‫الورحلة الثانية‬ ‫الجاهعة االسالهية‬

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2018-2017 ‫ أضواء هحود عبدالوجيد‬.‫ م‬.‫م‬

Lecture No.16
Binary Phase Diagrams
16.1 Introduction
Another type of extremely common phase diagram is one in which temperature
and composition are variable parameters, and pressure is held constant normally 1
atm. When only two elements or two compounds are present in a material, a binary
phase diagram can be constructed. If more than two components are present, phase
diagrams become extremely complicated and difficult to represent. An explanation of
the principles governing and the interpretation of phase diagrams can be
demonstrated using binary alloys even though most alloys contain more than two
components.
There are three different types of binary equilibrium diagrams, namely those in
which the characteristics of the diagram are governed by the extent to which one
metal forms a solid solution with the other. The possibilities are that:
1. The two metals are completely soluble in each other in all proportions in the solid
state (binary isomorphous system).
2. The two metals are partially soluble in each other in the solid state (binary eutectic
system).
3. The two metals are completely insoluble in each other in the solid state.
Binary phase diagrams are maps that represent the relationships between temperature
and the compositions and quantities of phases at equilibrium, which influence the
microstructure of an alloy. Many microstructures develop from phase
transformations, the changes that occur when the temperature is altered (ordinarily
upon cooling).This may involve the transition from one phase to another, or the
appearance or disappearance of a phase.
16.2 Binary Isomorphous Systems

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An example of this type of system is afforded by the nickel-copper alloy series

(Figure 16.1a). Atoms of nickel and copper have the same crystal structure (FCC),
nearly identical atomic radii and electronegativities, and similar valences. It is not
surprising that they should form mixed crystals of a substitutional solid-solution type
when a liquid solution of the two metals solidifies. The copper–nickel system is
termed isomorphous because of this complete liquid and solid solubility of the two
components.
The resulting phase diagram will have been derived from a series of cooling
curves. Temperature is plotted along the ordinate, and the abscissa represents the
composition of the alloy, in weight percent (bottom) and atom percent (top) of nickel.
The composition ranges from 0 wt% Ni (100 wt% Cu) on the left horizontal
extremity to 100 wt% Ni (0 wt% Cu) on the right. Three different phase regions, or
fields, appear on the diagram, an alpha ( ) field, a liquid (L) field, and a two-phase 
+ L field. Each region is defined by the phase or phases that exist over the range of
temperatures and compositions delineated by the phase boundary lines.
The liquid L is a homogeneous liquid solution composed of both copper and
nickel. The  phase is a substitutional solid solution consisting of both Cu and Ni
atoms, and having an FCC crystal structure. At temperatures below about 1080C,
copper and nickel are mutually soluble in each other in the solid state for all
compositions.
The phase diagram consists of only two lines: First, the upper or liquidus line
is located between the L and  + L regions, above which any point represents in
composition and temperature an alloy in the completely molten state. Furthermore,
the lower or solidus line separating the  and  + L phase fields, below which any
point represents in composition and temperature an alloy in the completely solid
state.

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‫‪06‬‬
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2018-2017 ‫ أضواء هحود عبدالوجيد‬.‫ م‬.‫م‬

Figure 16.1 (a) The equilibrium phase diagrams for the Cu-Ni. (b) A portion of the
Cu-Ni phase diagram for which compositions and phase amounts are determined at
point B.
The solidus and liquidus lines intersect at the two composition extremities;
these correspond to the melting temperatures of the pure components. For
example, the melting temperatures of pure copper and nickel are 1085C and 1453C,
respectively. Heating pure copper corresponds to moving vertically up the left-hand
temperature axis. The solid-to-liquid transformation takes place at the melting
temperature, and no further heating is possible until this transformation has been
completed.
For any composition other than pure components, a solidification phenomenon
is occurs over the range of temperatures between the liquidus and solidus lines;
within this temperature range, two phases coexist in equilibrium: a liquid and a solid.
The latent heat of fusion is removed over this temperature range so that the cooling
curve shows a change in slope, rather than a flat plateau. For example, upon cooling
an alloy of composition 40 wt% Ni–60 wt% Cu (Figure 16.2), solidification begins at
approximately 1240C; the amount of solid phase continuously increases with
decrease of temperature until about 1280C, at which the alloy is completely solid.

06
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Figure 16.2 The cooling curve for an isomorphous alloy during solidification. The
changes in slope of the cooling curve indicate the liquidus and solidus temperatures,
in this case for a Cu-40%Ni alloy.
For a binary system of known composition and temperature that is at
equilibrium, at least three kinds of information are available:
1. the phases that are present,
2. the compositions of these phases, and
3. the percentages or fractions of the phases.

16.2.1 Phases Present

Often we are interested in which phases are present in an alloy at a particular
temperature. If we know the coordinates—temperature and alloy composition—we
can determine the phases present. For example, an alloy of composition 60 wt% Ni–
40 wt% Cu at 1100C would be located at point A in Figure 16.1a; because this is
within the  region, only the single  phase will be present. On the other hand, a 35
wt% Ni–65 wt% Cu alloy at 1250C (point B) will consist of both  and liquid
phases at equilibrium.
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16.2.2 Composition of Each Phase

For each phase we can specify a composition, expressed as the percentage of
each element in the phase. Usually the composition is expressed in weight percent
(wt%). The first step in the determination of phase compositions is to locate the
temperature–composition point on the phase diagram. When only one phase is
present in the alloy, the composition of the phase equals the overall composition of
the material. For example, consider the 60 wt% Ni–40 wt% Cu alloy at 1100C (point
A, Figure 16.1a). At this composition and temperature, only the  phase is present,
having a composition of 60 wt% Ni– 40 wt% Cu.
For an alloy having composition and temperature located in a two-phase
region, the situation is more complicated. Therefore, the tie line can be used to
determine the composition of the two phases. A tie line, or sometimes as an isotherm,
is a horizontal line within a two-phase region drawn at the temperature of interest. In
an isomorphous system, the tie line connects the liquidus and solidus points at the
specified temperature. The ends of the tie line are dropped perpendiculars from these
intersections to the horizontal composition axis, from which the composition of each
of the respective phases is read.
For any alloy with overall or bulk composition lying between CL and C, the
composition of the liquid is CL and the composition of the solid a is C.
The following example illustrates how the concept of the tie line is used to
determine the composition of different phases in equilibrium.

Example 16.1 Determine the composition of each phase in a 35 wt% Ni-Cu alloy at
1300C, 1250C, and 1200C. (See Figure 16.1a.)
Solution

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The vertical line at 35 wt% Ni represents the overall composition of the alloy:
 1300C: Only liquid is present. The liquid must contain 35 wt% Ni, the overall
composition of the alloy.
 1250C: Two phases are present. A horizontal line within the  +‫ ‏‬L field is
drawn. The endpoint at the liquidus, which is in contact with the liquid region,
is at 31.5 wt% Ni-68.5 wt% Cu. The endpoint at the solidus, which is in
contact with the  region, is at 42.5 wt% Ni-516.5 wt% Cu. Therefore, the
liquid contains 31.5 wt% Ni-68.5 wt% Cu and the solid contains 42.5 wt% Ni-
516.5 wt% Cu.
 1200C: Only solid a is present, so the solid must contain 35 wt% Ni.

16.2.3 Amount of Each Phase

The relative amounts (as fraction or as percentage) of each phase present at
equilibrium in the alloy can be obtained from the phase diagram. The single and two-
phase situations must be treated separately. The solution is obvious in the single-
phase region: because only one phase is present, the alloy is composed entirely of that
phase; that is, the phase fraction is 1.0 or, alternatively, the percentage is 100%. From
the previous example for the 60 wt% Ni–40 wt% Cu alloy at 1100C (point A in
Figure 16.1a), only the  phase is present; hence, the alloy is completely or 100% .

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If the composition and temperature position is located within a two-phase

region, things are more complex. The tie line must be utilized in conjunction with a
procedure that is often called the lever rule (or the inverse lever rule), which is
applied as follows:
1. The tie line is constructed across the two-phase region at the temperature of the
alloy.
2. The overall alloy composition is located on the tie line.
3. The fraction of one phase is computed by taking the leg of the lever opposite to
the composition of the phase, whose amount we are calculating, and dividing
by the total length of the lever
4. The fraction of the other phase is determined in the same manner.
5. If phase percentages are desired, each phase fraction is multiplied by
100.When the composition axis is scaled in weight percent, the phase fractions
computed using the lever rule are mass fractions—the mass (or weight) of a
specific phase divided by the total alloy mass (or weight). The mass of each
phase is computed from the product of each phase fraction and the total alloy
mass.
In the employment of the lever rule, tie line segment lengths may be determined
either by direct measurement from the phase diagram using a linear scale, preferably
graduated in millimeters, or by subtracting compositions as taken from the
composition axis.
Consider again the example shown in Figure 16.1b, in which at 1250C both 
and liquid phases are present for a 35 wt% Ni–65 wt% Cu alloy. The tie line has been
constructed that was used for the determination of  and L phase compositions. Let
the overall alloy composition be located along the tie line and denoted as C0, and
mass fractions be represented by WL and W for the respective phases. From the lever
rule, WL may be computed according to
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2018-2017 ‫ أضواء هحود عبدالوجيد‬.‫ م‬.‫م‬

WL =
or, by subtracting compositions,

WL =

Composition need be specified in terms of only one of the constituents for a binary
alloy. Similarly, for the  phase,

W =

With regard to fractional phase amounts (e.g., mass fraction of the  or liquid
phase), when a single phase exists, the alloy is completely that phase. For a two-
phase alloy, on the other hand, the lever rule is utilized, in which a ratio of tie line
segment lengths is taken.
The following example reinforces the application of the lever rule for
calculating the amounts of phases for an alloy at different temperatures. This is one
way to track the solidification behavior of alloys.

Example 16.2
Determine the amount of each phase in the 35 wt% Ni-Cu alloy shown in Figure
16.1b at 1300C, 1250C, and 1200C.
Solution
 1300C: There is only one phase, so 100% L.

 1250C: WL = × 100 = 68%

W = × 100 = 32%

Of course, identical answers are obtained if compositions are expressed in weight

percent copper instead of nickel.

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 1200C: There is only one phase, so 100% .

7.1 Development of Microstructure in Isomorphous Alloys

Let us consider what happens when the copper-nickel alloy, containing 35 wt%
Ni 65 wt% Cu, cools and solidifies extremely slowly, so that its structure is able to
reach equilibrium at every stage of the process. The region of the Cu–Ni phase
diagram in the vicinity of this composition is shown in Figure 16.3. Cooling of an
alloy of this composition corresponds to moving down the vertical dashed line. At
1300C, point a, the alloy is completely liquid (of composition 35 wt% Ni–65 wt%
Cu) and has the microstructure represented by the circle inset in the figure. As
cooling begins, no microstructural or compositional changes will be realized until we
reach the liquidus line (point b, ~1260C). Solidification will begin when the
temperature falls from this temperature. At this point, the first solid  begins to form,
which has a composition dictated by the tie line drawn at this temperature [i.e., 46
wt% Ni–54 wt% Cu, noted as (46 Ni)]; the composition of liquid is still
approximately 35 wt% Ni–65 wt% Cu [L(35 Ni)], which is different from that of the
solid . In fact, as the temperature falls slowly, solidification continues; and the
composition of the liquid changes along the liquidus line, whilst the composition of
the solid changes  by means of diffusion  along the solidus line. Furthermore, the
fraction of the  phase will increase with continued cooling. Note that the overall
alloy composition (35 wt% Ni–65 wt% Cu) remains unchanged during cooling even
though there is a redistribution of copper and nickel between the phases. Thus, by the
time the temperature has fallen to 1250C , point c in Figure 16.3, the liquid phase
has changed in composition to 32 wt% Ni–68 wt% Cu [L(32 Ni)], whilst the  phase
has changed in composition to 43 wt% Ni–516 wt% Cu [(43 Ni)].

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Figure 16.3 Schematic representation of the development of microstructure during

the equilibrium solidification of a 35 wt% Ni–65 wt% Cu alloy.

The solidification process must continue until we reach the solidus temperature
about 1220C, point d; the composition of the solid  is approximately 35 wt% Ni–
65 wt% Cu (the overall alloy composition), whereas that of the last remaining liquid
is 24 wt% Ni–166 wt% Cu. Just below the solidus, all of the solid must contain a
uniform concentration of 35 wt% Ni–65 wt% Cu composition (point e in the same

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figure), this is a polycrystalline -phase solid solution. Subsequent cooling will

produce no microstructural or compositional alterations.

Q. For the copper-nickel phase diagram in Figure 16.1, find the compositions of the
liquid and solid phases for a nominal composition of 60% Ni and 40% Cu at 1316°C.
Use the inverse lever rule to determine the proportions of liquid and solid phases
present in the alloy.

Q. For the copper-nickel phase diagram in Figure 16.1, how many grams of nickel
must be added to 500 grams of copper to produce an alloy that has a liquidus
temperature of 1350oC? What is the ratio of the number of nickel atoms to copper
atoms in this alloy?

Q. For the copper-nickel phase diagram in Figure 16.1, how many grams of nickel
must be added to 500 grams of copper to produce an alloy that contains 50 wt% a at
1300oC?

Q. Given here are the solidus and liquidus temperatures for the A–B system.
Construct the phase diagram for this system and label each region
Composition (wt% A) Solidus Temperature (oC) Liquidus Temperature (oC)
0 350 350
20 400 350
40 600 380
60 1680 400
80 800 500
100 850 580

Q. Draw the microstructure during the equilibrium solidification of a 35 wt% A–65

wt% B alloy from beginning of pouring temperature to room temperature.
66
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Q. Draw the cooling curve for the alloy 35 wt% A–65 wt%

Q. Given here are the solidus and liquidus temperatures for the copper–gold system.
Construct the phase diagram for this system and label each region.
Composition (wt% Au) Solidus Temperature (oC) Liquidus Temperature (oC)
0 1085 1085
20 1019 1042
40 9162 996
60 934 962
80 922 935
100 911 911
o
1. For alloy that 30% Cu, at 940 C and have 200 g of the alloy. (a) Determine the
amount and composition of each phase. (b) Calculate the mass of phases present. (c)
Calculate the amount of Cu and Au in each phase. (d) Draw the microstructure during
the equilibrium solidification of this alloy from beginning of pouring temperature to
room temperature. (e) Draw the cooling curve for this alloy.
2. What alloy composition would correspond to 30% liquid at 960 oC.

Q. Determine the liquidus temperature, solidus temperature, and freezing range for
the following MgO-FeO ceramic compositions.
(a) MgO-25 wt% FeO; (b) MgO-45 wt% FeO;
(c) MgO-65 wt% FeO; (d) MgO-80 wt% FeO.

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2018-2017 ‫ أضواء هحود عبدالوجيد‬.‫ م‬.‫م‬

Q. Determine the phases present, the compositions of each phase, and the amount of
each phase in wt% for the following MgO-FeO ceramics at 2000oC. (i) MgO- 25 wt%
FeO; (ii) MgO-45 wt% FeO; (iii) MgO- 60 wt% FeO; and (iv) MgO-80 wt% FeO.

Q. How many grams of MgO must be added to 1 kg of NiO to produce a ceramic that
has a solidus temperature of 2200oC?

Q. How many grams of MgO must be added to 1 kg of NiO to produce a ceramic that
contains 25 mol% solid at 2400oC?

Q. Equal moles of MgO and FeO are combined and melted. Determine (a) the
liquidus temperature, the solidus temperature, and the freezing range of the ceramic;
and (b) determine the phase(s) present, their composition(s), and their amount(s) at
1800oC.
Q. A Nb-60 wt% W alloy is heated to 2800oC. Determine (a) the composition of the
solid and liquid phases , (b) the amount of each phase

66
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