can be eliminated by means of a homogenization heat treatment carried out at

temperatures below the alloy’s solidus. During the process, atomic diffusion produces grains
that are compositionally homogeneous.
 Mechanical Properties: Cu-Ni System

• Effect of solid solution strengthening on:

--Tensile strength (TS) --Ductility (%EL,%AR)

--Peak as a function of Co --Min. as a function of Co

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 Binary Isomorphous Systems

Cu-Ni system:
• The liquid L is a homogeneous liquid solution composed
of Cu and Ni.
• The α phase is a substitutional solid solution consisting
of Cu and Ni atoms with an FCC crystal structure.
• At temperatures below 1080 C, Cu and Ni are mutually
soluble in each other in the solid state for all
compositions.
• The complete solubility is explained by their FCC
structure, nearly identical atomic radii and electro-
negativities, and similar valences.
• The Cu-Ni system is termed isomorphous because of
this complete liquid and solid solubility of the 2
components.
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 Criteria for Solid Solubility

Simple system (e.g., Ni-Cu solution)

Crystal
Structure electroneg r (nm)

Ni FCC 1.9 0.1246

Cu FCC 1.8 0.1278

• Both have the same crystal structure (FCC) and have

similar electronegativities and atomic radii suggesting high
mutual solubility.
• Ni and Cu are totally soluble in one another for all proportions.

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 Isomorphous Binary Phase Diagram

• Phase diagram:
Cu-Ni system. T(°C)
• System is: 1600
Cu-Ni
-- binary 1500 L (liquid) phase
2 components: diagram
Cu and Ni. 1400
-- isomorphous
i.e., complete 1300
solubility of one
1200 a
component in
another; a phase 1100
(FCC solid
field extends from solution)
0 to 100 wt% Ni. 1000
0 20 40 60 80 100 wt% Ni

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 Importance of Phase Diagrams

What is the correlation between microstructure

and mechanical properties?

Why Phase Diagram?

• There is a strong correlation between microstructure and

mechanical properties, and the development of alloy
microstructure is related to the characteristics of its phase
diagram.
• Phase diagrams provide valuable information about
melting, casting, crystallization and other phenomena.

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 Microstructure

• In metal alloys, microstructure is characterized by

the number of phases, their proportions, and the
way they are arranged.
• The microstructure depends on:
– Alloying elements
– Concentration
– Heat treatment (temperature, time, rate of cooling)

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