Contents

• Construction of Phase diagram

• Binary alloy Phase Diagram
• Cu-Ni Phase Diagram
• Cu-Zn Phase Diagram
• Pb-Sn Phase Diagram
• Fe-Fe3c Phase Diagram
• Invariant Reactions
• Microstructural Changes of HYPO- Eutectoid and Hyper Eutectoid
Steels
• TTT and CCT Diagram
 Isomorphous binary system
➢ An isomorphous system – phase diagram and
corresponding microstructural changes.
 Tie line – Lever rule
➢ At a point in a phase diagram, phases present and their composition
(tie-line method) along with relative fraction of phases (lever rule)
can be computed.

➢ Procedure to find equilibrium concentrationsof phases

(refer to the figure in previous slide):
- A tie-line or isotherm (UV) is drawn across two-phase
region to intersect the boundaries of the region.
-Perpendiculars are dropped from these intersections to the
composition axis, represented by U’ and V’, from which each of each
phase is read. U’ represents composition of liquid phase and V’
represents composition of solid phase as intersection U meets
liquidus line and V meets solidus line.
 Tie line – Lever rule
(contd….)
➢ Procedure to find equilibrium relative amounts of
phases (lever rule):
-A tie-line is constructed across the two phase region at
the temperature of the alloy to intersect the region
boundaries.
-The relative amount of a phase is computed by taking
the length of tie line from overall composition to the
phase boundary for the other phase, and dividing by the
total tie- line length. In previous figure, relative amount
of liquid and solid phases is given respectively by:

cV Uc
CL CS CL CS 1
UV UV
DEVELOPMENT OF MICROSTRUCTURE IN ISOMORPHOUS ALLOYS

Equilibrium Cooling (Cu-Ni System)

Figure (a) The copper–nickel phase

diagram (Adapted from Phase Diagrams of Binary
Nickel Alloys, P. Nash, Editor, 1991. Reprinted by
permission of ASM International, Materials
Park, OH.)
Figure (b) A portion of the copper–nickel
phase diagram for which compositions and
phase amounts are determined at point B.
Nonequilibrium Cooling

Readjustments in the compositions of the liquid and solid

phases in accordance with the phase diagram (i.e., with the
liquidus and solidus lines)

These readjustments are accomplished by diffusional

processes—that is, diffusion in both solid and liquid phases
and also across the solid–liquid interface.

Diffusion is a time-dependent and temperature phenomenon,

Diffusion rates (i.e., the magnitudes of the diffusion

coefficients) are especially low for the solid phase and, for
both phases, decrease with diminishing temperature

All practical solidification situations, cooling rates are

much too rapid
Nonequilibrium Cooling Microstructure in Cu- Ni System
Considering a 35 wt.% Ni–65 wt.% Cu alloy,
Let us begin cooling from a temperature of about 1300C; this is indicated by point a in the liquid
region.
At point b (approximately 1260C), 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 c (about 1240C), the liquid composition has shifted to 29 wt.% Ni–71 wt.% Cu

α- phase that solidified is 40 wt.% Ni–60 wt.% Cu [(40 Ni)]

Diffusion in the solid phase is relatively slow, the phase that formed at point b has not changed

At point d (~1220C) and for equilibrium cooling rates, solidification should be completed.

Nonequilibrium solidification finally reaches completion at point e (~1205C). The composition of the last
phase to solidify at this point is about 31 wt. % Ni
The degree of displacement of the nonequilibrium solidus curve from the equilibrium one will depend on
the rate of cooling. The slower the cooling rate, the smaller is this displacement

Important consequences for Non equilibrium cooling of isomorphous alloys

The distribution of the two elements within the grains is nonuniform, a phenomenon termed segregation.
Concentration gradients are established across the grains

The center of each grain, which is the first part to freeze, is rich in the high-melting element (e.g., nickel
for this Cu–Ni system), whereas the concentration of the low-melting element increases with position
from this region to the grain boundary. This is termed a cored structure, which gives rise to less than
the optimal properties
BINARY EUTECTIC SYSTEMS
➢ Many of the binary systems with limited solubility are of eutectic type – eutectic alloy of
eutectic composition solidifies at the end of solidification at eutectic temperature.
E.g.: Cu-Ag, Pb-Sn
Three single-phase regions are found on the diagram: α, β and
liquid
Eutectic system – Cooling curve –
Microstructure
(contd….)
Eutectic system – Cooling curve –
Microstructure
(contd….)
Eutectic system – Cooling curve –
Microstructure
(contd….)
BINARY EUTECTIC SYSTEMS (Cu-Ag)

The phase is a solid solution rich in copper; it has silver as the solute component and an FCC crystal
structure. The -phase solid solution also has an FCC structure, but copper is the solute. Pure copper
and pure silver are also considered to be and phases, respectively.

The solubility in each of these solid phases is limited, in that at any temperature below line BEG only
a limited concentration of silver will dissolve in copper (for the phase), and similarly for copper in
silver (for the phase)

The solubility in each of these solid phases is limited, in that at any temperature below line BEG only a
limited concentration of silver will dissolve in copper (for the phase), and similarly for copper in silver
(for the phase)
At temperatures below 79C (1434F), the solid solubility limit line separating the and phase regions is
termed a solvus line; the boundary AB between the and L fields is the solidus line

The maximum solubility of copper in the phase, point G (8.8 wt.% Cu), also occurs at 779C (1434F).
This horizontal line BEG, which is parallel to the composition axis and extends between these
maximum solubility positions, may also be considered a solidus line

An important reaction occurs for an alloy of composition CE as it changes temperature in passing

through TE; this reaction may be written as follows:
 The Iron–Carbon System
IRON–IRON CARBIDE (Fe–Fe3C) PHASE DIAGRAM
At room temperature the stable form, called ferrite, or -iron, has a BCC crystal structure. Ferrite experiences a

polymorphic transformation to FCC austenite, or -iron, at 912 °C (1674F). This austenite persists to 1394°C (2541F),

at which temperature the FCC austenite reverts back to a BCC phase known as -ferrite, which finally melts at 1538 °C

(2800F).

The composition axis in Figure 10.28 extends only to 6.70 wt% C; at this concentration the intermediate

compound iron carbide, or cementite (Fe3C), is formed, which is represented by a vertical line on the

phase diagram
Carbon is an interstitial impurity in iron and forms a solid solution with each α- and δ-ferrites and also
with ϒ- austenite, as indicated by the α, δ, and ϒ single-phase fields.

In the BCC -ferrite, only small concentrations of carbon are soluble; the maximum solubility is 0.022
wt.% at 727C.

This particular iron–carbon phase is

relatively soft, may be made magnetic
at temperatures below 768C (1414F),
and has a density of 7.88 g/cm3
The austenite, or phase, of iron, when alloyed with carbon alone, is not stable below 727C (1341F), as indicated
in Figure 10.28. The maximum solubility of carbon in austenite, 2.14 wt%, occurs at 1147C (2097F).This
solubility is approximately 100 times greater than the maximum for BCC ferrite because the FCC interstitial
positions are larger and, therefore, the strains imposed on the surrounding iron atoms are much lower.

δ-ferrite is virtually the same as -ferrite, except for the range of temperatures over which each exists. Because the
δ -ferrite is stable only at relatively high temperatures, it is of no technological importance

Cementite (Fe3C) forms when the solubility limit of carbon in -ferrite is exceeded below 727C (1341F) (for
compositions within the Fe3C phase region).

Fe3C will also coexist with the phase between 727C and 1147C (1341F and 2097F). Mechanically, cementite is very
hard and brittle; the strength of some steels is greatly enhanced by its presence.
Hypoeutectoid Alloys
 The fraction of proeutectoid , W, is
computed as follows

Fractions of both total (eutectoid and proeutectoid) and cementite are determined
using the lever rule and a tie line that extends across the entirety of the Fe3C phase
region, from 0.022 to 6.70 wt.
Hypereutectoid Alloys
Two nonequilibrium effects of practical importance are (1) the occurrence of phase
changes or transformations at temperatures other than those predicted by phase boundary lines on the
phase diagram, and (2) the existence at room temperature of nonequilibrium phases that do not appear
on the phase diagram
The peritectic reaction is another invariant
reaction involving three phases at
equilibrium. With this reaction, upon
heating, one solid phase transforms into a
liquid phase and another solid phase. A
peritectic exists for the copper–zinc system
 Isothermal transformation diagram for an iron–carbon alloy of eutectoid composition

Pearlite
Isothermal transformation diagram for an iron–carbon alloy of eutectoid composition
The transformation rate increases with decreasing temperature such that at 540 C (1000 F) only

about 3 s is required for the reaction to go to 50% completion.

Conditions of constant temperature are termed isothermal thus, plots are referred to as isothermal
transformation diagrams or sometimes as time–temperature–transformation (or T–T–T) plots
An actual isothermal heat treatment curve (ABCD) is superimposed on the isothermal transformation
diagram for a eutectoid iron–carbon alloy
a) coarse pearlite b) fine pearlite
Bainite
In addition to pearlite, other microconstituents that are products of the austenitic transformation exist;
one of these is called bainite.

The microstructure of bainite consists of ferrite and cementite phases, and thus diffusional processes
are involved in its formation. Bainite forms as needles or plates, depending on the temperature of the
transformation; the microstructural details of bainite are so fine that their resolution is possible only
using electron microscopy.
Austenite-to-pearlite
(A–P) and austenite-to-bainite (A–B)
transformations
The isothermal transformation diagram for an iron–carbon alloy of eutectoid composition that has
been extended to lower temperatures. All three curves are C-shaped and have a “nose” at point N,
where the rate of transformation is a maximum. As may be noted, whereas pearlite forms above the
nose [i.e., over the temperature range of about 540 C to 727 C (1000 F to 1341 F)], at temperatures
between about 215 C and 540 C , bainite is the transformation product.

the pearlitic and bainitic transformations are really competitive with each other, and once some
portion of an alloy has transformed into either pearlite or bainite, transformation to the other
microconstituent is not possible without reheating to form austenite.
If a steel alloy having either pearlitic or bainitic microstructures is heated to, and left at, a temperature
below the eutectoid for a sufficiently long period of time—for example, at about 700 C (1300 F) for
between 18 and 24 h—yet another microstructure will form. It is called spheroidite
Instead of the alternating ferrite and cementite lamellae (pearlite) or the microstructure observed for
bainite, the Fe3C phase appears as spherelike particles embedded in a continuous -phase matrix

Instead of the alternating ferrite and cementite lamellae (pearlite) or the microstructure observed for
bainite, the Fe3C phase appears as spherelike particles embedded in a continuous -phase matrix
Martensite

Another microconstituent or phase called martensite

is formed when austenitize iron–carbon alloys are
rapidly cooled (or quenched) to a relatively low
temperature (in the vicinity of the ambient)

Martensite is a nonequilibrium single-phase structure

that results from a diffusion less transformation of
austenite. It may be thought of as a transformation
product that is competitive with pearlite and bainite.
The martensitic transformation occurs when the
quenching rate is rapid enough to prevent carbon
diffusion. Any diffusion whatsoever will result in the
formation of ferrite and cementite phases.
Photomicrograph showing the martensitic
microstructure. The needle-shaped grains are the
martensite phase, and the white regions are austenite
that failed to transform during the rapid quench
Microstructural Determinations for Three Isothermal Heat Treatments

Using the isothermal transformation diagram for an iron–carbon alloy of eutectoid composition (Figure
11.23), specify the nature of the final microstructure (in terms of microconstituents present and
approximate percentages) of a small specimen that has been subjected to the following time–
temperature treatments. In each case assume that the specimen begins at 760 C (1400 F) and that it has
been held at this temperature long enough to have achieved a complete and homogeneous austenitic
structure.

(a) Rapidly cool to 350 C (660 F), hold for 104 s, and quench to room temperature.
(b) Rapidly cool to 250 C (480 F), hold for 100 s, and quench to room temperature.
(c) Rapidly cool to 650 C (1200 F), hold for 20 s, rapidly cool to 400 C (750 F), hold for 103 s,
and quench to room temperature.
CONTINUOUS-COOLING TRANSFORMATION DIAGRAMS

Most heat treatments for steels involve the continuous cooling of a specimen to room temperature. An

isothermal transformation diagram is valid only for conditions of constant temperature; this diagram

must be modified for transformations that occur as the temperature is constantly changing. For

continuous cooling, the time required for a reaction to begin and end is delayed. Thus the isothermal

curves are shifted to longer times and lower temperatures

A plot containing such modified beginning and ending reaction curves is termed a continuous- Cooling
transformation (CCT) diagram.