Phase Diagrams

Some terms used in this chapter:

Component is frequently used in this discussion; components are pure metals and/or compounds of which an alloy is composed.

System has two meanings:

First, “system” may refer to a specific body of material under consideration (e.g., a ladle of molten steel).
Second, may relate to the series of possible alloys consisting of the same components, but without regard to alloy composition (e.g., the
iron–carbon system)

SOLUBILITY LIMIT

For many alloy systems and at some specific temperature, there is a maximum concentration of solute atoms that may dissolve in the solvent
to form a solid solution; this is called a solubility limit.

If we keep on adding more solvent beyond this solubility limit then this will result in the formation of another solid solution or compound
that has a distinctly different composition.

Example:
1. Consider the sugar–water (C12H22O11–H2O) system. Initially, as sugar is added to water, a sugar–water solution or syrup forms.
2. Initially, as sugar is added to water, a sugar–water solution or syrup forms.
3. As more sugar is introduced, the solution becomes more concentrated, until the solubility limit is reached, or the solution becomes
saturated with sugar.
4. At this time the solution is not capable of dissolving any more sugar, and further additions simply settle to the bottom of the container.
5. Thus, the system now consists of two separate substances: a sugar–water syrup liquid solution and solid crystals of undissolved sugar.
• This solubility limit of sugar in water depends on the temperature of the water and may be represented in graphical form on a plot of
temperature along the y-axis and composition (in weight percent sugar) along the x-axis.

• The sum of the concentrations at any composition will equal 100 wt%.

• The solubility limit is represented as the nearly vertical line in the figure.

• For compositions and temperatures to the left of the solubility line, only the syrup liquid solution exists; to the right of the line, syrup
and solid sugar coexist.

• For this system solubility limit increases slightly with rising temperature.
PHASES
A phase may be defined as a homogeneous(same properties) portion of a system that has uniform physical and chemical characteristics.

Every pure material is considered to be a phase and also every solid, liquid, and gaseous solution.

For example, the sugar–water syrup solution just discussed is one phase, and solid sugar is another.

Each has different physical properties (one is a liquid, the other is a solid);

Each is different chemically (i.e., has a different chemical composition); one is virtually pure sugar, the other is a solution of H2O
and C12H22O11.

If more than one phase is present in a given system, each will have its own distinct properties and there will be boundaries separating
them.

It is not necessary that all the properties will be different. Even if one of the properties is different

For example: When water and ice are present in a container, two separate phases exist; they are physically dissimilar (one is a solid, the
other is a liquid) but identical in chemical makeup.

Sometimes, a single-phase system is termed “homogeneous.” Systems composed of two or more phases are termed “mixtures” or
“heterogeneous systems.”
MICROSTRUCTURE
Many times, the physical properties and, in particular, the mechanical behaviour of a material depend on the microstructure(basic unit
cell structure).

Microstructure usually consists of information about:

• Number of phases present
• Proportion of each phase
• Distribution or arrangement

The microstructure of an alloy depends on:

• alloying elements present
• concentration of each element
• the heat treatment of the alloy (i.e. he heating time at temperature, and the rate of cooling to room temperature)

After appropriate polishing and etching, the different phases may be distinguished by their appearance. For example, for a two-phase
alloy, one phase may appear light and the other phase dark.
PHASE EQUILIBRIA

Free energy: It is a function of the internal energy of a system, and also the randomness or disorder of the atoms or molecules (or entropy).

A system is at equilibrium if its free energy is at a minimum under some specified combination of temperature, pressure, and composition.

A change in temperature, pressure, and/or composition for a system in equilibrium will result in an increase in the free energy and in a
possible spontaneous change to another state whereby the free energy is lowered.

Phase equilibrium, often used in the context of this discussion, refers to equilibrium as it applies to systems in which more than one phase
may exist.

Example:
Suppose that a sugar–water syrup is contained in a closed vessel and the solution is in contact with solid sugar at 200C.

If the system is at equilibrium, the composition of the syrup is 65 wt% C12H22O11 35 wt% of H2O and the amounts and compositions of the
syrup and solid sugar will remain constant with time.

If the temperature of the system is suddenly raised—say, to 1000C this equilibrium or balance is temporarily upset in that the solubility limit
has been increased to 80 wt% C12H22O11 20 wt% of H2O.

Thus, some of the solid sugar will go into solution in the syrup. This will continue until the new equilibrium syrup concentration is
established at the higher temperature.
It is often the case, especially in solid systems, that a state of equilibrium is never completely achieved because the rate of approach to
equilibrium is extremely slow; such a system is said to be in a non-equilibrium or metastable state.

Often, metastable structures are of more practical significance than equilibrium ones.

For example, some steel and aluminium alloys rely for their strength on the development of metastable microstructures during carefully
designed heat treatments.

Thus not only is an understanding of equilibrium states and structures important, but also the speed or rate at which they are established and
the factors that affect the rate must be considered.
ONE-COMPONENT (OR UNARY) PHASE DIAGRAMS

Much of the information about the control of the phase structure of a particular system is displayed in what is called a phase diagram, also
often termed an equilibrium diagram.

There are three externally controllable parameters that will affect phase structure:
• Temperature
• Pressure
• Composition

Phase diagrams are constructed when various combinations of these parameters are plotted against one another.

One of the simplest phase diagram to understand is that for a one-component system, in which composition is held constant (i.e., the
phase diagram is for a pure substance); this means that pressure and temperature are the variables.

This one-component phase diagram (or unary phase diagram) [sometimes also called a pressure–temperature (or P–T) diagram] is represented
as a two-dimensional plot of pressure (y-axis) versus temperature (abscissa, or x-axis). Most often, the pressure axis is scaled logarithmically.
Here it may be noted that regions for three different phases—solid, liquid, and vapour—are delineated on the plot.

The three curves shown on the plot (labeled aO, bO, and cO) are phase boundaries; at any point on one of these curves, the two phases on
either side of the curve are in equilibrium (or coexist) with one another.

Also, upon crossing a boundary (as temperature and/or pressure is altered), one phase transforms to another.

All three of the phase boundary curves intersect at a common point, which is labelled O (and for this system, at a temperature of 273.16 K
and a pressure of 6.04x10-3 atm).

This means that at this point only, all of the solid, liquid, and vapour phases are simultaneously in equilibrium with one another

Appropriately, this, and any other point on a P–T phase diagram where three phases are in equilibrium, is called a triple point; sometimes it
is also termed an invariant point in as much as its position is distinct, or fixed by definite values of pressure and temperature.
BINARY ISOMORPHOUS SYSTEMS

Copper–nickel system
A portion of the copper–nickel phase diagram for which compositions
and phase amounts are determined at point B.
Three different phase regions, or fields, appear on the diagram, an alpha (α) field, a liquid (L) field, and a two-phase field(α + L).

The liquid L is a homogeneous liquid solution composed of both copper and nickel

The α phase is a substitutional solid solution consisting of both Cu and Ni atoms and having an FCC crystal structure.

At temperatures below 1080 0C about copper and nickel are mutually soluble in each other in the solid state for all compositions.

The copper–nickel system is termed isomorphous because of this complete liquid and solid solubility of the two components.

Use of symbols for graphs:

First, for metallic alloys, solid solutions are commonly designated by lowercase Greek letters (α, β, γ etc.).

Furthermore, with regard to phase boundaries, the line separating the L and α phase fields is termed the liquidus line. the liquid phase is
present at all temperatures and compositions above this line.

The solidus line is located between the α and α+L regions, below which only the solid phase exists.

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 10850C and 14530C respectively.
INTERPRETATION OF PHASE DIAGRAMS
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.

Phases Present:

An alloy of composition 60 wt% Ni – 40 wt% Cu at 1100 0C would be located at point A in figure. At this point only single α phase is present.

Determination of Phase Compositions:

In two-phase regions, one may imagine a series of horizontal lines, one at every temperature; each of these is known as a tie line, or
sometimes as an isotherm.

To compute the equilibrium concentrations of the two phases, the following procedure is used:

1. A tie line is constructed across the two-phase region at the temperature of the alloy.
2. The intersections of the tie line and the phase boundaries on either side are noted.
3. Perpendiculars are dropped from these intersections to the horizontal composition axis, from which the composition of each of the
respective phases is read.
For example, consider again the 35 wt% Ni–65 wt% Cu alloy at located at point B. The problem is to determine the composition (in wt% Ni and
Cu) for both the α and liquid phases.

The perpendicular from the intersection of the tie line with the liquidus boundary meets the composition axis at 31.5 wt% Ni–68.5 wt% Cu, which
is the composition of the liquid phase, CL.

Likewise, for the solidus–tie line intersection, we find a composition for the solid-solution phase, Cα of 42.5 wt% Ni–57.5 wt% Cu.
Determination of Phase Amounts

Consider again the example shown in Figure 9.3b, in which at both and liquid phases are present for a 35 wt% Ni–65 wt% Cu alloy.

The problem is to compute the fraction of each of the α and liquid phases. The tie line has been constructed that was used for the
determination of α 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 Wα for the
respective phases.

From the lever rule WL and Wα may be calculated as:

Few Important points:

1. For any alloy consisting of a single phase, the composition of that phase is the same as the total alloy composition.
2. If two phases are present, the tie line must be employed, the extremities of which determine the compositions of
the respective phases.
3. 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.
4. 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.
Lever Rule Derivation

Consider the phase diagram for copper and nickel and alloy of composition Co at
1250oC and let CL, Cα WL and Wα represent the same parameters as above.

Since only two phases are present, the sum of their mass fractions must be equal to unity

WL + Wα = 1

the mass of one of the components (either Cu or Ni) that is present in both of
the phases must be equal to the mass of that component in the total alloy,

CL WL + Cα Wα = Co

Simultaneous solution of these two equations leads to the lever rule expressions for this particular situation
For multiphase alloys, it is often more convenient to specify relative phase amount in terms of volume fraction rather than mass fraction.

For an alloy consisting of α and β phases, the volume fraction of the α phase, Vα is defined as

Where vα and vβ denote the volumes of the respective phases in the alloy

for an alloy consisting of just two phases, it is the case that

On occasion conversion from mass fraction to volume fraction (or vice versa) is desired. Equations that facilitate these conversions are as follows:
DEVELOPMENT OF MICROSTRUCTURE IN ISOMORPHOUS ALLOYS
Equilibrium Cooling

Here we treat the situation where the cooling occurs very slowly, in this phase
equilibrium is continuously maintained.

Cooling of an alloy of the composition 35 wt% Ni–65 wt% Cu corresponds to moving

down the vertical dashed line.

At point a, 1300 0C the alloy is completely liquid 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, ~ 12600C ). At this point, the first solid α 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)];

Similarly, we find composition for point c and d.

Upon crossing the solidus line, this remaining liquid solidifies; the final product then is a
polycrystalline α-phase solid solution that has a uniform 35 wt% Ni–65 wt% Cu composition
(point e, Figure 9.4). Subsequent cooling will produce no microstructural or compositional alterations.
Non-equilibrium Cooling

When the rate of cooling is extremely slow, and when temperature is changed, there must
be readjustments in the compositions of the liquid and solid phases in accordance with
the phase diagram (i.e., with the liquidus and solidus lines), as discussed in previous slide.

However, the microstructure and solidus and liquidus lines are different when the rate of
cooling is rapid.

Some of the consequences of nonequilibrium solidification for isomorphous alloys will

now be discussed here by considering a 35 wt% Ni–65 wt% Cu alloy.

At a’ the composition will be completely liquid. At point b’ (approximately 12600C),

α-phase particles begin to form, which, from the tie line constructed, have a
composition of 46 wt% Ni–54 wt% Cu [ (46 Ni)].

Upon further cooling to point (about ), the liquid composition has shifted to
29 wt% Ni–71 wt% Cu; furthermore, at this temperature the composition of the phase
that solidified is 40 wt% Ni–60 wt% Cu [ (40 Ni)].

The composition of the grains has continuously changed with radial position, from
46 wt% Ni at grain centers to 40 wt% Ni at the outer grain perimeters.

At point (d’, 12200C) and for equilibrium cooling rates, solidification should be completed.
However, for this nonequilibrium situation, there is still an appreciable proportion of liquid remaining, and the
phase that is forming has a composition of 35 wt% Ni [ (35 Ni)]; also the average -phase composition at this point
is 38 wt% Ni [ (38 Ni)].
Nonequilibrium solidification finally reaches completion at point (e’, 12050C). The composition of the last α-phase to solidify at this point is
about 31 wt% Ni; the average composition of the α-phase at complete solidification is 35 wt% Ni. The inset at point shows the
microstructure of the totally solid material.

The degree of displacement of the nonequilibrium solidus curve from the equilibrium one will depend on rate of cooling.

The slower the cooling rate, the smaller this displacement; that is, the difference between the equilibrium solidus and average solid
composition is lower. Furthermore, if the diffusion rate in the solid phase is increased, this displacement will be diminished.
MECHANICAL PROPERTIES OF ISOMORPHOUS ALLOYS

We shall now briefly explore how the mechanical properties of solid isomorphous
alloys are affected by composition as other structural variables (e.g., grain size) are held constant.

For all temperatures and compositions below the melting temperature of the lowest-melting
component, only a single solid phase will exist. Therefore, each component will experience solid-
solution strengthening, or an increase in strength and hardness by additions of the other
component.

This effect is demonstrated in Figure 1 as tensile strength versus composition for the copper–
nickel system at room temperature; at some intermediate composition, the curve necessarily passes
through a maximum.

Plotted in Figure 2 is the ductility (%EL)–composition behavior, which is just the opposite of
tensile strength; that is,
ductility decreases with additions of the second component, and the curve exhibits
a minimum.