CONSTITUTION OF ALLOYS

&
Binary thermal equilibrium Diagrams
 CONSTITUTION OF ALLOYS
 Introduction An alloy is a substance that has metallic properties and is composed of two or more
chemical elements, of which at least one is a metal
An alloy system contains all the alloys that can be formed by several elements combined in all possible
proportions.
 If the system is made up of two elements, it is called a binary alloy system; three elements, a
ternary alloy system; etc.
Classification of Alloys: Alloys may be homogeneous (uniform) or mixtures.
 If the alloy is homogeneous it will consist of a single phase. and ,
 If it is a mixture it will be a combination of several phases.

 A phase is anything which is homogeneous and physically distinct.

 The uniformity of an alloy phase is not determined on an atomic scale, such as the composition of
each unit lattice cell, but rather on a much larger scale.
 Any structure which is visible as physically distinct microscopically may be considered a phase.
 For most pure elements the term phase is synonymous with state. There is, therefore, for pure
elements, a gaseous, liquid, and solid phase.
 Some metals are allotropic in the solid state and will have different solid phases. When the metal undergoes a
change in crystal structure, it undergoes a phase change since each type of crystal structure is physically
 In the solid state there are three possible phases: (1) pure metal, (2) intermediate alloy phase or compound,
and (3) solid solution.
 If an alloy is homogeneous (composed of a single phase) in the solid state, it can be only a
solid solution or a compound. If the alloy is a mixture, it is then composed of any
combination of the phases possible in the;
solid state. It may be a mixture of two pure metals, or two solid solutions, or two
compounds, or a pure metal and a solid solution, and so on. The mixture may also vary in
degree of fineness.
The term under equilibrium
conditions implies conditions of extremely
slow heating and cooling.
 In other words, if any change is to occur
sufficient time must be allowed for it to
take place.
 If a cooling curve is plotted for a pure
metal, it will show a horizontal line at the
melting or freezing point (Fig1.
Figure.1 Time-temperature cooling curve for the
solidification of a small crucible of liquid antimony
Solid Solutions : Any solution is composed of two parts: a solute and a solvent. The solute is the minor
part of the solution or the material which dissolved, while the solvent constitutes the major portion of the
solution.
 There are two types of solid solutions, substitutional and interstitial.
 Substitutional Solid Solution In this type of solution, the atoms of the solute substitute for atoms of the
solvent in the lattice structure of the solvent.
 For example, silver atoms may substitute for gold atoms without losing the f.c.c. (face-centered cubic)
structure of gold. and gold atoms may substitute for silver atoms in the f.c.c. lattice structure of silver. All
alloys in the silver-gold system consist of an f.c.c. lattice with silver and gold atoms distributed at random
through the lattice structure.
 This entire system consists of a continuous series of solid solutions.
Several factors are now known, largely through the work of Hume Rothery, that control the range of solubility
in alloy systems.
1. Crystal-structure Factor : Complete solid solubility of two elements is never attained unless the elements
have the same type of crystal lattice structure
2. Relative-size Factor: The size factor is favorable for solid-solution formation when the difference in
atomic radii is less than about 15 percent,; the relative size factor is greater than 8 percent but less than 15
percentage the alloy system usually shows a minimum If the relative-size factor greater than 15 percent,
solid-solution formation is very limited.
3. Chemical-affinity Factor: The greater the chemical affinity of two metals the more restricted is their
solid solubility and the greater is the tendency toward compound formation.
4. Relative-valence Factor: metal of lower valence tends to dissolve more of a metal of higher valency
than vice versa.
 For example, in the aluminum-nickel alloy system, both metals are face-centered cubic. The relative-
size factor is approximately 14 percent. However, nickel is lower in valence than aluminum, and
accordingly with the relative-valence factor solid nickel dissolves 5 percentage of aluminum, but the
higher valence aluminum dissolves only 0.04 percentage of nickel.

Interstitial Solid Solutions These are formed when atoms of small atomic radii fit into the spaces
or interstices of the lattice structure of the larger solvent atoms.
 Since the spaces of the lattice structure are restricted in size, only atoms with atomic radii less
than 1 angstrom are likely to form interstitial solid solutions. These are hydrogen (0.46), boron
(0.97). Carbon (0.77), nitrogen (0.71), and oxygen (0.60).
 Interstitial solid solutions normally have very limited solubility and generally are of
little importance.
 Carbon in iron is a notable exception and forms the basis for hardening steel
oThe maximum solubility of carbon in y iron (f.c.c.) is 2.14 percent at 1148oC, while the
maximum solubility of carbon in a iron (b.c.c.) is only 0.025 percent at 727°C.
Fig.2 Schematic representation of both types of solid
solutions. (a) Substitutional; (b) interstitial

Summary of the possible alloy structures is shown in Fig.4

Fig.4 Possible alloy structure

Summary of the possible alloy
structures is shown in Fig.4
Binary thermal equilibrium
Diagrams
PHASE DIAGRAMS
 Introduction In the previous chapter it was, indicated that there were many
possibilities for the structure of an alloy. Since the properties of a material depend to a
large extent on the type, number, amount, and form of the phases present, and can be
changed by altering these quantities, it is essential to know
(1) the conditions under which these phases exist and
(2) the conditions under which a change in phase will occur

 Ideally, the phase diagram will show the phase relationships under equilibrium conditions,
that is, under conditions in which there will be no change with time.
 Equilibrium conditions may be approached by extremely slow heating and cooling. so that if a
phase change is to occur, sufficient time is allowed.
 In actual practice, phase changes tend to occur at slightly higher or lower temperatures,
depending upon the rate at which the alloy is heated or cooled.
 Rapid variation in temperature, which may prevent
 phase changes that would normally occur under equilibrium conditions, will distort and
sometimes limit the application of these diagrams
 PHASE DIAGRAMS
 It is beyond the scope of this text to cover all the possible conditions of equilibrium between phases in
binary alloys. Only the most important will be considered, and they may be classified as follows:

1 Components completely soluble in the liquid state

a) Completely soluble in the solid state (Type I)
b Insoluble in the solid state: the eutectic reaction (Type II)
c Partly soluble in the solid state: the eutectic reaction (Type Ill)
d Formation of a congruent-melting intermediate phase (Type IV)
e The peritectic reaction (Type V)

2 Components partly soluble in the liquid state: the Monotectic reaction (Type VI)
3 Components insoluble in the liquid state and insoluble in the solid state (Type VII)
4 Transformations in the solid state
a Allotropic change
b Order-disorder
c The eutectoid reaction
d The peritectoid reaction
PHASE DIAGRAMS
 Coordinates of Phase Diagrams Phase diagrams are usually plotted with temperature, in
degrees centigrade or Fahrenheit, as the ordinate and the alloy composition in weight
percentage 'as the abscissa. :
 1 - Type I- Two Metals Completely Soluble in the Liquid and Solid States
Since the two metals are completely soluble in the solid state, the only type of solid
phase formed will be a substitutional solid solution. The two metals will generally have
the same type of crystal structure and differ in atomic radii by less than 8 percent
 The result of running a series of cooling curves for various combinations or alloys
between metals A and 5, varying in composition from 100 percent A 0 percent B to 0
percent A 100 percent 8, is shown in Fig.5
 In order to see the relationship between the cooling curves, they have been plotted on a single
set of axes. However, the student should realize that each cooling curve has its own
coordinates'
 In other words, each cooling curve is a separate experiment starting from zero time. The
cooling curves for the pure metals A and B show only a horizontal line because the beginning
and end of solidification take place at a constant temperature. However, since intermediate
compositions form a solid solution, these cooling curves show two breaks or changes in slope.
 In other words, each cooling curve is a separate experiment starting from zero time.
The cooling curves for the pure metals A and B show only a horizontal line because the
beginning and end of solidification take place at a constant temperature.
 However, since intermediate compositions form a solid solution, these cooling curves
show two breaks or changes in slope.

 For an alloy containing 80A and 208, the first break is at temperature T1, which indicates the
beginning of solidification, and the lower break at T2, indicates the end of solidification.
 All intermediate alloy compositions will show a similar type of cooling curve

o The sense of the phase diagram, or some idea of its form, may be obtained by drawing a line
connecting all the points that show the beginning of solidification, the upper dotted line in
Fig. 5.1, and another line connecting all the points that show the end of solidification, which
is the lower dotted line in Fig. 5.1

o It is now possible to determine the actual phase diagram by plotting temperature vs.
composition.
  The appropriate points are taken from the series of cooling curves and plotted on the
new diagram. For example, in Fig. 6.2, since the left axis represents the pure metal A,
T, is plotted along this line. Similarly, T, is plotted. Since all intermediate compositions
are percentages of A and B, for simplicity the percent sign will be omitted. A vertical
line representing the alloy 80A-20B is drawn, and T1, and T2, from Fig. 6.1 are plotted
. along this line. The same procedure is used for the other compositons

o The phase diagram consists of two points, two lines, and three areas, The two points TA and
TB represent the freezing points of the two pure metals
 The upper line, obtained by connecting the points showing the beginning of solidification,
is called the liquidus line; and
 the lower tine, determined by connecting the points showing the end of solidification, is
called the solidus line.
 The area above the liquidus line is a single-phase region, and any alloy in that region
will consist of a homogeneous liquid solution. Similarly, the area below the solidus line is
a single-phase region, and any alloy in this region will consist of a homogeneous solid
solution.
 It is common practice, in the labeling of equilibrium diagrams, to represent solid
solutions and sometimes intermediate alloys by Greek letters.
 Let us label the solid solution alpha (α )
 Uppercase letters such as A and B will be used to represent the pure metals. Between
the liquidus and solidus lines there exists a two-phase region. Any alloy in this region
will consist of a mixture of a liquid solution and a solid solution.
 It is sometimes desirable to know the actual chemical composition and the relative
amounts of the two phases that are present. In order to determine this information, it
is necessary to apply two rules.
Fig.5
Fig. 5.2 Phase diagram of two metals
completely soluble in the liquid and
solid state
Fig. 5-1 Series of cooling curves for different alloys in a completely soluble
system. The dotted lines indicate the form of the phase diagram
Rule I--Chemical Composition of Phases To determine the actual
chemical composition of the phases of an alloy, in equilibrium at
any specified temperature in a two-phase region, draw a
horizontal temperature line, called a tie line, to the boundaries of
the field. These points of intersection are dropped to the base line,
and the composition is read directly as shown in figure 5-3

In the figure 5-3, consider the alloy composed of 80A-20B

at the temperature T
 The alloy is in a two-phase region. To find the composition,
draw the tie line mo to the boundaries of the field.
 Point m, the intersection of tie line with the solidus line, when
dropped to the base line, gives the composition of the phase
that exists at that boundary. In this case, the phase is a solid
solution of α of composition 90A-10B.
 Similarly, point o, when dropped to the base line, will give the
composition of the other phase constituting the mixture, in this
case the liquid solution of composition 74A-26B
Figure 5.3 Diagram showing the tie line
mo drawn in the two-phase region at
temperature T.
Rule Il--Relative Amounts of Each Phase
To determine the relative amounts of the two phases in
equilibrium at any specified temperature in a two phase
region,
 draw a vertical line representing the alloy and a horizontal
temperature line to the boundaries of the field.
 The vertical line will divide the horizontal line into two parts
whose lengths are inversely proportional to the amount of
the phases present.
 This is also known as the lever rule. The point where the
vertical line intersects the horizontal line may be considered
as the fulcrum of a lever system.
 The relative lengths of the lever arms multiplied by the
amounts of the phases present must balance. Figure 5.3 Diagram showing the tie
 In Fig. 5.3, the vertical line, representing the alloy 20 B, line mo drawn in the two-phase
divides the horizontal tie line mo into two parts, mn and no. region at temperature T.
Rule Il--Relative Amounts of Each Phase continued
……
o If the entire length of the tie line mo is taken to
represent 100 percent, or the total weight of the two
phase present at temperature T, the lever rule may
be expressed mathematically as

o If the tie line is removed from the phase diagram

and the numerical values are inserted, it will appear The tie line mo removed from Fig.
as shown in Fig. 5.4. Applying the above equations, 5.4 to illustrate application of the
lever rule.
Equilibrium Cooling of a Solid
Solution Alloy
 Phase changes that occur at
various stages during equilibrium
cooling of a solid solution alloy
from liquid state to solid state are
explained below.
 The process is explained with
reference to the phase diagram
given below by showing what
happens in a particular alloy 70A-
30B as it is cooled from liquid
state to solid state.

Equilibrium Cooling of a Solid Solution Alloy

Example of isomorphous system: Cu-Ni

 In one-component system
melting occurs at a well-defined
melting temperature.
 In multi-component systems
melting occurs over the
range of temperatures,
between the solidus and
liquidus lines.
 Solid and liquid phases are in
equilibrium in this temperature
range.
50/50 wt % composition in Cu-Ni
 ‫منحنى التوازن الحراري لحالة الذوبان التام في الحالة الصلبة‬
‫)‪Solid Solution thermal equilibrium diagram (Cu-Ni‬‬
‫امنحنى النحاس والنيكل‬
 (a) The copper–nickel phase diagram.
(b) A portion of the copper–nickel phase
diagram for which compositions and phase
amounts are determined at point B.

‫منحنى التوازن الحراري لحالة الذوبان التام في الحالة الصلبة‬

Solid Solution thermal equilibrium diagram (Cu-Ni)
‫امنحنى النحاس والنيكل‬
Example Problem:
At point B (35 wt% Ni, 1250ºC) on figure 10.3b, what are the
mass fraction liquid and the mass fraction solid?
This must be solved using the lever rule, or the inverse lever
rule, I have heard both terminologies used.

The reason that some people call this the inverse lever rule
is the line segment (S) chosen to calculate the mass fraction
liquid is on the solid side of the phase diagram, not the
liquid side. Similarly:

Obviously, these must add up to 1.0.

‫ نيكل‬%35 ‫بنية سبيكة بتركيز‬
‫تحت ظروف او معدالت تبريد‬
‫متزنة‬
Phases exists in an alloy
of composition 35% Ni

CU-Ni phase diagram

Solid Solution type alloy
system
Example Problem:
Calculate the amount of each phase present in 1 kg of a 50 wt.  Note that when determining the mass fraction of
% Ni- 50 wt.% Cu alloy at a) 1400°C, b) 1300°C and c) the liquid (solid) phase, the numerator contains the
1200°C. composition of the solid (liquid) phase. This seems
a) For a 50 wt.% Ni- 50 wt.% Cu alloy at 1400°C, we are in the backwards to some people, and they refer to the
liquid (L) region of the phase diagram. Therefore, we have 1 kg lever rule as the inverse lever rule to remind
of liquid (L). themselves of this.
b) For a 50 wt.% Ni- 50 wt.% Cu alloy at 1300°C, we are in the  To ensure that you get the correct answer, you
solid + liquid (α+L) region of the phase diagram. Here we must should always look at the problem visually and
use the lever rule to calculate the mass fraction of each phase. determine which mass fraction is larger. Then you
Unfortunately, figure 10.2 does not contain an insert enlarging can check the answer. In addition, the two mass
the α+L region of the phase diagram, so accurate reading of fractions (0.67 and 0.33) must add to 1.
this figure is difficult. However, if we draw a tie line across the c) For a 50 wt.% Ni- 50 wt.% Cu alloy at 1200°C, we
α+L region at 1300°C, the endpoints are at about 45 wt.% Ni are in the solid (α) region of the phase diagram.
and 60 wt.% Ni. Therefore, the mass fractions are:. Therefore, we have 1 kg of solid (α).
Example Problem:
Calculate the amount of each phase present in 1 kg of a  Note that when determining the mass fraction
50 wt.% Ni- 50 wt.% Cu alloy at a) 1400°C, b) 1300°C of the liquid (solid) phase, the numerator
and c) 1200°C. contains the composition of the solid (liquid)
a) For a 50 wt.% Ni- 50 wt.% Cu alloy at 1400°C, we are phase. This seems backwards to some people,
in the liquid (L) region of the phase diagram. Therefore, and they refer to the lever rule as the inverse
we have 1 kg of liquid (L). lever rule to remind themselves of this.
b) For a 50 wt.% Ni- 50 wt.% Cu alloy at 1300°C, we are in the  To ensure that you get the correct answer, you
solid + liquid (α+L) region of the phase diagram. Here we must should always look at the problem visually
use the lever rule to calculate the mass fraction of each phase. and determine which mass fraction is larger.
Unfortunately, figure 10.2 does not contain an insert enlarging
Then you can check the answer. In addition,
the α+L region of the phase diagram, so accurate reading of
this figure is difficult. However, if we draw a tie line across the
the two mass fractions (0.67 and 0.33) must
α+L region at 1300°C, the endpoints are at about 45 wt.% Ni add to 1.
and 60 wt.% Ni. Therefore, the mass fractions are:. c) For a 50 wt.% Ni- 50 wt.% Cu alloy at 1200°C,
we are in the solid (α) region of the phase
diagram. Therefore, we have 1 kg of solid (α).
  Solid-Solution Strengthening
In metallic materials, one of the important effects of solid-solution
formation is the resultant solid-solution strengthening (Figure 10-
7).( Askuland p-301)This strengthening, via solid-solution
formation, is caused by increased resistance to dislocation
motion. This is one of the important reasons why brass (Cu-Zn
alloy) is stronger than pure copper. Similarly small levels of
carbon strengthen iron. We will learn later that carbon also plays
another role in additional strengthening of steels by forming iron
carbide (Fe3C) and other phases (Chapter 12). Jewelry could be
made out of pure gold or silver. However, pure gold and pure
silver are extremely soft and malleable and the jewelry pieces
made will not retain their shape. This is also why jewelers add
copper to gold or silver.
 In the copper-nickel (Cu-Ni) system, we intentionally introduce
a solid substitutional atom (nickel) into the original crystal
structure (copper). The copper-nickel alloy is stronger than Figure 10-7
pure copper. The effects of several alloying elements on the yield strength of
 Similarly, if less than 30% Zn is added to copper, the zinc copper. Nickel and zinc atoms are about the same size as
behaves as a substitutional atom that strengthens the copper- copper atoms, but beryllium and tin atoms are much different
zinc alloy, as compared with pure copper. from copper atoms.
Increasing both atomic size difference and amount of alloying
element increases solid-solution strengthening.
 Solid-Solution Strengthening
Degree of Solid-Solution Strengthening The degree of solid-solution
strengthening depends on two factors.
1. First, a large difference in atomic size between the original
(host or solvent) atom and the added (guest or solute) atom increases
the strengthening effect. A larger size difference produces a greater
disruption of the initial crystal structure, making slip more difficult
(Figure 10-7)
2. Second, the greater the amount of alloying element added, the greater
the strengthening effect (Figure 10-7). A Cu-20% Ni alloy is stronger
than a Cu-10% Ni alloy.

Figure 10-8
The effect of additions of zinc
to copper on the properties of
the solid-solution-
Figure 10-7
strengthened alloy.
The effects of several alloying elements on the yield strength of
The increase in % elongation
copper. Nickel and zinc atoms are about the same size as
with increasing zinc content is
copper atoms, but beryllium and tin atoms are much different
not typical of solid-solution
from copper atoms.
strengthening.
Increasing both atomic size difference and amount of alloying
element increases solid-solution strengthening.
Show Figure, which illustrates strain hardening for both pure Cu and pure Ni,
when small amounts of the other are added.
Design of a Melting Procedure for a Casting
You need to produce a Cu-Ni alloy having a minimum yield strength
of 20,000 psi, a minimum tensile strength of 60,000 psi, and a
minimum % elongation of 20%.You have in your inventory a Cu-20%
Ni alloy and pure nickel. Design a method for producing castings
having the required properties.

The mechanical properties of copper-nickel

alloys. Copper is strengthened by up to 67% Ni,
and nickel is strengthened by up to 33% Cu
Cooling curves are shown in Figure
10-25 for several Mo-V alloys.
Based on these curves, construct the
Mo-V phase diagram

Figure 10-25
Type-II 11-Two Metals Completely Soluble in the Liquid State and
Completely Insoluble in the Solid State
( Simple-eutectic Alloy System)
 • ‫منحنى التوازن الحراري لحالة انعدام الذوبان في الحالة الصلبة‬
‫انضمة السبائك من نوع اليوتكتك البسيط‬
Type-II Two Metals Completely Soluble in the Liquid State and Completely
Insoluble in the Solid State
( Simple-eutectic Alloy System)
 Technically, no two metals are completely insoluble in each other. However, in some
cases the solubility is so restricted that for practical purposes they may be considered
insoluble
 Raoult's law states that the freezing point of a pure substance will be lowered by the
addition of a second substance provided the latter is soluble in the pure substance when liquid
and insoluble when solidified. The amount of lowering of the freezing point is proportional to
the molecular weight of the solute.
 This phase diagram can be developed from a series of cooling curves in a manner analogous
to that used for the solid solution diagram described; previously, but in this case, the
experimental curves show a different kind of behavior
 The series of cooling curves for the pure metals and various alloys, and the room temperature
microstructures, are shown in Fig. 5.15.
 The cooling curves for the pure metals A and 8 show a single horizontal line at their freezing
points, as expected. As B is added to A, the temperature for the beginning of solidification is
lowered. As A is added to B, the temperature for the beginning of solidification for those
alloys is also lowered.
Fig. 5-6 Eutectic-type phase diagram

Fig. 5.15 Cooling curves and room-temperature microstructures for a series of alloys of
two metals that are insoluble in the solid state. The upper dotted line indicates the form of
the liquidus and the lower dotted line the form of the solidus line
 This phase diagram consists of four
areas.
 The area above the liquidus
line is a single-phase homogeneous
liquid solution, since the two metals
are soluble in the liquid state.
 The remaining three areas are two-
phase areas. Every two-phase area
on a phase diagram must be
bounded along a horizontal line by
single phases.
 If the single-phase areas are
 This line intersects the liquidus at L which means that the liquid is
labeled first, then the two-phase one of the phases existing in the two-phase area and intersects the
areas may be easily determined. left axis at point 0.
 For example, in Fig. 5. 6, to determine the  The left axis represents a single phase, the pure metal A, which
phases that exist in the two-phase area below its melting point is solid. Therefore, the two phases existing
MFE, a horizontal tie line OL is drawn. in the area MFE are liquid and solid A.
 The same reasoning is applied to determine the two phases that exist
in area NEG
 These are liquid and solid B. The above
ideas may be applied to any phase
diagram and will be useful to the student
for the labeling of more complex
diagrams. .
 Since the two metals are assumed to be completely
insoluble in the solid state, it should be apparent
that when freezing starts the only solid that can form
is a pure metal. Also, every alloy when completely
solidified must be a mixture of the two pure metals
 It is common practice to consider alloys to the left of
the eutectic composition as hypoeutectic alloys and
those to the right as hypereutectic alloys.

 It is common practice to consider alloys to the left of

the eutectic composition as hypoeutectic alloys and Fig. 6. 7 Eutectic-type phase diagram.
those to the right as hypereutectic alloys.
 Alloy 1 in Fig. 6.7 is the eutectic composition 40A-
 The way in which solidification takes place is of 60B. As it is cooled from temperature To, it remains a
interest and will now be studied by following the uniform liquid solution until point E the eutectic-
slow cooling of several alloys. temperature tine, is reached.
 Alloy 1 in Fig. 6.7 is the eutectic composition 40A-
60B. As it is cooled from temperature To, it remains a
uniform liquid solution until point E the eutectic-
temperature tine, is reached.
 Since this is the intersection of the liquidus and solidus
lines, the liquid must now start to solidify, and the
temperature cannot drop until the alloy is completely
solid.
 The liquid will solidify into a mixture of two phases.
These phases are always the ones that appear at either
end of the horizontal eutectic-temperature line, in this
case point F, which is the pure metal A, and point G,
the pure metal B

 Since solidification of the eutectic alloy occurs at constant Fig. 6. 7 Eutectic-type phase diagram.
temperature, its cooling curve would be the same as that for
a pure metal or any congruent-melting alloy.
 The eutectic solidification, however, is incongruent since
there is a difference in composition between the liquid and
Lead-bismuth eutectic mixture
the individual solid phases.
Alloy 2, a hypoeutectic alloy composed of 80A-20B,
remains a uniform liquid solution until the liquidus line,
temperature T1, is reached. At the point the liquid L, is
saturated in A, and as the temperature is dropped
slightly, the excess A must solidify. The liquid, by depositing
crystals of pure A, must become richer in B. Applying Rule
I at temperature T2, show the solid phase to be pure A and
the liquid composition L2, as 70A-30B. The amount which
has solidified up to this temperature would be found by
applying Rule II:

The microstructure would appear as in Fig. 6. 9a

Fig. 6. 7 Eutectic-type phase diagram.

 As solidification continues, the amount of pure solid A increases
gradually by continued participation from the liquid. The liquid
composition, becoming richer in B and is slowly traveling
downward and to the right along the liquidus line while the amount
of liquid is gradually decreasing. When the alloy reached x E,, the
eutectic line, the liquid is at point E. The conditions existing E
The microstructure would appear as in Fig. 6.9b.
 The remaining liquid (33 percent), having reached the
eutectic point, now solidifies into the fine intimate mixture of
A and B as described under alloy 1.
 When solidified, the alloy will consist of 67 percent of
grains of primary A or proeutectic A (which formed between
T1, and TE, or before the eutectic reaction) and 33 percent
eutectic (A + B) mixture (Fig. 6.9c)
 Every alloy to the left of the eutectic point E, when
solidified, will consist of grains of proeutectic A and the
eutectic mixture. The closer the alloy composition is to the
eutectic composition, the more eutectic mixture will be
present in the solidified alloy (see microstructures in Fig.
5.15).

Fig. 6. 7 Eutectic-type phase diagram.

 Alloy 3, a hypereutectic alloy composed of 10A-90B,
undergoes the same cooling process as alloy 2 except
that when the liquidus line is reached the liquid deposits
crystals of pure B instead of A.
 As the temperature is decreased, more and more B will
solidify, leaving the liquid richer in A.
 The amount of liquid gradually decreases, and its
composition gradually moves down and to the left along
the liquidus line until point E is reached at the eutectic
temperature.
 The remaining liquid now solidifies into the eutectic (A
+ B) mixture. After solidification, the alloy will consist
of 75 percent grains of primary B or proeutectic B and
25 percent eutectic (A + B) mixture.
 The student should verify these figures and sketch the
microstructure at room temperature.
 Every alloy to the right of the eutectic point, when Fig. 6. 7 Eutectic-type phase diagram.
solidified. will consist of grains of proeutectic B and the
eutectic mixture.
 The only difference will be in the relative amounts (see
microstructures in Fig. 6.15).
‫منحنى التوازن الحراري لحالة انعدام الذوبان في الحالة الصلبة‬
‫انضمة السبائك من نوع اليوتكتك البسيط‬
‫‪Simple-eutectic Alloy System‬‬
‫بنية سبيكة اليوتكتك تحت المجهرلو عندنا مجهر بقوة تكبير عشرة مليون مرة‬
‫ا‬
(Type Ill)Partly soluble in the solid state: the
eutectic reaction
Binary Eutectic Alloy System
Eutectic phase diagrams:
• What happens when two
materials are not completely
soluble, the more typical
situation? In the simplest
case, a binary eutectic
phase diagram is observed.
Show figure -1 and figure -2.
The eutectic reaction

Figure-1 The copper–silver phase diagram

Eutectic phase diagrams:
• The lead–tin phase diagram.

Example problem1:
Determination of Phases Present and
Computation of Phase Compositions
For a 40 wt% Sn–60 wt% Pb alloy at
150 0C (300 0F), (a)what phase(s) is
(are) present?
(b)What is (are) the composition(s) of
the phase(s)?

The lead–tin phase diagram.

EXAMPLE PROBLEM 2
Relative Phase Amount Determinations—
Mass and Volume Fractions
For the lead–tin alloy in Example Problem 1,
calculate the relative amount of each phase
present in terms of (a)mass fraction and
(b)volume fraction. At 150C, take the
densities of Pb and Sn to be 11.23 and 7.24
g/cm3 , respectively.

The lead–tin phase diagram. For a 40 wt% Sn–60 wt%

Pb alloy at 150 0C (point B), phase compositions and
relative amounts are computed in Example
The lead–tin phase diagram. For a 40 wt% Sn–60
wt% Pb alloy at 150 0C (point B), phase
compositions and relative amounts are computed
in Example
Photomicrograph showing the microstructure
of a lead–tin alloy of eutectic composition. This
microstructure consists of alternating layers of a
lead-rich α -phase solid solution (dark layers),
and a tin-rich β-phase solid solution (light
layers). 375 X

Schematic representation of
the formation of the eutectic
Schematic representations of the equilibrium microstructures
structure for the
for a lead–tin alloy of eutectic composition C3 above and below
lead–tin system.
the eutectic temperature
EX: Pb-Sn Eutectic System (2)

• For a 40 wt% Sn-60 wt% Pb alloy at 200°C, find...

--the phases present: a + L Pb-Sn
--compositions of phases: T(°C) system
CO = 40 wt% Sn
Ca = 17 wt% Sn 300
L (liquid)
CL = 46 wt% Sn L+ a
--the relative amount 220 a
200 R S L+b b
of each phase: 183°C
CL - CO 46 - 40
Wa = = 100
C L - C 46 - 17 a+b
6
= = 21 wt%
29 100
0 17 20 40 46 60 80
CO - C 23 C Co CL C, wt% Sn
WL = = = 79 wt% Adapted from Fig. 9.8,
CL - C  29 Callister 7e.
Microstructures In Eutectic Systems: I

• Co < 2 wt% Sn T(°C) L: Co wt% Sn

400
• Result: L
a
--at extreme ends 300 L
--polycrystal of a grains
i.e., only one solid phase. L+ a
200
a
a: Co wt% Sn
(Pb-Sn
TE
System)

100
a+b

0 10 20 30
Adapted from Fig. 9.11,
Co Co , wt% Sn
Callister 7e. 2%
(room Temp. solubility limit)
Microstructures in Eutectic Systems: II
L: Co wt% Sn
• 2 wt% Sn < Co < 18.3 wt% Sn 400T(°C)
• Result: L
 Initially liquid +  L
300 a
 then  alone L+a
 finally two phases a: Co wt% Sn
a
 a polycrystal 200
TE
 fine -phase inclusions a
b
100
a+ b Pb-Sn
system
0 10 20 30
Adapted from Fig. 9.12, 2 Co Co , wt% Sn
Callister 7e. (sol. limit at T room ) 18.3
(sol. limit at TE)
Microstructures in Eutectic Systems: III
• Co = CE
• Result: Eutectic microstructure (lamellar structure)
--alternating layers (lamellae) of a and b crystals.
Micrograph of Pb-Sn
T(°C) eutectic
L: Co wt% Sn microstructure
300 L
Pb-Sn
system
L+ a
200 a 183°C L b
TE

100 160 m
a : 97.8 wt% Sn
Adapted from Fig. 9.14, Callister 7e.
: 18.3 wt%Sn

0 20 40 60 80 100 45.1%  and 54.8% 

18.3 CE 97.8
Adapted from Fig. 9.13, 61.9 C, wt% Sn
Callister 7e.
Lamellar Eutectic Structure

Adapted from Figs. 9.14 & 9.15, Callister

7e.
 Microstructures in Eutectic Systems: IV
• 18.3 wt% Sn < Co < 61.9 wt% Sn
• Result: a crystals and a eutectic microstructure
• Just above TE :
T(°C) L: Co wt% Sn a L
L
C a = 18.3 wt% Sn
300 a CL = 61.9 wt% Sn
L
Pb-Sn
L+a Wa = S = 50 wt%
system R+S
200
a R S L+b b WL = (1- Wa ) = 50 wt%
TE S
R
• Just below TE :
100 a +b C a = 18.3 wt% Sn
primary a Cb = 97.8 wt% Sn
eutectic a
eutectic b Wa = S = 72.6 wt%
0 20 40 60 80 100 R+S
18.3 61.9 97.8 Wb = 27.4 wt%
Adapted from Fig. 9.16,
Callister 7e. Co, wt% Sn
 Hypoeutectic & Hypereutectic Compositions
300
L
T(°C)
a L+ a
200 L+b b (Pb-Sn
TE
Adapted from Fig. 9.8,
Callister 7e. (Fig. 9.8 adapted from
a+b System)
Binary Phase Diagrams, 2nd ed., Vol. 3,
T.B. Massalski (Editor-in-Chief), ASM
International, Materials Park, OH, 1990.)
100

0 20 40 60 80 100 Co, wt% Sn

eutectic
hypoeutectic: Co = 50 wt% Sn 61.9 hypereutectic: (illustration only)
(Figs. 9.14 and 9.17 from
Metals Handbook, 9th ed.,
Vol. 9, Metallography and
eutectic: Co = 61.9 wt% Sn
a
Microstructures, American
Society for Metals, Materials
Park, OH, 1985.)
b
a b
a a b b
a b
a b
175 mm 160 mm
Adapted from eutectic micro-constituent Adapted from Fig. 9.17,
Fig. 9.17, Callister 7e. Adapted from Fig. 9.14, Callister 7e. (Illustration
Callister 7e. only)
“Intermetallic” Compounds

Adapted from
Fig. 9.20, Callister 7e.

An Intermetallic
Compound is also
an important part of

Mg2Pb the Fe-C system!

Note: an intermetallic compound forms a line - not an area -

because stoichiometry (i.e. composition) is exact.
 Eutectoid & Peritectic
Peritectic transition  + L 

Cu-Zn Phase diagram

Adapted from
Fig. 9.21, Callister 7e.
Eutectoid transition  +
The Iron–Carbon System
THE IRON–IRON CARBIDE (Fe–Fe3C)
PHASE DIAGRAM
 Of all binary alloy systems, the one that is possibly the most important is that for
iron and carbon. Both steels and cast irons, primary structural materials in every
techno-logically advanced culture, are essentially iron–carbon alloys.
  Figure 9.24 would be more
appropriately labeled the Fe–Fe3C
phase diagram because Fe3C is now
considered to be a component.

 Carbon is an interstitial impurity in

iron and forms a solid solution
with each of α- and δ-ferrites and
also with austenite ɤ, as indicated
by the α, δ, and ɤ single-phase
fields in Figure 9.24.

9.24. The iron–iron

carbide phase diagram.
Photomicrographs of (a) a-ferrite (90X ) and (b) austenite (325X)
(Copyright 1971 by United States Steel Corporation.
Eutectoid & Peritectic – some definitions
• Eutectic: a liquid in equilibrium with two solids
L  +heat

cool

 Eutectoid: solid phase in equilibrium with two solid phases

S2 S1+S3 intermetallic compound - cementite

cool
  + Fe3C (727ºC)
heat

 Peritectic: liquid + solid 1 in equilibrium with a single solid

2 (Fig 9.21)
S1 + L S2 cool
+L 
heat (1493ºC)
Iron-Carbon (Fe-C) Phase Diagram
T(°C) Max. C solubility in  iron = 2.11 wt%
• 2 important
1600
points d
-Eutectic (A): 1400 L
L Þ g + Fe3C g g +L
1200 1148°C
A L+Fe3C
-Eutectoid (B): (austenite)

Fe3C (cementite)
R S
g Þ a + Fe3C 1000 g g
g g g+Fe3C

a+
800
a B 727°C = T eutectoid

g
R S
600
a +Fe3C
400
0 1 2 3 4 5 6 6.7
(Fe) 0.76 4.30 Co, wt% C
120 mm C eutectoid
Result: Pearlite = Fe3C (cementite-hard)
alternating layers of a (ferrite-soft)
a and Fe3C phases
(Adapted from Fig. 9.27, Callister 7e.) Adapted from Fig. 9.24,Callister 7e.
PHASE COMPOSITIONS OF THE IRON-
CARBON ALLOYS AT ROOM TEMPERATURE

Hypoeutectoid steels (carbon content from 0.008% to 0.73%) consist of primary

proeutectoid) ferrite (according to the curve A3) and pearlite.

Eutectoid steel (carbon content 0.83%) entirely consists of pearlite.

Hypereutectoid steels (carbon content from 0.76 to 2.14%) consist of primary

(proeutectoid) cementite (according to the curve ACM) and pearlite.

Cast irons (carbon content from 2.06% to 4.3%) consist of proeutectoid cementite
C2 ejected from austenite according to the curve ACM , pearlite and transformed
ledeburite (ledeburite in which austenite transformed to pearlite.
Hypoeutectoid Steel
T(°C)
1600
d
1400 L (Fe-C
g g g g +L System)
g g 1200 1148°C L+Fe3C

Fe3C (cementite)
(austenite)
g g 1000
g g g + Fe3C Adapted from Figs. 9.24
and 9.29,Callister 7e.
a (Fig. 9.24 adapted from
a g
g 800 r s 727°C Binary Alloy Phase
g ag aRS Diagrams, 2nd ed., Vol.
1, T.B. Massalski (Ed.-in-
w a =s/(r +s) 600
wg =(1- wa )
a + Fe3C Chief), ASM International,
Materials Park, OH,
1990.)
400
a 0 1 2 3 4 5 6 6.7
(Fe) Co , wt% C
0.76

C0
pearlite
w pearlite = wg
Hypoeutectoid
w a =S/(R+S) 100 mm
steel
w Fe3C =(1-w a )
pearlite proeutectoid ferrite
Adapted from Fig. 9.30,Callister 7e.
 Hypereutectoid Steel
T(°C)
1600
d
1400 L (Fe-C
g g g +L System)
1200
g
gg 1148°C L+Fe3C

Fe3C (cementite)
(austenite)
g g 1000
gg g +Fe3C Adapted from Figs. 9.24
and 9.32,Callister 7e.
Fe3C (Fig. 9.24 adapted from
gg 800 r s Binary Alloy Phase
gg a R S
Diagrams, 2nd ed., Vol.
1, T.B. Massalski (Ed.-in-
600
w Fe3C =r/(r +s) a +Fe3C Chief), ASM International,
Materials Park, OH,
wg =(1-w Fe3C ) 1990.)
400
0 1 Co 2 3 4 5 6 6.7
0.76

(Fe)
pearlite Co , wt%C
w pearlite = wg
w a =S/(R+S)
w Fe3C =(1-w a ) 60 mmHypereutectoid
steel
pearlite proeutectoid Fe3C
Adapted from Fig. 9.33,Callister 7e.
 Example: Phase Equilibria

For a 99.6 wt% Fe-0.40 wt% C at a temperature just below the

eutectoid, determine the following:
a) composition of Fe3C and ferrite ()
b) the amount of carbide (cementite) in grams that forms per 100 g of steel
c) the amount of pearlite and proeutectoid ferrite ()
 Solution:
CO = 0.40 wt% C
a) composition of Fe3C and ferrite () Ca = 0.022 wt% C
CFe C3 = 6.70 wt% C
b) the amount of carbide
(cementite) in grams that
forms per 100 g of steel
1600
Fe3C Co  C d
 x100 1400 L
Fe3C   CFe 3 C  C T(°C) g+L
g

Fe3C (cementite)
1200 1148°C L+Fe3C
0.4  0.022 (austenite)
 x 100  5.7g
6.7  0.022 1000
g + Fe3C
800 727°C
Fe3C  5.7 g R S
600 a + Fe3C
  94.3 g
400
0 1 2 3 4 5 6 6.7
C CO Co , wt% C CFe
3C
 Solution, cont:
c) the amount of pearlite and proeutectoid ferrite ()
note: amount of pearlite = amount of g just above TE

Co = 0.40 wt% C
1600
Ca = 0.022 wt% C d
L
Cpearlite = C = 0.76 wt% C T(°C)
1400

g g+L

Fe3C (cementite)
 C  C 1200 1148°C L+Fe3C
 o x 100  51.2 g (austenite)
   C  C 1000
g + Fe3C
800
pearlite = 51.2 g 727°C
RS
proeutectoid  = 48.8 g 600
 a + Fe3C
400
0 1 2 3 4 5 6 6.7
C C C Co , wt% C
Looking at the Pearlite: O

11.1% Fe3C (.111*51.2 gm = 5.66 gm) & 88.9%  (.889*51.2gm = 45.5 gm)
 total  = 45.5 + 48.8 = 94.3 gm
Figure 9.34The dependence of eutectoid Figure 9.35 The dependence of eutectoid
temperature on alloy concentration for composition (wt% C) on alloy concentration
several alloying elements in steel. for several alloying elements in steel.
Alloying Steel with More Elements
• Teutectoid changes: • Ceutectoid changes:

(wt%C)
Ti Si
T Eutectoid (°C)
Mo Ni
W
Cr

C eutectoid
Cr Si
Mn
Mn W
Ti Mo
Ni

wt. % of alloying elements wt. % of alloying elements

Adapted from Fig. 9.34,Callister 7e. (Fig. 9.34 from Edgar Adapted from Fig. 9.35,Callister 7e. (Fig. 9.35 from Edgar
C. Bain, Functions of the Alloying Elements in Steel, C. Bain, Functions of the Alloying Elements in Steel,
American Society for Metals, 1939, p. 127.) American Society for Metals, 1939, p. 127.)
SUMMARY
• Equilibrium phase: diagrams are a convenient and concise way of representing the most
stable relationships between phases in alloy systems.
• A phase is some portion of a body of material throughout which the physical and chemical
characteristics are homogeneous.
• Three microstructural characteristics that are important for multiphase alloys are
The number of phases present The relative proportions of the phases The manner in which
the phases are arranged
• Three factors affect the microstructure of an alloy:
oWhat alloying elements are present
oThe concentrations of these alloying elements
oThe heat treatment of the alloy