EG 244 Material Science I

Phase Diagrams

Welcome!

Enzoh Langi (PhD)

enzoh.langi@cbu.ac.zm/enzohlangi@yahoo.com

Office: HOD Mechanical Department – School of Engineering

 Phase diagrams

Introduction ( Binary Phase diagrams)

❑ A different kind of phase diagram which is very common is

where the temperature and composition are varied when the
pressure is held constant → 1 atm
❑ We will focus on binary- alloys
❑ Binary phase diagrams are helpful in predicting phase
transformations and the resulting microstructure
❑ Therefore, binary phase diagrams are maps representing the
relationships between temperature and compositions as well
as quantities of phases at equilibrium
 Phase diagrams

Objectives

❑ Determine for a given binary phase diagram

• Phase(s) present
• Composition of the phase(s)
• Mass fraction of the phase(s)
❑ Locate the temperature and compositions of all eutectic,
eutectoid, peritectic and congruent phase transforms
❑ Be able to write reactions for all the transforms for either
heating or cooling
 Phase diagrams

Binary Phase diagrams (Isomorphous systems)

❑ The easiest type of binary phase diagrams to understand and

interpret is a copper-nickel system
❑ The system is said to be isomorphous because the
(components) are completely soluble in liquid and solid
forms
 Phase diagrams

Binary Phase diagrams (Isomorphous systems)

Note:
In the phase diagrams for
metallic alloys, solid
solutions are commonly
designated by Greek letter
α, β, γ etc.
Consider the copper – nickel
phase diagram given below
 Phase diagrams
Binary Phase diagrams (Isomorphous systems)
❑ In the phase diagrams, there are
three different phase regions or
fields
▪ (𝛼) an alpha field
▪ (𝐿) a liquid field
▪ (𝛼 + 𝐿) two-phase field
❑ Each region is defined by the
phase or phases that exist over
the range of temperatures and
compositions
❑ The phases are delimited by
phase boundaries
 Phase diagrams
Binary Phase diagrams (Isomorphous systems)
❑ The liquid 𝐿 is a homogeneous
solution composed of nickel and
copper
❑ 𝛼 phase is a substitutional solid
solution with both copper and
nickel having an FCC crystal
structure
❑ At temperatures below 1080℃,
copper and nickel are mutually
soluble in each other in the
solid state at all compositions
Why?
 Phase diagrams

Criteria for Solid Solubility

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

Crystal Structure electronegative 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 (W. Hume – Rothery
rules) suggesting high mutual solubility.
❑ Ni and Cu are totally soluble in one another for all
proportions.
 Phase diagrams
Interpretation of Phase diagrams

❑ In a binary system with known composition and

temperature at equilibrium, at least three kinds of
information are available
▪ Phase(s) present
▪ Composition of the phases present
▪ Percentages or fractions of the phases
❑ We now show how to determine these three pieces of
information in a nickel-copper system
 Phase diagrams

Interpretation of Phase diagrams

Phases Present
▪ In order to determine the phase(s) present, one needs to
know the temperature and composition at a point on the
phase diagram e.g., 60 wt % 𝑁𝑖 − 40𝑤𝑡 % 𝐶𝑢 at 1100℃
 Phase diagrams
Interpretation of Phase diagrams

35 wt% Ni and 65 wt% Cu

 Phase diagrams
Interpretation of Phase diagrams
How to determine the Phase compositions
❑ Locate the temperature - composition point on the phase
diagram.
❑ For a single phase, the composition is just the same as the
overall composition of an alloy.
❑ To determine the phase composition for an alloy with
composition and temperature located in a two-phase region
is not easy but can be determined using a tie line
❑ A tie line, can be thought of as a horizontal lines with same
temperature (isotherm)
❑ They are drawn so as to terminate at phase boundary lines
on either side
 Phase diagrams

Interpretation of Phase diagrams

How to determine the Phase compositions

❑ Using the tie line we can compute the equilibrium
concentrations of the two phase (only) using the following
procedure:
▪ Draw a tie line across the two – phase region at the
temperature of the alloy
▪ Note the intersection points on the phase boundaries
▪ Drop the perpendiculars from intersection points to
composition axis where each respective phase is read
 Phase diagrams

Interpretation of Phase
diagrams

How to determine the Phase

compositions

Example:
Determine the phase
composition for copper-nickel
alloy at 35 𝑤𝑡 % 𝐶𝑢 and
65 𝑤𝑡 % 𝑁𝑖 alloy at 1250℃
 Phase diagrams
Interpretation of Phase diagrams
How to determine the Phases compositions
Solution
The problem is to determine the composition in 𝑤𝑡 % of both
𝐶𝑢 and 𝑁𝑖 for both the 𝛼 and 𝐿 phases
 Phase diagrams
Interpretation of Phase diagrams
How to determine the Phase compositions
Solution
▪ Liquidus boundary is by the composition axis at 31.5 𝑤𝑡 % Ni
and 68.5 𝑤𝑡 %Cu at 𝐶𝐿
▪ Solidus tie line intersection , 𝐶𝛼 42.5 𝑤𝑡 % 𝑁𝑖 −
57.5 𝑤𝑡 % 𝐶𝑢
 Phase diagrams
Interpretation of Phase diagrams

How to determine the Phase amounts

❑ It is important to determine the relative amounts as fractions or

percentage of the phases present at equilibrium
❑ In a single phase, only one phase is present therefore the
fraction is 1.0 or 100% as a percentage
❑ If the composition and temperature position is located within a
two – phase region, one needs to think
❑ Here again the tie line in conjunction with a procedure called
lever rule must be applied.
 Phase diagrams
Interpretation of Phase diagrams
How to determine the Phase amounts
❑ In the lever rule, the following procedure is followed
i. Draw a tie line across the two-phase region at the
temperature of the alloy
ii. Overall alloy composition is located on the tie line
iii. To compute the fraction of one phase, take the length of
the tie line from the overall alloy composition to the phase
boundary for the other phase and divide by the total tie
length.
iv. Use the above steps to determine the fraction of the other
phase
v. Multiply the phase fractions by 100 to get the phase
percentages
 Phase diagrams

Interpretation of Phase diagrams

How to determine the Phase amounts

❑ How do you determine the tie line segment lengths?

i. Either by direct measurement from phase diagram
using a linear scale graduated in millimeters or
ii. By subtracting compositions as taken from the
composition axis
 Phase diagrams
Interpretation of Phase diagrams
How to determine the Phase amounts
❑ Consider the diagram below, we want to compute the fraction
of each of the 𝛼 and liquidus phase
 Phase diagrams

Interpretation of Phase diagrams

How to determine the Phase amounts
▪ Locate the overall alloy composition along the tie line and
denoted by 𝐶𝑜 and the mass fraction 𝑊𝐿 and 𝑊𝛼 for respective
phases
▪ From the lever rule

𝑆
𝑊𝐿 = using direct measurement
𝑅+𝑆

𝐶𝛼 −𝐶𝑜
𝑊𝐿 = 𝐶𝛼 −𝐶𝐿
by subtraction using compositions
 Phase diagrams
Interpretation of Phase diagrams
How to determine the Phase amounts
NOTE:
▪ Composition need to be specified in terms of only one of the
constituents for a binary alloy: so far we have made our
computations in weight percent nickel i.e. 𝐶𝑜 =
35 𝑤𝑡% 𝑁𝑖,𝐶𝛼 = 42.5 𝑤𝑡% 𝑁𝑖, 𝐶𝐿 = 31.5 𝑤𝑡% 𝑁𝑖

𝑆 𝐶𝛼 − 𝐶𝑜 42.5 − 35
𝑊𝐿 = = = = 0.68
𝑅 + 𝑆 𝐶𝛼 − 𝐶𝐿 42.5 − 31.5
For the 𝛼 phase
𝑅 𝐶0 − 𝐶𝐿 35 − 31.5
𝑊𝛼 = = = = 0.32
𝑅 + 𝑆 𝐶𝛼 − 𝐶𝐿 42.5 − 31.5
 Phase diagrams

Interpretation of Phase diagrams

How to determine the Phase amounts
▪ We can conclude by stating that the lever rule can be employed
to determine the relative amounts or fractions of phases in any
two-phase region for a binary alloy if temperature and
composition are known and if equilibrium has been established.

Important
▪ Compositions of phases are expressed in terms of 𝑤𝑡 % of
components i.e. 𝑤𝑡 % 𝐶𝑢, 𝑤𝑡 % 𝑁𝑖
▪ Fractional phase amounts (e.g. mass fraction of 𝛼 or liquid
phase) of a two –phase alloy
 Phase diagrams

Interpretation of Phase diagrams

How to determine the Phase amounts

Home work
▪ Derive the lever rule for determining mass fraction of a two-
phase region
(see example 9.1 ) William D Callister Jr.
 Phase diagrams

Interpretation of Phase diagrams

How to determine the Phase amounts

❑ For multiphase alloys, it is often more convenient to specify

relative phase amounts in terms of volume fraction rather than
mass fraction.
❑ Phase volume fractions can be examined from examination of
the microstructure
❑ Similarly, properties of multiphase alloy may be estimated on the
basis of volume fractions
 Phase diagrams
Interpretation of Phase diagrams
How to determine the Phase amounts

▪ For an alloy consisting of 𝛼 and β phases, the volume fraction of

the 𝛼 phase, 𝑉𝛼 is defined as

𝑣𝛼
𝑉𝛼 =
𝑣𝛽 + 𝑣𝛼
Where
𝑣𝛼 and 𝑣𝛽 denote the volumes of the respective phases
in the alloy
▪ We also know that for an alloy with two phases

𝑉𝛼 + 𝑉𝛽 = 1
 Phase diagrams
Interpretation of Phase diagrams
How to convert from mass fraction to volume fraction and vice
versa
▪ Converting from mass fraction to volume fraction

𝑊𝛼
𝜌𝛼
𝑉𝛼 =
𝑊𝛼 𝑊𝛽
𝜌𝛼 + 𝜌𝛽

𝑊𝛽
𝜌𝛽
𝑉𝛽 =
𝑊𝛼 𝑊𝛽
+
𝜌𝛼 𝜌𝛽
 Phase diagrams

Interpretation of Phase diagrams

How to convert from mass fraction to volume fraction and vice

versa

▪ Converting from volume fraction to mass fraction

𝑉𝛼 𝜌𝛼
𝑊𝛼 =
𝑉𝛼 𝜌𝛼 + 𝑉𝛽 𝜌𝛽

𝑉𝛽 𝜌𝛽
𝑊𝛽 =
𝑉𝛼 𝜌𝛼 + 𝑉𝛽 𝜌𝛽
 Phase diagrams
Interpretation of Phase diagrams
How to convert from mass fraction to volume fraction and vice
versa
Note :
𝜌𝛼 and 𝜌𝛽 are the densities of respective phases and their
appropriate values can be found by using the equation:

100
𝜌𝑎𝑣𝑒 =
𝐶1 𝐶2
+
𝜌1 𝜌2

𝐶1′ 𝐴1 + 𝐶2′ 𝐴2
𝜌𝑎𝑣𝑒 = ′
𝐶1 𝐴1 𝐶2′ 𝐴2
𝜌1 + 𝜌2
 Phase diagrams
Development of microstructure in Isomorphus alloys
Consider the figure below (uniform equilibrium cooling)

❑ We are interested in determining

the development of microstructure
that occurs for isomorphous alloys
during solidification
❑ Solidification occurs very slowly, in
that phase equilibrium is
continuously maintained.
❑ The overall composition remains
unchanged during cooling even
though there is a redistribution of
copper and nickel between phases
and is along the dashed solid
line
 Phase diagrams

Development of microstructure in Isomorphus alloys

Non - equilibrium cooling (self study)

William D callister Jr (2009), Material Science and Engineering,
an Introduction, 7th Edition, chapter 9
 Phase diagrams

BINARY EUTECTIC (EASILY MELTED) SYSTEMS

 Phase diagrams
Binary eutectic (easily melted) systems
❑ For the copper-silver system shown in the phase diagram called eutectic
phase diagram, there are a number of features which are important and
worth noting

The copper-silver
phase diagram
 Phase diagrams

The copper-silver phase diagram

Phase diagrams
 Phase diagrams

Binary eutectic (easily melted) systems

❑ The three single phase regions are found i.e. 𝛼, 𝛽 and liquid
❑ 𝛼 phase is a solid solution rich in copper and has silver as the
solute component (an FCC crystal structure)
❑ 𝛽 phase is a solid solution rich in silver with copper as the solute
( FCC crystal structure)
❑ 𝛼 and 𝛽 are pure copper and pure silver respectively
❑ Solubility of these solid phases is limited since at any
temperature below line BEG only a limited concentration of
silver will dissolve in copper (for the 𝛼 phase)
❑ Similarly, for copper in silver ( for 𝛽phase)
 Phase diagrams

Binary eutectic (easily melted) systems

❑ Solubility limit for the 𝛼 phase corresponds to the boundary line
CBA between the 𝛼Τ(𝛼 + 𝛽) and 𝛼 Τ(𝛼 + 𝐿) phase regions
❑ The solubility increases with temperature to a maximum (
8.0 𝑤𝑡 % 𝐴𝑔 𝑎𝑡 779℃) at point B and decreases back to zero at
the melting temperature of pure copper at point A (1085℃)
❑ The maximum solubility of copper in the 𝛽 phase point G
(8.8 𝑤𝑡 % 𝐶𝑢) also occurs at 779℃
❑ Line BEG represents the lowest temperature at which a liquid
phase may exist for any copper-silver alloy that is at equilibrium
 Phase diagrams

Binary eutectic (easily melted) systems

❑ Note:
❑ There are three two-phase regions for the copper-silver system,
i.e. 𝛼 + 𝐿, 𝛽 + 𝐿 and α + 𝛽
❑ compositions and relative amounts for the phases may be
determined using tie lines and the lever rule
❑ Point E is called the invariant point designated by 𝐶𝐸 (71.6 𝑤𝑡 %)
and temperature 𝑇𝐸 (779℃)
 Phase diagrams

Binary eutectic (easily melted) systems

❑ At the invariant point 𝐶𝐸 (71.6 𝑤𝑡 %), as it changes temperature

in passing through 𝑇𝐸 , the reaction is expressed as

❑ This equation is called eutectic reaction in which 𝐶𝐸 and 𝑇𝐸

represent the eutectic composition and temperatures
respectively
❑ 𝐶𝛼𝐸 and 𝐶𝛽𝐸 are the respective compositions of the 𝛼 and 𝛽
phases at 𝑇𝐸
❑ For this reaction
 Phase diagrams

Binary eutectic (easily melted) systems

❑ The horizontal solidus line at 𝑇𝐸 is called eutectic isotherm
❑ Note:
❑ The eutectic reaction upon cooling is similar to solidification and
is always two-phases , where as for pure component only a
single phase forms
❑ Phase diagrams similar to the one discussed here are termed
eutectic phase diagrams and components which exhibit this
behaviour comprise a eutectic system
 Phase diagrams

Binary eutectic (easily melted) systems

❑ When constructing a binary phase diagram, it is important to

understand that one or at most two phases may be in equilibrium
within a phase field
❑ For a eutectic system, three phases (𝛼, 𝛽 and 𝐿) may be in
equilibrium but only at a point along the eutectic isotherm
❑ The other general rule is that a single-phase regions are always
separated from each other by a two phase region that consists of
two single phases that it supports

Homework ( Example 9.2 and 9.3)