UNIT-1

ALLOYS AND PHASE DIAGRAMS

SYLLABUS
Alloy
Pure Metal
solution
Solid solutions
Solid solutions
Solid solutions
Substitutional solid solution
Substitutional solid solution
Substitutional solid solution
types
Ordered Substitutional solid solution
disOrdered Substitutional solid solution
Interstitial solid solution
Interstitial solid solution
Compounds
 Phase Diagrams
Phase diagrams are an important tool in the armory of an materials scientist
Phase diagrams are also referred to as “EQUILIBRIUM PHASE DIAGRAMS”
Broadly two kinds of phase diagrams can be differentiated* →those involving
time and those which do not involve time.
In this chapter we shall deal with the phase diagrams not involving time. This
type can be further sub-classified into Those with composition as a variable (e.g.
T vs %Cu), Those without composition as a variable (e.g. P vs T)
Time-Temperature-Transformations (TTT) diagrams and Continuous-Cooling-
Transformation (CCT) diagrams involve time.
Phase
• Physically distinct, chemically homogenous and mechanically separable region of a system
(e.g. gas, crystal, amorphous...).
Gases:
► Gaseous state always a single phase →mixed at atomic or molecular level.
Liquids:
►Liquid solution is a single phase →e.g. NaCl in H2O
►Liquid mixture consists of two or more phases →e.g. Oil in water (no mixing at the
atomic/molecular level)
Solids:
► In general due to several compositions and crystals structures many phases are possible
► For the same composition different crystal structures represent different phases. E.g. Fe
(BCC) and Fe (FCC) are different phases
► For the same crystal structure different compositions represent different phases. E.g. in
Au-Cu alloy 70%Au-30%Cu & 30%Au-70%Cu are different phases
 kinds of Phases

• Based on state - Gas, Liquid, Solid

• Based on atomic order - Amorphous, Quasicrystalline, Crystalline
• Based on Band structure - Insulating, Semi-conducting, Semi-metallic,
Metallic
• Based on Property - Paraelectric, Ferromagnetic, Superconducting, …..
• Based on Stability - Stable, Metastable, (also- Neutral, unstable)
• Also sometimes- Based on Size/geometry of an entity - Nanocrystalline,
mesoporous, layered, …
Phase transformation
Phase Transformation is the change of one phase into another. E.g.: ►Water →Ice
► α - Fe (BCC) → γ -Fe (FCC)
► γ - Fe (FCC) → α - Fe (ferrite) + Cementite (this involves change in composition)
►Ferromagnetic phase →Paramagnetic phase (based on a property)

Grain
► The single crystalline part of polycrystalline metal separated by similar entities by
a grain boundary.

Microstructure
►(Phases + defects + residual stress) & their distributions
► Structures requiring magnifications in the region of 100 to 1000 times OR
The distribution of phases and defects in a material.
 The GIBBS PHASE RULE
• The phase rule connects the Degrees of Freedom, the number of
Components in a system and the number of Phases present in a
system via a simple equation.
• To understand the phase rule one must understand the variables in
the system along with the degrees of freedom.
Degrees of Freedom:
• It is also known as variance of system.
• It is defined as number of external or internal factors of the system
(temperature, pressure and concentration) that can be independently
changed without altering equilibrium i.e. without causing
disappearance of a phase or formation of a new phase in the system.
Contd…..
• For a system in equilibrium
•F=C-P+2
Where,
F – Degrees of Freedom
C – Number of Components
P – Number of Phases
• The digit 2 stands for these two variables – temperature and pressure.
• Gibb’s phase rule to the metal systems, the pressure is considered as remaining
fixed at one atmosphere. Thus, the effect of pressure is neglected, leaving only
one variable factor i.e. temperature.
• The phase rule equation then simplifies to F = C – P + 1
Unary phase diagram
• If a system consists of just one component(e.g.:water), equilibrium of
phases exists depicted by unary phase diagram. The component may
exist in different forms, thus variables here are–temperature and
pressure.
• The unary system wherein there is just one component.
BINARY ISOMORPHOUS SYSTEMS
Types of reactions in binary phase diagrams
Types of reactions in binary phase diagrams
 Eutectoid Reaction
• In eutectoid system, a solid phase replaces
the liquid phase of eutectic system.
• The eutectoid system involves the
transformation of a solid phase into two
other solid phases on cooling and vice
versa, and expressed as
• γ (solid phase) → α+β (solid Phase).
• In the Fe-C system, there is a eutectoid
point at approximately 0.8wt% C, 723°C.
• Austenite –> ferrite + cementite (Fe3C)
 Eutectoid Reaction
• The eutectoid reaction describes the
phase transformation of one solid into two
different solids.
• The phase just above the eutectoid
temperature for plain carbon steels is
known as austenite or gamma.
• We now consider what happens as this
phase is cooled through the eutectoid
temperature (723°C).
• Austenite –> ferrite + cementite (Fe3C)
Eutectoid Reaction

δ↔γ+ε
 Peritectoid Reaction
Peritectoid phase diagrams involve transformation of two solid
phases into a different solid phase on cooling and vise versa.
γ + β phase → α solid Phase.
Peritectoid Reaction
 THE IRON–IRON CARBIDE (Fe–Fe3C) PHASE
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.

•
 THE IRON–IRON CARBIDE (Fe–Fe3C) PHASE
DIAGRAM
• Its not a true equilibrium phase diagram because iron carbide is not a stable phase.

• Iron carbide decomposes into iron and carbon (graphite).

•Even at elevated temperature (like 700C), it will take several years for decomposition.

•Hence for all practical purpose Iron-Iron carbide phase diagram represents equilibrium changes.


 Cooling curve for pure iron
• -austenite (FCC)  -ferrite (BCC) d
 Max solubility of C is 2.14 wt % Max solubility of BCC structure
-ferrite (BCC) C is 0.022 wt % Paramagnetic
 Stableonly at high T g austenite
• -austenite
 Max solubility of C is 0.10 wt % FCC structure
(FCC)
Non-magnetic
-ferrite (BCC) Max solubility of
ductile
 Stableonly at high T C is 2.14 wt %
a ferrite
 Max solubility of C is 0.10 wt %
 -ferrite (BCC) BCC structure
Stable only at high T Ferromagnetic
Max solubility of C is 0.10 Fairly ductile
wt %
 -ferrite (BCC)
Stable only at high T
Max solubility of C is
0.10 wt %
 -austenite
(FCC)
Max solubility of
C is 2.14 wt %
 -ferrite (BCC)
Max solubility of
C is 0.022 wt %

 Fe3C cementite
Orthorhombic structure

Hard
brittle
 Crystal
Phase Characteristics
structure
Ferrite BCC Soft, ductile, magnetic

Soft, moderate
Austenite FCC strength, non-
magnetic

Compound of Iron
Cementite & Carbon Fe3C Hard &brittle
• 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 723C and it dissolves only 0.008 % C at
room temperature.
• It is the softest structure that appears on the diagram.
 Average properties are:
 Tensile strength = 40,000 psi;
 Elongation = 40 % in 2 in;
 Hardness > Rockwell C 0 or > Rockwell B 90
 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).
 Average properties are:
 Tensile strength = 120,000 psi;
 Elongation = 20 % in 2 in.;
 Hardness = Rockwell C 20, Rock­well B 95-100, or BHN 250-
300.
 Austenite is an interstitial solid solution of Carbon dissolved in 
(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.
 Average properties are:
 Tensile strength = 150,000 psi;
 Elongation = 10 percent in 2 in.;
 Hardness = Rockwell C 40, approx; and
 toughness = high
 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.

 Ledeburite is the eutectic mixture of austenite and cementite.

 It contains 4.3 percent C and is formed at 1130°C.
 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
 It’s a Non Equilibrium Phase: Does not appear on Phase Diagram
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.

•Solid Lines are Diffusional
•Dotted is Diffusionless
Bainite :
Upper bainite consists of
needles of ferrites
separated by long
cementite particles
 It occurs in the T ~300 -
540C
Lower bainite consists of
thin plates of ferrite
containing very fine rods
or blades of cementites
 It occurs in T~200-300C
 CLASSIFICATION OF STEEL AND CAST IRON MICROSTRUCTURE,
PROPERTIES AND APPLICATION

• Carbon being a very small atom gets into the interstitial of ferrite/
austenite phases to form solid solution.

• Ferrous metals - based on iron, comprises about 75% of metal tonnage in

the world. Broadly three main alloys.
 Iron = C content < 0.008 wt%
 Steel = Fe-C alloy (0.008 to 2.11% C)
 Cast iron = Fe-C alloy (2.11% to 6.7% C)
 Steels
Steels can be categorized as
Low carbon steels (C < 0.3 %)
Medium carbon steels (0.3 < C <0.6)
High carbon steels (C>0.6 %)
 Steels can also be grouped as (a) plain carbon steels,
(b) low alloy steels (c) stainless steels and (d) tool
steels
 Eutectoid steels (C = 0.77%)
Hypoeutectoid steels (C between 0.022 to 0.77%) and
Hypereutectoid steels ( C > 0.77%)
 Microstructure of Eutectoid steel
When Fe-alloy of 0.77% of C is
cooled slowly it transforms
from single phase of austenite
to pearlite structure, a lamellar
or layered structure of two
phases: ferrite and cementite

In the micrograph, dark

regions are cementite and
bright regions are ferrite
 Cont…….
Layered structures are
formed because of
redistribution of C atoms
between ferrite (0.022 wt %)
and cementite (6.7 wt %) by
diffusion.
Mechanical properties of
pearlite are in between that
of ferrite (soft) and
cementite (brittle)
Microstructure of hypoeutectoid steel
Microstructure of hypereutectoid steel
 Cast Iron

Cast Iron, as defined earlier, has C concentration greater than

2.11 % and less than 6.7%.
Cast iron can be further subdivided into two categories.

White cast iron: carbon is present in the form of cementite.

Grey cast iron : carbon is present in the free form as graphite.

 Cont…
Grey cast iron : carbon is present in the free form as graphite

 Contains Si (1 to 3 %) which causes formation of graphite flakes distributed throughout

the cast product upon solidification.
 Presence of graphite gives a grey color to the fractured surface
 Good vibration damping because of dispersion of graphite flakes.
 Internal lubricating qualities which make it machinable.
 Products made from gray cast iron include automotive engine
blocks and heads, machine tool bases.
 When chemically treated to form spheroids rather than flakes,
we end up with ductile iron. It is stronger and more ductile.
 Cont…
White cast iron: carbon is present in the form of cementite
 Contains 0.5 to 2% Si and lower C content
 Formed by rapid cooling of the molten metal
 Its hard, brittle and excellent wear resistance
 Applications include railway brake shoes
 When cast iron is heat treated to separate carbon out of solution and
form graphite, resulting metal is called malleable (upto 20%)
 Malleable cast iron is utilized for pipe fitting and flanges
 Microstructures of eutectic cast Iron
On solidification,
ledeburite is formed

On further cooling,

excess carbon comes
out as cementite from
eutectic austenite

At 727 C, eutectic

austenite would
contain 0.77 % C and
would decompose
into pearlite
 Microstructures of hypoeutectic cast Iron
In this case, at
temperature just below
1147 C, consists of
proeutectic austenite
and ledeburite
On further cooling,
excess carbon comes
out as cementite from
proeutectic and eutectic
austenite
At 727 C, both eutectic
and proeutectic
austenite would contain
0.77 % C and would
decompose into pearlite
Microstructures of hypereutectic cast Iron
In this case, at
temperature just
below 1147 C, consists
of proeutectic
cementite and
ledeburite.
On further cooling,
excess carbon comes
out as proeutectoid
cementite from
eutectic austenite.
At 727 C, eutectic
austenite would
decompose into
pearlite.
PROPERTIES
 APPLICATIONS
 (a) plain carbon steels
Low-C: automobile sheet metal
Medium-C : engine parts (crank-shaft)
High-C: springs, blades
(b) low alloy steels:
Various automotive components
 (c) stainless steels
Austenitic: chemical & food processing equipment
Ferritic: kitchen utensils to jet engine components
Martensitic: cutlery, surgical instruments
(d) tool steels:
high speed tool, shock-resistant tools, die
Cont…
Dual-phase steel (ferrite + martensite):
Automotive structural parts, longitudinal beams
Duplex stainless steel (austenite + ferrite):
Heat exchangers, turbocharger pumps
Precipitation hardening stainless stee:
Aerospace and nuclear application
 Gray cast iron
Automotive engine blocks and heads, machine tool bases
White cast iron
pipe fitting and flanges