18.

Phase Diagrams I

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 Questions
• Does combining two metals always result in
an alloy which averages the properties of
the two metals? or can the alloy be greater
than the sum of its parts?

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 Learning Objectives

• Identify different phases and compositions from a

phase diagram.
• Apply the lever rule to determine the mass
fraction of phases from a phase diagram.
• Recognize the limitations of using phase diagrams
in equilibrium and non-equilibrium conditions.

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 1-component (Unary) Phase Diagram
Example - Water (Note: Pressure vs Temperature)

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 2-component (binary) phase diagram
Example - Sugar/Water Phase Diagram
(Note: Temperature vs Composition)

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 Phase Diagrams
• May be plotted as [temperature vs. composition] or
[pressure vs. temperature] – normally [temp vs.
composition], as most manufacturing processes operate at
atmospheric pressure.
• Need to study phase diagrams to understand aspects of the
following:
– Alloying
– Heat treatments and microstructure
– Solidification (important during casting and welding)
• Phase diagrams depict equilibrium conditions:
– Represent the system after a long period of time has elapsed, or have
evolved slowly.
– Represent how the system would behave if mass diffusion rates were
infinitely fast (typical mass diffusion rates in materials are much, much,
lower than thermal diffusions rates - e.g. D = 10-17 m2/s for gallium in
silicon, = 10-11 m2/s for C in in steel at 9270C)
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 Phase Diagrams
• In real manufacturing processes the times involved are
finite and hence equilibrium is often not achieved – e.g.
kinetics become important.
• We will use Phase Diagrams to understand what phases
are present under long-term equilibrium conditions.
• Definition of a Phase
– “A homogeneous portion of a system that has uniform physical
and chemical characteristics”
– Examples are: solids of a similar structure, liquid, gas
– For a solid, allotropes are solids with different structural forms
(eg. FCC, BCC, HCP), and are considered different phases even if
they have the same composition.
– Many materials have multiple phases present at a given
temperature and composition – e.g. a solid and liquid, or two
different solid phases.

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Example - Water/Salt phase diagram
Lowest effective
temperature for NaCl
as a practical de-icer
is ~-7oC (~10 percent
salt required to
create all liquid. For
practical purposes,
too much salt is
needed to melt at
lower temperatures!)

This is an example of
a Binary Eutectic
System, discussed in
a few slides.

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Binary Isomorphous Systems
• Binary - Two elements
• Isomorphous - “Liquid and solid regions each
contain only one phase”
• Observe the phase changes along the 0% and
100% vertical axes to see how the pure elements
behave, and compare it to any other composition.
• Cu-Ni is a good example of an isomorphus system
– Copper and Nickel both have FCC crystal structure,
nearly identical atomic radii and electronegativity
values, and similar valence structures.

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Cu-Ni Phase Diagram (binary isomorphus system)
Liquid phase is
present at all
temperatures
homogeneous and
liquid solution compositions
above this line

By convention,
each different
solid phase given
a greek label
(here it is a)

Substitutional
solid solution Solid phase a
consisting of both only exists
Cu and Ni atoms,
FCC structure
below this line
Cu, Ni have
nearly identical
atomic radii, FCC
structure, etc.,..

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 Cu-Ni Phase Diagram (binary isomorphus system)
Melt
temperature of
pure Ni:
Liquidus Line - 14530C
Boundary between
100% liquid and
the liquid/solid two
phase region

Solidus Line - Melting

Boundary between ends at
100% solid and the 1320 0C
liquid/solid two
phase region Solid and
liquid present
in equlibrium

Melting
starts at
1280 0C
Melt
temperature of
pure Cu:
10850C
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 Cu-Ni System -
Tensile Strength and Ductility (%elongation)

As a result of continuous solubility of Cu in Ni (and Ni in Cu), there is a smooth

and continuous variation in mechanical properties (Note: non-linear though).
NB – Tensile strength of Cu-Ni mix is often HIGHER than either Copper or Nickel
in its pure form. This is Solid-solution strengthening. (see Lecture #14 –
Strengthening of Crystals) 12
 Use of Phase Diagrams
• Three kinds of information can be obtained from Phase
Diagrams (note: again limitations of equilibrium
assumption):

1. What phases are present at a given temperature +

composition?
 Go to the temperature and composition of interest and
identify the region (generally single or two phases)
2. What is the composition of each of these phases?
3. How much is present of each phase (i.e. the percentage or
fractions of these phases)? Either by % mass or %
volume.

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 2. Determination of Phase Composition
• For Single Phase Regions
(L, or a-solid) 
Composition = C0
• For a Two Phase Region
– Draw a horizontal line at
temperature of interest
through the point. This is
called a “tie line”
– Intersection of the tie line
and the phase boundaries
gives composition of
respective phase
In the example, the point B is
composed of a liquid with
~32% Ni, and an a-solid with
~43% Ni

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 2. Determination of Phase Composition -
notes
Note that the overall
composition of the a +
Liquid mixture remains at
C0 (i.e. the relative volume
fraction of Nickel present
in liquid at CL and solid a
at Ca add to yield an
overall composition of C0)

In the example, the masses

of Cu and Ni are
redistributed between the
solid and liquid phases, but
with a weighted average of
C0 = 35% Nickel
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 3. Determination of fractions of
each phase
• The Lever-Rule is a commonly used mathematical model to predict
fractions of a particular phase at a given temperature T.
• It is based on the assumption of infinite diffusion in the solid and liquid and
therefore mimics the phase diagram.
 Ignores mass transfer
 Ignores heat transfer
• At a given temperature and composition, both the solid and liquid have a
uniform composition given by the phase diagram.
• Because of the assumption infinite diffusion, the mass is redistributed
instantaneously. This obviously is not found in the reality but is a useful first
approximation.

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 3. Determination of fractions of
Lever Rule:
each phase, cont
– Draw tie line (length R + S)
– Mark intersection with phase
boundaries
– Calculate the fraction of the length of Overall composition = C0
the tie line on the OPPOSITE side of
the overall composition point vs. the
overall tie line length. This fraction
the same as the mass fraction of each
phase
WL , Wa = mass fraction of liquid, a-solid

𝑆 𝐶𝛼 − 𝐶0
𝑊𝐿 = =
𝑅 + 𝑆 𝐶𝛼 − 𝐶𝐿
𝑅 𝐶0 − 𝐶𝐿
𝑊𝛼 = =
𝑅 + 𝑆 𝐶𝛼 − 𝐶𝐿

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3 Determination of fractions of
each phase, cont.
In the example (T = 1250oC):
C0  35% Ni ;
Ca  42.5% Ni ;
CL  315%
. Ni

Apply Lever Rule…

𝐶𝛼 −𝐶0 42.5−35
𝑊𝐿 = = = 0.68 mass fraction liquid
𝐶𝛼 −𝐶𝐿 42.5−31.5

𝐶 −𝐶 35−31.5
𝑊𝛼 = 𝐶0 −𝐶𝐿 = 42.5−31.5 = 0.32 mass fraction a - solid
𝛼 𝐿

𝑊𝛼 + 𝑊𝐿 = 0.68 + 0.32 = 1 overall mass conservation condition

(weight of nickel in 𝛼) + (weight of nickel in Liquid ) species conservation

𝑊𝛼 𝐶𝛼 + 𝑊𝐿 𝐶𝐿 = 0.68 × 31.5 + 0.32 × 42.5 = 35%𝑁𝑖 condition
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 3. Determination of fractions of
each phase, notes
• Lever rule is derived from a calculation of mass conservation (relatively easy
calculation, can find online very easily)
• The lever rule makes sense when the point is close to a phase boundary line – in
this case, length of the tie line on the OPPOSITE side of the overall composition
point is relatively long, which means the mass fraction for the phase at the phase
boundary will be relatively large.

• To calculate volume fraction V𝛼 and VL , incorporate the density of each phase rL

ra
𝑊𝛼 𝑊𝐿
r𝛼 r𝐿
𝑉a = 𝑉𝐿 =
𝑊𝐿 𝑊𝛼 𝑊𝐿 𝑊𝛼
+ +
r 𝐿 r𝛼 r𝐿 r𝛼
 Equilibrium Cooling
• Starting from the liquid (point a),
the process of solidification
begins with nucleation of primary
solid a-phase (point b)
• As solid grows, there is
redistribution in species in both
phases (point c). In equilibrium
cooling, it is assumed that the
temperature is changing slowly
enough such that the
concentration within both the
liquid and solids are uniformly
distributed and change
continuously as more solid is
formed (points d, e).
• The compositions of the starting
liquid and the final solid are
identical and uniform (a, e)
• Amount of solid and liquid at any
given time can be calculated
from Lever Rule
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 Non-Equilibrium Cooling
• Assume no or very little
diffusion in Solid, but
instantaneous diffusion in Liquid
• Can also assume no or little
compositional changes in solid
over time.
• This means that the
composition is non-uniform in
the solid – the centre of the
solid particles may be more
highly concentrated than the
outer regions of the solid.
• This is an example of
microstructure – grains and
phase structures are visible with
a microscope, and can influence
the properties of the material.

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 Learning Objectives (review)

• Identify different phases and compositions from a

phase diagram.
• Apply the lever rule to determine the mass
fraction of phases from a phase diagram.
• Recognize the limitations of using phase diagrams
in equilibrium and non-equilibrium conditions.

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