Alloy and Phase Diagram
Outline
Definition of structures
Iron-Carbon equilibrium phase diagram – Sketch
The Iron-Iron Carbide Diagram - Explanation
The Austenite to ferrite / cementite transformation
Nucleation & growth of pearlite
Effect of C %age on the microstructure of steel
a ‘map’ used to indicate/identify phases present
and in what amount.
Properties of an Engineering Material depend on:
Which phases are present in the material
How those phases are arranged (the microstructure)
There is a strong correlation between microstructure
and mechanical properties and development of microstructure
can be understood from the phase diagrams.
Moreover phase diagrams can be used to obtain information about
melting, casting, crystallization, etc.
Phase
(J. Willard Gibbs)
State matter which is uniform throughout not only in chemical
composition but also in physical state
The physically and chemically distinct material
regions that result
Components
The elements or compounds which are mixed initially
Systems with one phase are homogeneous
Systems with more than one phase are heterogenous
A system is at equilibrium if at constant temperature,
pressure and composition the system is chemically and
structurally stable, not changing with time.
Equilibrium is the state that is achieved given sufficient time.
But sometimes it will take too much time to achieve equilibrium
due the kinetics, hence a state along the path to the equilibrium
may appear to be stable. This is called a meta-stable state.
Unstable
Free Energy
Metastable
Stable
time
In thermodynamics the equilibrium is described as the state
of system that corresponds to the minimum of
thermodynamic function called the free energy.
The state of stable thermodynamic equilibrium is the one
with minimum free energy.
a system at a meta stable state is trapped in a local
minimum of free energy that is not the global one.
How do we know which phase is which?
1. Solid solution
2. Intermetallic compounds
3. Intermediate phase
Solid Solution
1. Solid Solution
Alloying to produce a solid solution usually
increases the tensile strength (TS)
decreases the ductility.
Substitutional interstisial
When the amount of the dissolving element in the alloy exceeds the
solid solubility limit of the base metal, a second phase forms in the
alloy.
Intermediate phase
I II Its properties are between two pure elements
Here, the system has two elements (A,B) and two phases: solid solution (I) and
intermediate phase (II)
The microstructure developed depends on
the overall composition and the cooling rate
Eutectic Peritectic
Incongruent Melting
L+B
L
A+L
AB + B
SS
A + AB
A AB B
Unlimited Solubility Limited Solubility
In Solid State In Solid State
Solidus and Liquidus
because of their different crystal structures, some
metals are not miscible
phase-composition diagram
Mg2Pb
intermetallic compound forms a line - not an area -
because stoichiometry (i.e. composition) is exact.
Composition of Phases
The Lever Arm Rule
What is the mass of A phase when the average
composition is X and the Temperature is T.
C
D
Tie line – connects the phases in equilibrium with each other –
essentially an isotherm
ML M
C
D
R S
M S M L R
ML S C C0 R C CL
WL W 0
M L M R S C CL R S C CL
Cu-Ni System Cu-Ni System
T(°C)
A
TA tie line
35% Ni 1300 L (liquid)
B
TB
1200 (solid)
D
TD
20 3032 35 40 43 50
C LC o C wt% Ni
Iron-Carbon System
• Pure iron when heated
experiences 2 changes in crystal
structure before it melts.
• At room temperature the stable
form, ferrite ( iron) has a BCC
crystal structure.
• Ferrite experiences a
polymorphic transformation to
FCC austenite (g iron) at 912 ˚C
(1674 ˚F).
• At 1394˚C (2541˚F) austenite
reverts back to BCC phase d
ferrite and melts at 1538 ˚C (2800
˚F).
33
2. CARBON ALLOTROPY
• Amorphous: charcoal
• Graphite: soft, conductivity.
• Diamond: diamond lattice, extremely hard.
c/a=2,74 diamond lacttice
IRON-CARBON DIAGRAM
Eutectic
eutectoid
Pearlite and
Cementine
Austenite
Ferrite
Pearlite and
Carbide
Pearlite
Steel Cast iron
Definition of structures
Various phases that appear on the
Iron-Carbon equilibrium phase
diagram are as under:
•Austenite
•Ferrite
•Pearlite
•Cementite
•Martensite*
•Ledeburite
Unit Cells of Various Metals
• FIGURE - The unit cell for (a) austentite, (b) ferrite, and (c) martensite. The effect
of the percentage of carbon (by weight) on the lattice dimensions for martensite is
shown in (d). Note the interstitial position of the carbon atoms and the increase in
dimension c with increasing carbon content. Thus, the unit cell of martensite is in
the shape of a rectangular prism.
Microstructure of different phases of steel
Definition of structures
• Ferrite is known as α solid solution.
• It is an interstitial solid solution of a small amount
of carbon dissolved in α (BCC) iron.
• stable form of iron below 912 deg.C
• The maximum solubility is 0.025 % C at 723C and
it dissolves only 0.008 % C at room temperature.
• It is the softest structure that appears on the
diagram.
Definition of structures
Ferrite
• Average properties are:
– Tensile strength = 40,000 psi;
– Elongation = 40 % in 2 in;
Definition of structures
• Pearlite is the eutectoid mixture containing 0.80 % C
and is formed at 723°C on very slow cooling.
• It is a very fine platelike or lamellar mixture of ferrite
and cementite.
• The white ferritic background or matrix contains thin
plates of cementite (dark).
Definition of structures
Pearlite
• Average properties are:
– Tensile strength = 120,000 psi;
– Elongation = 20 % in 2 in.;
– Hardness = Rockwell B 95-100, or BHN 250-300.
Pearlite
– Laminated pearlite, 200÷220 HB.
– Spherical pearlite, 180 HB.
Xe F
Xe
F
Definition of structures
• Austenite is an interstitial solid solution of Carbon
dissolved in g (F.C.C.) iron.
• Maximum solubility is 2.0 % C at 1130°C.
• High formability, most of heat treatments begin with
this single phase.
• It is normally not stable at room temperature. But,
under certain conditions it is possible to obtain
austenite at room temperature.
Definition of structures
Austenite
• Average properties are:
– Tensile strength = 150,000 psi;
– Elongation = 10 percent in 2 in.
– Hardness = Rockwell C 40
– Toughness = high
Definition of structures
• Cementite or iron carbide, is very hard, brittle
intermetallic compound of iron & carbon, as Fe3C,
contains 6.67 % C.
• It is the hardest structure that appears on the
diagram, exact melting point unknown.
• Its crystal structure is orthorhombic.
• It is has
– low tensile strength (approx. 5,000 psi), but
– high compressive strength.
Definition of structures
• Ledeburite is the eutectic mixture of austenite and
cementite.
• It contains 4.3 percent C and is formed at 1130°C.
Definition of structures
• Martensite - a super-saturated solid solution of carbon
in ferrite.
• It is formed when steel is cooled so rapidly that the
change from austenite to pearlite is suppressed.
• The interstitial carbon atoms distort the BCC ferrite
into a BC-tetragonal structure (BCT); responsible for
the hardness of quenched steel
The Iron-Iron Carbide Diagram
• A map of the temperature at which different phase
changes occur on very slow heating and cooling in
relation to Carbon, is called Iron- Carbon Diagram.
• Iron- Carbon diagram shows:
– the type of alloys formed under very slow
cooling,
– proper heat-treatment temperature and
– how the properties of steels and cast irons can
be radically changed by heat-treatment.
Various Features of Fe-C diagram
Phases present
L
ferrite
d BCC structure
BCC structure Ferromagnetic
Paramagnetic Fairly ductile
g austenite Fe3C cementite
FCC structure Orthorhombic
Reactions Non-magnetic Hard
ductile brittle
Peritectic L + d = g
Max. solubility of C in ferrite=0.022%
Eutectic L = g + Fe3C
Eutectoid g = + Fe3C Max. solubility of C in austenite=2.11%
Three Phase Reactions
• Peritectic, at 1490 deg.C, with low wt% C
alloys (almost no engineering importance).
• Eutectic, at 1130 deg.C, with 4.3wt% C, alloys
called cast irons.
• Eutectoid, at 723 deg.C with eutectoid
composition of 0.8wt% C, two-phase mixture
(ferrite & cementite). They are steels.
How to read the Fe-C phase diagram
Eutectic
eutectoid
Pearlite and
Cementine
Austenite
Ferrite
Pearlite and
Carbide
Pearlite
Steel Cast iron
The Iron-Iron Carbide Diagram
The diagram shows three horizontal lines which indicate
isothermal reactions (on cooling / heating):
• First horizontal line is at 1490°C, where peritectic
reaction takes place:
Liquid + d ↔ austenite
• Second horizontal line is at 1130°C, where eutectic
reaction takes place:
liquid ↔ austenite + cementite
• Third horizontal line is at 723°C, where eutectoid
reaction takes place:
austenite ↔ pearlite (mixture of ferrite &
cementite)
Simplified Iron-Carbon phase diagram
austenite ↔ pearlite (mixture of ferrite & cementite)
Hypereutectoid Steel
T(°C)
1600
d
1400 L
Fe3C g g +L
g g 1200 1148°C L+Fe3C
Fe3C (cementite)
(austenite)
g g 1000
W g =x/(v + x)
g +Fe3C
W =(1-W g)
800 v x
Fe3C
V X
600
+Fe3C
pearlite
400
0 1 C0 2 3 4 5 6 6.7
0.76
(Fe) C, wt%C
W pearlite = W g
W = X/(V + X)
Microstructures for iron-iron carbide alloys that have
W =(1 - W )
Fe3C’ compositions between 0.76 and 2.14 wt% carbon are
hypereutectoid (more than eutectoid).
Hypereutectoid Steel
T(°C)
1600
d
1400 L
g g g g +L
g 1200 L+Fe3C
g 1148°C
Fe3C (cementite)
(austenite)
g g 1000
g g g +Fe3C
Fe3C
g g 800
g g
600
+Fe3C
400
0 1 C0 2 3 4 5 6 6.7
0.76
(Fe) C, wt%C
pearlite
56
Hypereutectoid Steel (1.2 wt% C)
pearlite
Proeutectoid: formed above the Teutectoid (727°C)
The Austenite to ferrite / cementite transformation in
relation to Fe-C diagram
Critical temperatures:
A=arret means arrest
A0= a subcritical temperature (<A1) = Curie temperature of
cementite=210°C
A1=Lower critical temperature=eutectoid temperature=727°C
A2=Curie temperature of ferrite=768/770°C
A3=upper critical temperature=γ+α /γ phase field boundary
=composition dependent=910-727°C
A4=Eutectic temperature=1147°C
A5=Peritectic temperature=1495°C
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The Austenite to ferrite / cementite
transformation in relation to Fe-C diagram
In order to understand the transformation
processes, consider a steel of the eutectoid
composition. 0.8% carbon, being slow cooled along
line x-x‘.
• At the upper temperatures, only austenite is
present, with the 0.8% carbon being dissolved in
solid solution within the FCC. When the steel cools
through 723°C, several changes occur
simultaneously.
The Austenite to ferrite / cementite
transformation in relation to Fe-C diagram
• The iron wants to change crystal structure
from the FCC austenite to the BCC ferrite,
but the ferrite can only contain 0.02%
carbon in solid solution.
• The excess carbon is rejected and forms
the carbon-rich intermetallic known as
cementite.
Pearlitic structure
• The net reaction at the eutectoid
is the formation of pearlitic
structure.
• Since the chemical separation
occurs entirely within crystalline
solids, the resultant structure is a
fine mixture of ferrite and
cementite.
Schematic picture of the formation and
growth of pearlite
Cementite
Ferrite
Austenite
boundary
Nucleation & growth of pearlite
The Austenite to ferrite / cementite transformation in relation to
Fe-C diagram
• Hypo-eutectoid steels: Steels having less than 0.8%
carbon are called hypo-eutectoid steels (hypo means "less
than").
• Consider the cooling of a typical hypo-eutectoid alloy
along line y-y‘.
• At high temperatures the material is entirely austenite.
• Upon cooling it enters a region where the stable phases
are ferrite and austenite.
• The low-carbon ferrite nucleates and grows, leaving the
remaining austenite richer in carbon.
The Austenite to ferrite / cementite transformation in
relation to Fe-C diagram
• Hypo-eutectoid steels- At
723°C, the remaining austenite
will have assumed the eutectoid
composition (0.8% carbon), and
further cooling transforms it to
pearlite.
• The resulting structure, is a
mixture of primary or pro-
eutectoid ferrite (ferrite that
forms before the eutectoid
reaction) and regions of pearlite.
The Austenite to ferrite / cementite transformation in relation to
Fe-C diagram
• Hyper-eutectoid steels (hyper means "greater than") are those
that contain more than the eutectoid amount of Carbon.
• When such a steel cools, as along line z-z' , the process is
similar to the hypo-eutectoid steel, except that the primary or
pro-eutectoid phase is now cementite instead of ferrite.
The Austenite to ferrite / cementite transformation in relation to
Fe-C diagram
• As the carbon-rich phase nucleates and grows, the remaining
austenite decreases in carbon content, again reaching the
eutectoid composition at 723°C.
• This austenite transforms to pearlite upon slow cooling
through the eutectoid temperature.
• The resulting structure consists of primary cementite and
pearlite.
• The continuous network of primary cementite will cause the
material to be extremely brittle.
The Austenite to ferrite / cementite transformation in
relation to Fe-C diagram
Hypo-eutectoid steel showing primary cementite along grain
boundaries pearlite
The Austenite to ferrite / cementite transformation
in relation to Fe-C diagram
• It should be noted that the transitions as discussed, are
for equilibrium conditions, as a result of slow cooling.
• Upon slow heating the transitions will occur in the
reverse manner.
The Austenite to ferrite / cementite transformation in
relation to Fe-C diagram
• When the alloys are cooled rapidly, entirely different
results are obtained, since sufficient time may not be
provided for the normal phase reactions to occur.
• In these cases, the equilibrium phase diagram is no longer
a valid tool for engineering analysis.
• Rapid-cool processes are important in the heat treatment
of steels and other metals (to be discussed later in H/T of
steels).
Principal phases of steel and their Characteristics
Crystal
Phase Characteristics
structure
Ferrite BCC Soft, ductile, magnetic
Soft, moderate
Austenite FCC strength, non-
magnetic
Compound of Iron
Cementite Hard &brittle
& Carbon Fe3C
Applications
• It is used tailor properties of steel and to heat
treat them.
• It is also used for comparison of crystal
structures for metallurgists in case of rupture
or fatigue.