Definitions: Components and Phases

• Component - chemically recognizable species (Fe and C in carbon steel,

H2O and NaCl in salted water).

• A binary alloy contains two components, a ternary alloy – three, etc.

• Phase – a portion of a system that has uniform physical and chemical

characteristics. Two distinct phases in a system have distinct physical or
chemical characteristics (e.g. water and ice) and are separated from each
other by definite phase boundaries.

• A phase may contain one or more components.

• A single-phase system is called homogeneous,

• systems with two or more phases are mixtures are heterogeneous systems.
 Definitions: Solubility Limit
• Solvent - host or major component in solution, solute - minor
component

• Solubility Limit of a component in a phase is the maximum

amount of the component that can be dissolved in it (e.g. alcohol
has unlimited solubility in water, sugar has a limited solubility, oil
is insoluble). The same concepts apply to solid phases: Cu and Ni
are mutually soluble in any amount (unlimited solid solubility),
while C has a limited solubility in Fe.
 Phase Diagrams
• A phase diagram, also called equilibrium diagram or a
constitutional diagram, graphically illustrates the relationships
among temperature, composition, and the phases present in a
particular alloy system.
 Interpretation of Phase Diagrams
• For a given temperature and composition we can use
phase diagram to determine:
1) The phases that are present
2) Compositions of the phases
3) The relative fractions of the phases
• Finding the composition in a two phase region:
1. Locate composition and temperature in diagram
2. In two phase region draw the tie line or isotherm
3. Note intersection with phase boundaries.
Read compositions at the intersections.
The liquid and solid phases have these compositions.
 GIBB’S PHASE RULE
• Gibb’s phase rule describes the thermodynamic state of a material.
• This famous rule is used to determine the number of phases that can
coexist in equilibrium in a given system.
• It has the general form: F = C – P + 2
• C is the number of components, usually elements or compounds, in
the system.
• F is the number of degrees of freedom, or number of variables, such
as temperature, pressure, or composition that are allowed to change
independently without changing the number of phases in
equilibrium.
• P is the number of phases present
• The constant “2” in the equation implies that both temperature and
pressure are allowed to change.
• For the triple point of water:
One component, i.e., water.
3 phases present, i.e. vapor, liquid, and solid.
F = 1 – 3 + 2 = 0, so this is an invariant point on the
diagram.
• Most binary phase diagrams used in materials
science are temperature and composition
diagrams at a constant 1 atmosphere of pressure.
• The constant pressure will reduce the degrees of
freedom from “2” in Gibb’s equation to “1” for a
binary phase diagram
• Thus, F = C – P + 1.
• A binary phase diagram between two elements A
and B. When an alloy is present in a two phase
region, a tie line at the temperature of interest
fixes the composition of the two phases. This is a
consequence of the Gibbs phase rule, which
provides for only one degree of freedom.
Phase Diagrams Containing Three-Phase Reactions

• In more complex phase diagrams, the type of melting is sometimes used to

describe the type of intermediate compound that occurs along with a
particular type of solid state reaction.
• Congruently melting compounds are those that maintain their specific
composition right up to the melting point.
• This appears as a localized “dome” in the liquidus region of the phase
diagram.
• Incongruent melting compounds do not occur directly from the liquidus,
but are formed by some form of solid-state reaction.
The five most important three-phase reactions that occur in phase diagrams
are:
• Eutectic – a liquid transforms into two solids upon cooling
• Eutectoid – a solid transforms into two new solids
• Peritectic – a liquid plus a solid transforms into a new solid
• Peritectoid – two solids transforms into a new solid
• Monotectic – a liquid transforms into a new liquid and a solid.
Three phase reaction type, reaction equation and appearance on a phase diagram.
 The Lever Rule
• Finding the amounts of phases in a two phase region:
• 1. Locate composition and temperature in diagram
• 2. In two phase region draw the tie line or isotherm
• 3. Fraction of a phase is determined by taking the length of the tie line to the
phase boundary for the other phase, and dividing by the total length of tie line
• The lever rule is a mechanical analogy to the mass balance calculation. The tie
line in the two-phase region is analogous to a lever balanced on a fulcrum.
 The Lever Rule

Mass fractions: WL = S / (R+S) = (Cα - Co) / (Cα- CL)

Wα = R / (R+S) = (Co - CL) / (Cα- CL)
 Derivation of the lever rule

• WL = (Cα - Co) / (Cα- CL)

1) All material must be in one phase or the other:
Wα + WL = 1
2) Mass of a component that is present in both phases equal to the mass
of the component in one phase + mass of the component in the
second phase:
WαCα + WLCL = Co
3) Solution of these equations gives us the Lever rule.
Wα = (Co - CL) / (Cα- CL)
Phase compositions and amounts. An
example.

Co = 35 wt. %, CL = 31.5 wt. %, Cα = 42.5 wt. %

Mass fractions: WL = (Cα - Co) / (Cα- CL) = 0.68
Wα = (Co - CL) / (Cα- CL) = 0.32
Iron-Carbon System
 Phases in Fe–Fe3C Phase Diagram
􀂾 α-ferrite - solid solution of C in BCC Fe
• Stable form of iron at room temperature.
• The maximum solubility of C is 0.022 wt%
• Transforms to FCC γ-austenite at 912 °C
􀂾 γ-austenite - solid solution of C in FCC Fe
• The maximum solubility of C is 2.14 wt %.
• Transforms to BCC δ-ferrite at 1395 °C
• Is not stable below the eutectic temperature (727 ° C) unless cooled rapidly (Chapter
10)
􀂾 δ-ferrite solid solution of C in BCC Fe
• The same structure as α-ferrite
• Stable only at high T, above 1394 °C
• Melts at 1538 °C
􀂾 Fe3C (iron carbide or cementite)
• This intermetallic compound is metastable, it remains as a compound indefinitely at
room T, but
decomposes (very slowly, within several years) into α-Fe and C (graphite) at 650 - 700
°C
• Fe-C liquid solution
 A few comments on Fe–Fe3C system
• C is an interstitial impurity in Fe. It forms a solid solution with α, γ, δ phases of
iron
• Maximum solubility in BCC α-ferrite is limited (max.0.022 wt% at 727 °C) - BCC
has relatively small interstitial positions
• Maximum solubility in FCC austenite is 2.14 wt% at 1147°C - FCC has larger
interstitial positions
• Mechanical properties: Cementite is very hard and brittle - can strengthen steels.
Mechanical properties also depend on the microstructure, that is, how ferrite and
cementite are mixed.
• Magnetic properties: α -ferrite is magnetic below 768 °C, austenite is non-
magnetic
• Classification. Three types of ferrous alloys:
• Iron: less than 0.008 wt % C in α−ferrite at room T
• Steels: 0.008 - 2.14 wt % C (usually < 1 wt % ) α-ferrite + Fe3C at room temperature
• Cast iron: 2.14 - 6.7 wt % (usually < 4.5 wt %)
 Eutectic and eutectoid reactions in Fe–Fe3C
Eutectic: 4.30 wt% C, 1147 °C
L ↔ γ + Fe3C

Eutectoid: 0.76 wt%C, 727 °C

γ(0.76 wt% C) ↔ α (0.022 wt% C) + Fe3C

Eutectic and eutectoid reactions are very important in heat treatment of steels
 Ferritre:
 The interstitial solid solution of carbon in α– iron is called Ferrite
 The maximum solubility of carbon in α– iron is 0.025% at 723oC
 It is very soft, ductile and does not respond to heat treatment
Austenite :
 The interstitial solid solution of carbon in γ– iron is called Austenite
 The maximum solubility of carbon in γ– iron is 2.0% at 1300oC
 It has high ductility and low yield strength
 It is non-magnetic
Cementite:
 Iron-Carbon alloy in the form of chemical compound (Fe3C) is called Cementite
and it contains 6.67% Carbon
 It is magnetic
Pearlite:
 The eutectoid mixture of Ferrite and Cementite is called pearlite
 It is more soft and ductile than cementite, but harder and stronger and stronger
than Ferrite
Ledeburite:
Prof.Roopa T. S. ME Department, RVCE
 The eutectic mixture of Austenite and Cementite is called Ledeburite
Bengaluru-59
17
Martensite:
• Martensite is a super saturated solid solution of carbon in α – Iron
• It is very hard and brittle
• Body Centred Tetragonal structure
Bainite:
• It is a mixture of ferrite and cementite and it is feather like in appearance
• It is obtained by an isothermal decomposition of austenite at about 350 –
450oC
Sorbite and troostite:
• Sorbite and Troostite possess the same structure of pearlite
(ferrite + Cementite), but only the difference is the size of particles
• Sorbite:
At lower temperature (600 C), i.e., higher rate of cooling, the austenite is
transformed into fine mixture of ferrite and cementite. This structure is
called Sorbite.
• Sorbite is weaker but more ductile than troostite
• Troostite:
• At still lower temperature 550 – 500oC, i.e., at very high rate of cooling,
austenite decompose to very fine lamellar structure of ferrite-cementite
mixture, it is called Troostite.
Prof.Roopa T. S. ME Department, RVCE
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Bengaluru-59
EFFECT OF COOLING RATE ON MICRO-STRUCTURE

Prof.Roopa T. S. ME Department, RVCE

19
Bengaluru-59
EFFECT OF COOLING RATE ON MICRO-STRUCTURE

Prof.Roopa T. S. ME Department, RVCE

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Bengaluru-59
 Variety of Cast Iron Microstructures

Gf , graphite flake
Gr , graphite rosettes
Gn, graphite nodules
P, pearlite = a + cementite
a, ferrite

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 Ferrous Alloys
Strengths
http://www.nickelinstitute.org/index.cfm?ci_id=8&la_id=1
1) Inexpensive stainless steel videos

2) Abundant supply of iron ore

3) Many applications due to wide range of
material properties.

Limitations
1) Relatively high densities
2) Relatively low electrical conductivities
3) Generally poor corrosion resistance
22
 Ferrous

Steels Cast iron

Low Alloy High Alloy

Stainless steel Tool steel

23
 Compact Graphite Iron (CGI)
 CGI graphite occurs as blunt flakes or
with a worm-like shape (vermicular).
 Microstructure and properties are a cross
between gray and ductile iron.
 Production requires other alloying
elements to minimize the sharp edges
and formation of spheroidal graphite.
 CGI retains much of the castability of gray CGI
iron, but has a higher tensile strength and
some ductility.
 Its matrix structure can be adjusted by
alloying or heat treatment.
 relatively high thermal conductivity
 good resistance to thermal shock
 lower oxidation at elevated temperatures
 Carbon content: 3.1 – 4.0 wt% CGI
 Silicon content: 1.7 – 3.00 wt %
24
 Grey Cast Iron Malleable Cast Iron Ductile Cast Iron White Cast Iron

Flakes of graphite in Obtained by heat treatment Also called nodular cast Freshly broken surface
pearlite/ferrite matrix leading of white cast iron. Contains iron- graphite exists as shows a bright white
to grey sooty appearance carbon as irregular round round particles/spheroid fracture
particles known as temper form in ferrite/pearlite
carbon matrix

Composition: 2.5- 3.8 % C; Composition: 2- 3%C; 0.6 Composition: 3.5- Composition: 1.8 –
1.1 – 2.8% Si; 0.15%P; 0.4 – – 1.3% Si; 0.15%P; 0.2 – 3.8%C; 1.1 – 3.5% Si; 3.6%C; 0.5 – 2% Si;
1% Mn;0.1%S 0.6% Mn;0.1%S 0.08%P; 0.3 – 0.8% 0.18%P; 0.2 – 0.8%
Mn;0.2%S Mn;0.1%S

Properties: Properties: High tensile Properties: High tensile Properties: Brittle-not

Lowest melting point- strength, good strength, high machinable under normal
1200ºC, High fluidity, Better machinability, high machinability, high wear conditions, excellent
machinability, High resistant toughness, high wear and corrosion resistance abrasive wear resistance
to wear, Good damping resistance and damping and good thermal shock
capacity, High compressive capacity resistance
strength

Applications: Machine tool Applications: Automobile Applications: Paper Applications: for

structures, Under ground industry, agricultural industries machinery, IC producing malleable iron
gas/water pipes, Machine implements, electrical line engines and castings, hard and
covers, IC engine cylinder hardware, conveyor chain automobiles, power abrasion resistance
block heads, Piston rings links, machine parts, hand transmission equipment, requirements
furnace parts Frames of tools farm implements and
electric motors tractors, earth moving 25
 Ferrous Materials  Steels
 Steels are iron-carbon alloys
that may contain other alloying Steels

elements.
 There are 1000s of alloys with Low alloy High alloy

different compositions and/or

heat treatments.
Stainless
 Low Alloy (<10 wt%)
Low
Carbon
 Low Carbon (<0.25 wt%)
 Medium Carbon (0.25 to 0.60 wt%)
Tool
Medium
 High Carbon (0.60 to 1.4 wt%) Carbon

 High Alloy
High
 Stainless Steel (> 11 wt% Cr) Carbon
 Tool Steel
 Low Carbon Steel
 Plain carbon steels have very little additives
(alloying elements) and small amounts of
manganese.
 Most prevalent type of steel is low carbon steel
(greatest quantity produced; least expensive).
 Low carbon not responsive to heat treatment; have
to cold work.
 Weldable and machinable.
 High Strength, Low Alloy (HSLA) steel contains
alloying elements (copper, vanadium, nickel and
molybdenum) up to 10 wt %; they have higher
strengths (than plain LC steels) and may be heat
treated.
Medium Carbon Steel
 These alloys may be (heat treated)
austenitized, quenched and then tempered to
improve mechanical properties (tempered
martensite).
 Cr, Ni, Mo improve the heat treating capacity
of plain medium carbon steels.

High Carbon Steel

 These steels alloyed with Cr, V, W, Mo are
used in blade applications and tools.
 Alloy steels
 Tool steels
 Stainless steels

 Structural steels

 High temperature steels

Tool steels: Used in machining and forming operations

Capable to work in high temperature
Properties: High strength and toughness, high wear and abrasion
resistance, high dimensional and thermal stability.
Types:
 HSS:

 Hot worked

 Cold worked

 Water hardening

 Shock resisting 29
 HSS – High Speed Steels
HSS-Mb based HSS-W based

Composition 0.7-1%C, 9%Mo, 5%W 0.7-1 %C, 18%W, 4%Cr, 1%V

Properties High strength and toughness, high High strength and toughness, high
resistance to wear and abrasion, resistance to wear and abrasion
high dimensional and thermal
stability

Applications Cutting tools, drill bits, reamers, High temperature dies, tools for
dies hard materials

30
 Hot work steels
 Alloying elements-W, Mo, V and Cr
 Used for high temperature applications like in hot
working tools and dies
 Cold work steels
 Oil or air hardening types
 Used in cold working operations
 Shock resisting steels
 Have high shock and impact resistance
 Used in header dies, punches, chisels
 Water hardening steels
 Plain carbon steels with high carbon content
 Used in most common machine tools for cutting
operations like in drill bits, shear blades, dies,
hammers 31
 Stainless steels
 Basically Cr, Ni, Fe based alloys
 Used mainly for corrosion and heat resistance
applications
 Corrosion resistance is because of the thin
adherent ,stable chromium oxide layer
 >10% Cr
 Classification: Based on microstructure
 Austenitic, Ferritic, Martensitic

33
 Austenitic:
 Composition: 18%Cr, 8%Ni, <0.1% C
 Temperature resistant (Ni stabilises austenitic
structure)
 Can be hardened only by cold working
 High resistant to corrosion
 Non magnetic
 It can undergo intergranular corrosion,
addition of titanium and niobium avoids this.
 Stronger, more ductile, have better fabrication
characteristics.

34
 Ferritic:
 Composition: 18 - 30%Cr, No Ni
 magnetic
 Has BCC structure
 Can be hardened by cold working but can not
be hardened by heat treatment
 Less corrosion resistance compared to
austenitic steels
 It can undergo intergranular corrosion,
addition of titanium and niobium avoids this.
 Stronger, more ductile, have better fabrication
characteristics.
35
 Martensitic:
 Composition: 12 - 17%Cr, No Ni
 Magnetic
 Have Body centered tetragonal structure
 Can be hardened by heat treatment
 Corrosion resistance under mild conditions

36
 High temperature steels
 Perform satisfactorily at high temperature
 Ex: 1. Mo and V alloys: up to 450 and up to 550ºC with 2% Cr
2. Austenitic steels: up to 900ºC
3. Ferritic steels: up to 800ºC
4. Martensitic steels: up to 650ºC
5. Super alloys (Ni and Co based): up to 1000ºC
 Applications: Pressure vessels, Super heater tubes,
aircraft parts, Furnace linings,
Exhaust systems

38
 Structural steels
High strength low alloy steels Ultra high strength low alloy steel
(HSLA UTS - 600-1000MPa) [Maraging steel – (martensitic +
aging) UTS- >1000 MPa]

Composition 0.15-0.25%C, 1.25%Mn, 0.3%Si, 0.03%C, 18-25% Ni, 8%Co

0.02%V

Properties Yield strength: 600MPa Yield strength: 2000MPa

Tensile strength: 750MPa % elongation 12%
% elongation 25%

Applications Automobiles, bridges, trains and

buildings
39
 Effects of Alloying Elements on Steel
 Manganese contributes to strength and hardness; dependent upon the carbon
content. Increasing the manganese content decreases ductility and weldability.
Manganese has a significant effect on the hardenability of steel.
 Phosphorus increases strength and hardness and decreases ductility and
notch impact toughness of steel. The adverse effects on ductility and toughness
are greater in quenched and tempered higher-carbon steels.
 Sulfur decreases ductility and notch impact toughness especially in the
transverse direction. Weldability decreases with increasing sulfur content. Sulfur
is found primarily in the form of sulfide inclusions.
 Silicon is one of the principal deoxidizers used in steelmaking. Silicon is less
effective than manganese in increasing as-rolled strength and hardness. In low-
carbon steels, silicon is generally detrimental to surface quality.
 Copper in significant amounts is detrimental to hot-working steels. Copper can be
detrimental to surface quality. Copper is beneficial to atmospheric corrosion
resistance when present in amounts exceeding 0.20%.
 Nickel is a ferrite strengthener. Nickel does not form carbides in steel. It remains
in solution in ferrite, strengthening and toughening the ferrite phase. Nickel
increases the hardenability and impact strength of steels.
 Molybdenum increases the hardenability of steel. It enhances the creep strength
of low-alloy steels at elevated temperatures. 40