MTPC2005

PHASE TRANSFORMATION AND HEAT

TREATMENT OF METALS

Complete University Exam Notes

(Detailed 16-Mark Answer Format)

Based on:
"Phase Transformations in Metals and Alloys" — Porter, Easterling & Sherif
"Heat Treatment: Principles and Techniques" — Rajan, Sharma & Sharma

Covers All 5 Modules | 30 Hours | Engineering Metallurgy

Metallurgical & Materials Engineering

 TABLE OF CONTENTS
MODULE I (6 Hrs)
1. Phase Transformations – Definition & Types
2. Free Energy – Ideal & Regular Solutions
3. Spinodal Decomposition & Miscibility Gap
4. Ternary Phase Diagrams

MODULE II (6 Hrs)
5. Order-Disorder Transformations
6. Crystal Interfaces & Microstructure
7. Recrystallization & Grain Growth

MODULE III (6 Hrs)

8. Iron-Carbon Alloy System & Graphitization
9. Pearlitic Transformation
10. Bainitic Transformation
11. Martensitic Transformation

MODULE IV (6 Hrs)
12. TTT Diagrams
13. CCT Diagrams
14. Annealing, Normalizing, Hardening & Tempering
15. Hardenability

MODULE V (6 Hrs)
16. Surface Heat Treatment Processes
17. Heat Treatment of Non-Ferrous Alloys
18. Maraging Steel & HSLA Steel
 MODULE I — Phase Transformations & Thermodynamics (6 Hrs)

TOPIC 1: Phase Transformations — Definition & Types

1. INTRODUCTION
Phase transformation is one of the most fundamental phenomena in materials science and metallurgy.
The properties of metals and alloys — hardness, strength, ductility, toughness — are directly governed by
the phases present and their distribution in the microstructure. Understanding phase transformations
enables metallurgists to tailor material properties through controlled heat treatment.

2. DEFINITION
Phase Transformation is defined as a change from one phase (or mixture of phases) to another, driven
by a reduction in the total free energy of the system. It involves a change in the crystal structure,
composition, or physical state of the material.

3. DRIVING FORCE
The driving force for any phase transformation is the difference in Gibbs free energy (∆G) between the
parent phase and the product phase:
∆G = ∆H – T∆S
where ∆H = enthalpy change, T = temperature (K), ∆S = entropy change.
• Transformation occurs when ∆G < 0 (product phase has lower free energy)
• At equilibrium temperature (T_e), ∆G = 0
• Supercooling (∆T) below T_e provides the driving force for transformation

4. CLASSIFICATION OF PHASE TRANSFORMATIONS

4.1 Based on Thermodynamics (Ehrenfest Classification):
<b>Order</b> <b>Description</b> <b>Example</b>

First Order Discontinuous change in 1st derivatives of G (volume, entropy).

Solidification,
Latent melting,
heat involved.
allotropic transformations

Second Order Continuous change; discontinuity in 2nd derivatives (heatOrder-disorder,

capacity, compressibility).
magnetic transitions
No latent (Curie
heat. point)

4.2 Based on Mechanism:

<b>Type</b> <b>Mechanism</b> <b>Characteristics</b> <b>Example</b>

Diffusional (Reconstructive)
Long-range diffusion of atoms Composition change, nucleation & growth
Pearlite, Widmanstätten ferrite

Displacive (Diffusionless)Coordinated atomic shear; no diffusion

No composition change, shape change
Martensitic transformation

Mixed / Semi-Diffusional Partial diffusion Intermediate character Bainitic transformation

4.3 Based on Kinetics:

• Nucleation & Growth — New phase nucleates at preferred sites then grows (most transformations)
• Spinodal Decomposition — Continuous decomposition without nucleation barrier (uphill diffusion)
• Massive Transformation — No composition change; interface migration controlled
• Martensitic — Athermal, diffusionless, instantaneous shear mechanism
5. NUCLEATION
5.1 Homogeneous Nucleation:
Nucleation occurring uniformly throughout the parent phase. The critical nucleus radius r* and activation
energy ∆G* are given by:
r* = −2γ / ∆Gv
∆G* = 16πγ³ / (3∆Gv²)
where γ = interfacial energy per unit area, ∆Gv = free energy change per unit volume.

5.2 Heterogeneous Nucleation:

Nucleation at grain boundaries, dislocations, inclusions, or free surfaces. The activation energy is
significantly reduced:
∆G*_het = ∆G*_hom × f(θ)
f(θ) = (2 + cosθ)(1 − cosθ)² / 4 [shape factor, 0 ≤ f(θ) ≤ 1]
• Heterogeneous nucleation is dominant in practical metallurgy
• Grain boundaries, phase boundaries, and dislocations act as preferred nucleation sites

6. GROWTH
After nucleation, the new phase grows by migration of the parent-product interface. Growth rate depends
on:
• Temperature (diffusivity)
• Driving force (degree of undercooling)
• Interface mobility
Growth Rate G ∝ D × ∆T / T_e

7. IMPORTANT KEYWORDS
★ Phase Transformation — change in crystal structure/composition driven by ∆G reduction
★ Driving Force — ∆G = ∆H – T∆S
★ Supercooling ∆T = T_e − T_actual
★ Homogeneous vs Heterogeneous Nucleation
★ Diffusional vs Displacive Transformation
★ Critical Nucleus Radius r*

8. APPLICATIONS
• Steel heat treatment (quenching → martensite for hardness)
• Age hardening of aluminium alloys (precipitation hardening)
• Shape memory alloys (reversible martensitic transformation)
• Solidification processing in casting and welding

9. VIVA / IMPORTANT QUESTIONS

Q1. Define phase transformation and state its driving force.
Q2. Distinguish between diffusional and displacive transformations with examples.
Q3. What is the significance of supercooling in phase transformations?
 Q4. Compare homogeneous and heterogeneous nucleation.
Q5. Derive the expression for critical nucleus radius.
Q6. What is the Ehrenfest classification of phase transformations?

TOPIC 2: Free Energy — Ideal & Regular Solutions

1. INTRODUCTION
The Gibbs free energy (G) is the central thermodynamic quantity governing phase stability and phase
transformations. The free energy of mixing determines whether atoms prefer to mix homogeneously or
separate into distinct phases.

2. GIBBS FREE ENERGY OF MIXING

∆G_mix = ∆H_mix − T·∆S_mix
For a binary A-B system with mole fraction X_B:
∆S_mix = −R(X_A ln X_A + X_B ln X_B) [always negative → always favors mixing]

3. IDEAL SOLUTION
Ideal Solution: A solution where the interaction energy between unlike atoms (E_AB) equals the average
of like-atom interactions:
E_AB = (E_AA + E_BB) / 2 → ∆H_mix = 0
∆G_mix = RT(X_A ln X_A + X_B ln X_B) [always negative]
• Free energy composition curve is always concave (∩ shape) — complete miscibility
• No miscibility gap; all compositions are stable
• Example: Cu-Ni system (complete solid solubility)

4. REGULAR SOLUTION
Regular Solution: A solution where ∆H_mix ≠ 0 but atoms are randomly distributed (ideal entropy of
mixing):
∆H_mix = Ω · X_A · X_B
Ω = N_A · z · (E_AB − (E_AA + E_BB)/2) [interaction parameter]
∆G_mix = Ω·X_A·X_B + RT(X_A ln X_A + X_B ln X_B)

Cases:
<b>Ω value</b> <b>Nature</b> <b>∆H_mix</b> <b>Effect</b>

Ω<0 Ordering tendency Negative (exothermic) Compound formation; ordered phases

Ω=0 Ideal solution Zero Random solid solution

Ω>0 Clustering tendency Positive (endothermic) Phase separation at low T; miscibility gap

5. FREE ENERGY COMPOSITION DIAGRAMS

The G-X (free energy vs composition) diagram is fundamental for predicting phase equilibria:
• Common tangent construction: connects points of equal chemical potential on two G-X curves →
gives two-phase region boundaries
• Inflection points (∂²G/∂X² = 0): define the spinodal region
• Convex region: two phases are more stable than one (phase separation)
• Concave region: single phase is stable

6. CHEMICAL POTENTIAL
µ_A = G + (1 − X_B) · (∂G/∂X_B)
µ_B = G − X_B · (∂G/∂X_B)
At equilibrium: µ_A(α) = µ_A(β) and µ_B(α) = µ_B(β) — the common tangent condition.

7. KEYWORDS
★ Gibbs Free Energy G = H − TS
★ Ideal Solution: ∆H_mix = 0
★ Regular Solution: Ω·X_A·X_B term for ∆H_mix
★ Common Tangent Construction
★ Chemical Potential µ
★ Interaction Parameter Ω

8. VIVA QUESTIONS
Q1. Distinguish between ideal and regular solutions.
Q2. What is the common tangent construction? What does it yield?
Q3. How does the interaction parameter Ω determine the miscibility gap?
Q4. Derive the expression for ∆G_mix for a regular solution.

TOPIC 3: Spinodal Decomposition & Miscibility Gap

1. INTRODUCTION
Spinodal decomposition is a unique phase separation mechanism that occurs without a nucleation energy
barrier. It is a continuous, spontaneous separation of a solid solution into two phases of different
compositions.

2. DEFINITION
Spinodal Decomposition: A phase separation mechanism that occurs when the second derivative of free
energy with respect to composition is negative (∂²G/∂X² < 0). It proceeds by uphill diffusion without a
nucleation barrier.

3. THERMODYNAMIC CONDITION
∂²G/∂X² < 0 → Spinodal region (unstable)
∂²G/∂X² > 0 → Metastable region (nucleation required)
∂²G/∂X² = 0 → Spinodal points (inflection points of G-X curve)
The locus of spinodal points at different temperatures forms the chemical spinodal on the phase diagram.

4. MECHANISM
 • Composition fluctuations grow spontaneously (no nucleation barrier)
• Diffusion is "uphill" — atoms diffuse from low to high concentration regions
• A characteristic wavelength λ develops and coarsens with time
• Produces a fine-scale, interconnected two-phase microstructure (tweed structure)
D_eff = D_0 · (∂²G/∂X²) / RT [effective diffusivity, negative in spinodal region]

5. MISCIBILITY GAP
Miscibility Gap: A region on the phase diagram (usually a dome-shaped region) where a single-phase
solid solution is thermodynamically unstable and decomposes into two phases.
• Located inside the solvus curve (binodal)
• The spinodal lies within the miscibility gap
• Between binodal and spinodal: metastable region (nucleation & growth)
• Inside spinodal: unstable region (spinodal decomposition)

6. COMPARISON: Spinodal vs Nucleation & Growth

<b>Feature</b> <b>Spinodal Decomposition</b> <b>Nucleation & Growth</b>

Driving Force ∂²G/∂X² < 0 ∂²G/∂X² > 0 but ∆G overall < 0

Nucleation Barrier None Activation energy ∆G*

Diffusion Uphill (up concentration gradient) Downhill (Fickian)

Microstructure Interconnected, wavelike Discrete particles in matrix

Composition Change Continuous, gradual Sharp interface from start

Example Cu-Ni-Fe, Al-Zn alloys Most precipitation reactions

7. INDUSTRIAL SIGNIFICANCE
• Alnico magnets (Al-Ni-Co): spinodal decomposition produces fine magnetic microstructure → superior
magnetic properties
• Fe-Cr alloys: σ-phase embrittlement via spinodal in nuclear reactor components
• Age-hardened Al alloys: GP zones formation related to spinodal-like clustering

8. KEYWORDS
★ Spinodal: ∂²G/∂X² < 0
★ Uphill Diffusion
★ Miscibility Gap — dome on phase diagram
★ Binodal (solvus) vs Spinodal
★ No nucleation barrier in spinodal

9. VIVA QUESTIONS
Q1. Define spinodal decomposition and state its thermodynamic criterion.
Q2. What is the difference between the binodal and spinodal curves?
Q3. Explain "uphill diffusion" in spinodal decomposition.
Q4. Give two industrial examples of spinodal decomposition and their applications.
 TOPIC 4: Ternary Phase Diagrams

1. INTRODUCTION
Most engineering alloys contain more than two components. Ternary phase diagrams represent
three-component systems and require three composition axes plus temperature — represented as a
triangular prism or isothermal sections.

2. GIBBS PHASE RULE FOR TERNARY SYSTEMS

F=C−P+2
For ternary (C=3): F = 5 − P

<b>Phases (P)</b> <b>Degrees of Freedom (F)</b> <b>Condition</b>

1 4 T, P, X1, X2 all variable

2 3 Three-phase field

3 2 Two variables fixed

4 1 Invariant line

5 0 Invariant point (quintuple point)

3. REPRESENTATION
• Gibbs Triangle: Equilateral triangle; corners = pure components; sides = binary systems; interior =
ternary compositions
• Composition read by drawing lines parallel to each side
• Isothermal sections at fixed T show phase fields
• Liquidus surface projected onto base triangle

4. ISOPLETH & LIQUIDUS PROJECTION

• Isopleth: vertical section at constant ratio of two components
• Liquidus projection: contour lines of liquidus temperature on Gibbs triangle
• Eutectic troughs (valleys) connect binary eutectics to ternary eutectic point
• Ternary eutectic point (E): invariant point where liquid + 3 solids coexist (F=0 at constant P)

5. LEVER RULE IN TERNARY SYSTEMS

In a two-phase region of an isothermal section, the lever rule applies along the tie line:
f_α / f_β = (X_B_o − X_B_β) / (X_B_α − X_B_o)
where X_B_o = overall composition, X_B_α, X_B_β = compositions of the two phases.

6. IMPORTANCE IN ENGINEERING
• Steel: Fe-C-Mn, Fe-C-Cr ternary diagrams guide alloying element additions
• Superalloys: Ni-Al-Cr ternary critical for γ/γ' phase field determination
• Soldering alloys: Sn-Pb-Bi ternary for low-melting eutectic compositions

7. VIVA QUESTIONS
Q1. How do you read composition from a Gibbs triangle?
Q2. State Gibbs phase rule for a ternary system and find degrees of freedom for 3-phase
equilibrium.
Q3. What is a ternary eutectic? What is its significance?
Q4. Distinguish between isopleth and isothermal section.
 MODULE II — Order-Disorder, Interfaces & Microstructure
Evolution (6 Hrs)

TOPIC 5: Order-Disorder Transformations

1. INTRODUCTION
In many alloy systems, atoms can arrange themselves either randomly (disordered) or in a specific pattern
on the crystal lattice (ordered). The transition between these states is called the order-disorder
transformation, and it significantly affects alloy properties.

2. DEFINITION
Ordered Structure: An alloy phase in which unlike atoms occupy specific, preferred lattice sites in a
regular, periodic arrangement. Also called a superlattice or intermetallic compound.
Disordered Structure: Atoms of different types are distributed randomly on lattice sites.

3. LONG-RANGE ORDER (LRO) & SHORT-RANGE ORDER (SRO)

Long-Range Order Parameter (S):
S = (r_A − X_A) / (1 − X_A)
where r_A = fraction of A-sites occupied by correct A atoms, X_A = mole fraction of A.

<b>S value</b> <b>Condition</b> <b>State</b>

S=1 All A atoms on α-sites Perfectly ordered

0<S<1 Partial ordering Partially ordered (antiphase domains)

S=0 Random distribution Completely disordered

Short-Range Order Parameter (σ or α_SRO):

α_SRO = 1 − P_AB / X_B
where P_AB = probability of finding B atom as neighbour of A.
• SRO can exist above the critical ordering temperature T_c
• SRO does not produce extra X-ray diffraction spots; LRO does (superlattice reflections)

4. EXAMPLES OF ORDERED STRUCTURES

<b>Alloy</b>
<b>Structure Type</b> <b>Ordered Lattice</b> <b>Properties</b>

Cu-Au (50-50) L1■ Au on corners/face centers; Cu on edge centers

Strong superlattice X-ray reflections

Cu■Au L1■ Au at corners; Cu at face centers Increased strength, reduced ductility

Fe-Al (FeAl) B2 (CsCl) Fe at corners; Al at body center High-temp structural applications

Ni■Al L1■ Al at corners; Ni at face centers γ' phase in Ni superalloys

Fe■Al D0■ Complex FCC superlattice High oxidation resistance

5. MECHANISM OF ORDERING
 • Ordering is a second-order (continuous) transformation for most systems
• Antiphase Domains (APDs): Ordered domains with different phase shifts grow from different nuclei
• Antiphase Boundaries (APBs): Interfaces between antiphase domains; raise energy
• As ordering proceeds, APDs coarsen to reduce APB area

6. INFLUENCE ON PROPERTIES
<b>Property</b> <b>Effect of Ordering</b> <b>Reason</b>

Yield Strength Increases (order strengthening) Superdislocations required; APB energy must be overcome

Ductility Generally decreases Reduced slip systems; APBs restrict dislocation motion

Electrical Resistivity Decreases significantly Reduced electron scattering in periodic potential

Magnetic Properties Can change drastically Modified spin arrangements in ordered lattice

Diffusion Decreases Ordered lattice has higher activation energy for atom jumps

7. DETECTION OF ORDER
• X-ray Diffraction: Superlattice reflections appear (extra peaks not present in disordered structure)
• Electron diffraction in TEM: sharp superlattice spots
• Measurement of LRO parameter S from intensity of superlattice reflections

8. INDUSTRIAL IMPORTANCE
• Ni■Al (γ') in Ni-base superalloys: provides high-temperature strength in turbine blades
• Fe■Al and FeAl: lightweight high-temperature structural alloys
• Cu■Au: model system for studying order-disorder thermodynamics

9. KEYWORDS
★ Long-Range Order Parameter S
★ Short-Range Order Parameter α_SRO
★ Superlattice / Intermetallic
★ Antiphase Domains & Boundaries
★ Superdislocations

10. VIVA QUESTIONS

Q1. Define long-range order and short-range order with parameters.
Q2. Explain the effect of ordering on yield strength (order strengthening mechanism).
Q3. What are antiphase domains and antiphase boundaries?
Q4. How is ordering detected experimentally?
Q5. Give two examples of ordered structures and their engineering applications.

TOPIC 6: Crystal Interfaces & Microstructure

1. TYPES OF INTERFACES IN CRYSTALLINE MATERIALS

<b>Interface Type</b> <b>Description</b> <b>Energy Range</b> <b>Example</b>
Free Surface Solid-vapour boundary; broken bonds on
~1–2
oneJ/m²
side Fracture surface

Grain Boundary Interface between grains of same phase,

0.25–1
different
J/m²orientation
Polycrystalline metals

Interphase Boundary α/β boundaries in steel

Interface between two different phases Varies by coherency

Stacking Fault Error in stacking sequence of close-packed

~0.01–0.3
planesJ/m² FCC metals

Twin Boundary Mirror-image relationship across boundary

~0.01–0.05 J/m² Twinned copper, brass

2. GRAIN BOUNDARIES
• Low-Angle Grain Boundary (LAGB): Misorientation < 15°; modelled as arrays of dislocations; low
energy
θ = b/D [Read-Shockley equation: misorientation vs dislocation spacing]
• High-Angle Grain Boundary (HAGB): Misorientation > 15°; disordered transition zone ~0.5 nm wide;
high energy
• Coincidence Site Lattice (CSL): Special HAGBs with periodic coinciding lattice points; lower energy

3. INTERPHASE BOUNDARIES — COHERENCY

<b>Type</b> <b>Description</b> <b>Strain Energy</b>
<b>Interfacial Energy</b> <b>Example</b>

Coherent Lattice planes continuous across interface;

High (elastic
atomsstrain)
in perfect
Veryregistry
low GP zones in Al-Cu

Semi-Coherent Partially matched; misfit dislocationsModerate

accommodate strainModerate θ' in Al-Cu aging

Incoherent No lattice matching; like grain boundary

Negligible High (~0.5 J/m²) θ (CuAl■) in overaged Al-Cu

4. MICROSTRUCTURE EVOLUTION
• Microstructure = spatial arrangement of phases, grains, precipitates, and defects
• Determined by: alloy composition, thermomechanical processing history, cooling rate
• Grain size: measured by ASTM grain size number N: n = 2^(N−1) grains/inch² at 100×

5. VIVA QUESTIONS
Q1. Classify crystal interfaces and compare their energies.
Q2. Distinguish between coherent, semi-coherent, and incoherent interphase boundaries.
Q3. What are coincidence site lattice grain boundaries?

TOPIC 7: Recrystallization & Grain Growth

1. INTRODUCTION
When metals are cold worked (deformed), they store energy as dislocations. When heated, this stored
energy drives microstructural evolution through recovery, recrystallization, and grain growth — the three
stages of annealing.

2. RECOVERY
Recovery: Initial stage of annealing involving rearrangement and annihilation of dislocations without
formation of new grain boundaries.
• Polygonization: dislocations rearrange into low-energy sub-grain boundaries
 • Small decrease in hardness; significant decrease in residual stress
• No change in grain structure observed in optical microscope

3. RECRYSTALLIZATION
Recrystallization: Formation of new strain-free grains from the deformed microstructure, driven by the
stored deformation energy.

Key Parameters:
<b>Parameter</b> <b>Effect on Recrystallization Temperature (T_r)</b>

Degree of cold work T_r decreases with increasing deformation

Initial grain size Finer initial grain → lower T_r

Purity of metal Impurities raise T_r (solute drag)

Annealing time Longer time → lower T_r (1 hr standard)

Alloying elements Increase T_r significantly

T_r ≈ 0.3 to 0.5 × T_m (Kelvin) [empirical rule for pure metals]

Laws of Recrystallization:
• Minimum degree of deformation required (critical strain ~2–8%)
• T_r decreases with increasing prior deformation
• Larger prior deformation → finer recrystallized grain size
• Longer annealing time = lower T_r (reciprocal relationship)
• Final grain size independent of initial grain size (depends on deformation)

4. GRAIN GROWTH
Grain Growth: Increase in average grain size after complete recrystallization, driven by reduction of grain
boundary energy.
D² − D_0² = K·t [parabolic grain growth law]
D^n − D_0^n = K·t [general: n ≈ 2 for pure metals, >2 with impurities]

Inhibition of Grain Growth:

• Second-phase particles (Zener pinning): particles pin grain boundaries
D_lim = 4r / (3f) [Zener limiting grain size; r = particle radius, f = volume fraction]
• Solute drag: solute atoms segregate to boundaries and reduce mobility
• Applied magnetic field (in some systems)

5. ABNORMAL (SECONDARY) GRAIN GROWTH

A few grains grow at the expense of others → bimodal grain size distribution.
• Occurs when normal grain growth is inhibited (by second phase) in some regions but not others
• Detrimental in sheet forming (earing in deep drawing)

6. INDUSTRIAL APPLICATIONS
<b>Process</b> <b>Stage Used</b> <b>Application</b>
Process Annealing Recrystallization Restore ductility in cold-drawn wire, sheet

Grain Refinement Controlled recrystallization Improved toughness in HSLA steels

Single Crystal Growth Controlled grain growth Turbine blades (directional solidification)

Texture Control Preferred orientation in recrystallization

Silicon steel transformer laminations

7. KEYWORDS
★ T_r ≈ 0.3–0.5 T_m (Kelvin)
★ Recovery → Recrystallization → Grain Growth
★ Parabolic Grain Growth: D² ∝ t
★ Zener Pinning: D_lim = 4r/3f
★ Critical Strain for Recrystallization

8. VIVA QUESTIONS
Q1. Distinguish between recovery, recrystallization, and grain growth.
Q2. State the laws of recrystallization.
Q3. What is Zener pinning? Give the expression for Zener limiting grain size.
Q4. What is the approximate recrystallization temperature of pure iron? (T_m = 1811 K → T_r ≈
540–900 K)
Q5. Explain abnormal grain growth and its industrial significance.
 MODULE III — Iron-Carbon System & Phase Transformations (6
Hrs)

TOPIC 8: Iron-Carbon Alloy System & Graphitization

1. IRON-CARBON PHASE DIAGRAM

The Fe-C phase diagram is the most important diagram in metallurgy. It forms the basis for understanding
all steels and cast irons.

Important Temperatures & Compositions:

<b>Point/Line</b> <b>Temperature (°C)</b>
<b>Carbon (wt%)</b> <b>Significance</b>

A■ 210 — Magnetic transition in cementite

A■ (PSK line) 727 0.022–6.67 Eutectoid temperature (γ → α + Fe■C)

A■ 768 — Curie temperature of ferrite (magnetic)

A■ 910 (pure Fe) 0–0.77 γ/α+γ boundary

A_cm Variable 0.77–2.0 γ/γ+Fe■C boundary

A■ 1395 — γ→δ transition

Eutectoid (S) 727 0.77 γ → α + Fe■C (pearlite)

Eutectic (C) 1147 4.3 L → γ + Fe■C (ledeburite)

Peritectic (B) 1495 0.17 δ+L→γ

2. MICROSTRUCTURAL CONSTITUENTS
<b>Constituent</b> <b>Structure</b> <b>C%</b>
<b>Hardness</b> <b>Properties</b>

Ferrite (α) BCC, interstitial C <0.022 ~80 HV Soft, ductile, magnetic

Austenite (γ) FCC, interstitial C Up to 2.0 ~200 HV Non-magnetic, parent phase for transformations

Cementite (Fe■C) Orthorhombic 6.67 ~800 HV Very hard, brittle

Pearlite Lamellar α + Fe■C 0.77 ~200 HV Good strength + ductility balance

Bainite Acicular α + Fe■C ~0.77 300–400 HV Good toughness

Martensite BCT ~0.77 500–900 HV Extremely hard, brittle

Ledeburite γ + Fe■C eutectic 4.3 Hard Found in cast irons

3. ALLOTROPY OF IRON
α-Fe (BCC) ←→ [912°C] ←→ γ-Fe (FCC) ←→ [1394°C] ←→ δ-Fe (BCC) ←→ [1538°C] ←→ Liquid
• α-Fe: stable below 912°C; magnetic below 768°C (Curie point)
• γ-Fe (austenite): stable 912–1394°C; non-magnetic; better C solubility (max 2.0%)
• δ-Fe: same BCC structure as α but at higher temperature
 4. AUSTENITE GRAIN SIZE & IMPORTANCE
Austenite Grain Size is critical because:
• Finer austenite grain → finer transformation products → better toughness
• Coarse austenite grain → coarser pearlite/bainite → lower toughness but better hardenability
• ASTM grain size measured at 100× magnification
N = 2^(n−1) where N = grains/inch², n = ASTM grain size number
• Grain coarsening temperature: temperature above which rapid austenite grain growth occurs
• Grain refiners: Al■O■, AlN, Nb(C,N) particles pin austenite grain boundaries

5. GRAPHITIZATION
Graphitization: The process by which metastable iron carbide (Fe■C/cementite) decomposes into iron
and graphite (the stable form of carbon in iron).
Fe■C → 3Fe + C(graphite) [∆G negative at high T, but kinetics slow in steels]

Factors Promoting Graphitization:

• High temperature and long annealing times
• High silicon content (Si strongly promotes graphitization)
• Low sulfur and manganese
• Slow cooling from melt

Factors Opposing Graphitization (promoting white iron):

• Rapid cooling
• High manganese content
• Low silicon content
• Chromium addition

Types of Cast Iron based on graphitization:

<b>Type</b> <b>Graphite Form</b> <b>Si%</b> <b>Cooling</b> <b>Properties</b>

White Iron None (Fe■C) <1 Rapid Hard, brittle, white fracture

Grey Iron Flake graphite 1–3 Slow Good damping, machinable, brittle in tension

Malleable Iron Temper carbon rosettes 1–1.8 Annealed white iron Good ductility and toughness

Ductile (SG) Iron Spheroidal graphite ~2.5 Mg/Ce inoculation Excellent strength + ductility

6. KEYWORDS
★ Eutectoid: 0.77% C, 727°C → pearlite
★ Eutectic: 4.3% C, 1147°C → ledeburite
★ A■, A■, A_cm temperatures
★ Graphitization: Fe■C → 3Fe + C
★ Austenite grain size — ASTM number

7. VIVA QUESTIONS
Q1. What is the eutectoid composition and temperature in the Fe-C system?
Q2. Explain the allotropy of iron and its significance.
Q3. What is graphitization? What factors promote or suppress it?
 Q4. Why is austenite grain size important in heat treatment?
Q5. Distinguish between white iron, grey iron, and ductile iron.

TOPIC 9: Pearlitic Transformation

1. DEFINITION
Pearlitic Transformation: The eutectoid decomposition of austenite (0.77% C) into a lamellar mixture of
ferrite (α) and cementite (Fe■C) called pearlite, occurring at or below 727°C via a diffusion-controlled
nucleation and growth mechanism.
γ (0.77%C) → α (0.022%C) + Fe■C (6.67%C)

2. MECHANISM
• Pearlite nucleates preferentially at austenite grain boundaries
• A colony of alternating ferrite and cementite lamellae grows into austenite
• Carbon diffuses from regions becoming ferrite (low C solubility) to regions becoming cementite (high C)
• The interlamellar spacing S■ decreases with increasing undercooling ∆T
S■ ∝ 1/∆T [finer spacing at greater undercooling]

3. MORPHOLOGY
<b>Type</b> <b>Temperature</b>
<b>Interlamellar Spacing</b>
<b>Hardness</b> <b>Properties</b>

Coarse Pearlite ~700–727°C (small ∆T) ~500 nm (0.5 µm) ~200 HV Soft, ductile, machinable

Fine Pearlite ~550–600°C (large ∆T) ~100–200 nm ~300 HV Harder, stronger

Sorbite ~600–650°C Very fine pearlite ~250–300 HV Good strength/ductility

Troostite ~500–550°C Extremely fine pearlite ~350–400 HV High strength

4. KINETICS
• Transformation follows sigmoidal (S-curve) kinetics: slow start, fast middle, slow finish
• Described by Avrami equation:
X = 1 − exp(−kt^n)
• Activation energy for pearlite growth ~ activation energy for carbon diffusion in austenite

5. INDUSTRIAL APPLICATIONS
• High-carbon steel wire (piano wire, tire cord): fine pearlite → UTS > 2000 MPa after drawing
• Rails and structural steel: coarse pearlite for toughness and wear resistance
• Normalizing of medium carbon steels produces fine pearlite (improved machinability)

6. VIVA QUESTIONS
Q1. Explain the mechanism of pearlitic transformation.
Q2. How does undercooling affect interlamellar spacing? What is the significance?
Q3. Distinguish between coarse pearlite, fine pearlite (sorbite), and troostite.
 TOPIC 10: Bainitic Transformation

1. DEFINITION
Bainite: A metastable transformation product of austenite that forms between the pearlite and martensite
transformation ranges (~550°C to M_s temperature), consisting of ferrite and carbide (Fe■C) with a
plate/lath morphology.

2. TYPES OF BAINITE
<b>Feature</b> <b>Upper Bainite (350–550°C)</b> <b>Lower Bainite (250–350°C)</b>

Ferrite morphology Lath/feathery Acicular/plate

Carbide location Between ferrite laths Within ferrite plates (at 60° to habit plane)

Carbide size Coarser Very fine

Hardness 300–400 HV 400–500 HV

Toughness Lower Better

Mechanism Displacive + diffusion of C out of ferrite Displacive; C trapped in ferrite initially

3. MECHANISM
• Mixed mechanism: Displacive (shear) for ferrite formation + diffusion of carbon
• Upper bainite: carbon diffuses OUT of ferrite before carbide precipitation
• Lower bainite: carbon precipitates WITHIN ferrite plates at 60° to habit plane
• No complete agreement on mechanism in literature (still debated)

4. MORPHOLOGY
• Feathery or acicular appearance in optical microscopy
• TEM reveals fine carbide distribution within and between ferrite laths
• Prior austenite grain boundaries visible

5. PROPERTIES & APPLICATIONS

• Excellent combination of strength and toughness compared to martensite
• Austempering: isothermal transformation to bainite
Austempering T: 250–400°C, then air cool
• Applications: high-strength springs, gears, crankshafts, bainitic rail steel
• No tempering needed (unlike martensite) → less distortion

6. VIVA QUESTIONS
Q1. Distinguish between upper and lower bainite in terms of mechanism, morphology, and
properties.
Q2. What is austempering? What are its advantages over conventional quench and temper?
Q3. Why does lower bainite have better toughness than upper bainite?
 TOPIC 11: Martensitic Transformation

1. INTRODUCTION
Martensite is the hardest and most important transformation product in steels. It is the basis of most
hardening heat treatments and is responsible for the extreme hardness achievable in high-carbon steels.

2. DEFINITION
Martensitic Transformation: A diffusionless, displacive phase transformation in which the parent phase
(austenite) transforms to martensite by a coordinated shear mechanism, without any change in
composition, at or below the martensite start temperature M_s.

3. CHARACTERISTICS
• Diffusionless: No long-range diffusion; atoms move < 1 atomic diameter
• Athermal: Transformation extent depends on temperature, not time
• Reversible: Austenite can be recovered on heating (shape memory alloys)
• First-order: Accompanied by a volume change (~4% expansion for Fe-C)
• Shape change: invariant plane strain (IPS) — shear + dilatation
• Habit plane: {225}γ for low-C, {259}γ for high-C martensite

4. CRYSTAL STRUCTURE
Martensite has a Body-Centred Tetragonal (BCT) structure — a supersaturated solid solution of carbon in
α-Fe:
c/a = 1 + 0.046 × (wt% C) [tetragonality increases with carbon content]

<b>Carbon %</b> <b>c/a ratio</b><b>Hardness (HRC)</b> <b>Structure</b>

0.0 1.00 ~20 BCC (no tetragonality)

0.2 1.009 ~35 BCT (slight)

0.4 1.018 ~52 BCT

0.6 1.028 ~62 BCT

0.8 1.037 ~65 BCT (highly tetragonal)

1.0 1.046 ~67 BCT (maximum hardness ~65–67 HRC)

5. MARTENSITE TEMPERATURES
M_s = Martensite Start Temperature
M_f = Martensite Finish Temperature (M_f ≈ M_s − 200°C approx.)
M_s (°C) = 539 − 423(%C) − 30.4(%Mn) − 17.7(%Ni) − 12.1(%Cr) − 7.5(%Mo) [Andrews equation]
• High carbon and alloying elements depress M_s and M_f
• If M_f < room temperature → retained austenite present after quenching
• Retained austenite can transform to martensite on sub-zero cooling (cryogenic treatment)

6. MORPHOLOGY OF MARTENSITE
<b>Type</b> <b>Carbon Range</b>
<b>Habit Plane</b> <b>Morphology</b> <b>Sub-structure</b>

Lath (Low-C) <0.6 wt%C {111}γ Parallel laths in packets High dislocation density

Plate (High-C) >1.0 wt%C {225}γ or {259}γ Lens-shaped plates (needle in 2D)
Twinned (micro-twins)

Mixed 0.6–1.0 wt%C Mixed Both morphologies Dislocations + twins

7. HARDENING MECHANISM
• Solid solution hardening: Carbon atoms distort BCT lattice, impeding dislocation motion
• High dislocation density (lath martensite): ~10¹■–10¹■ m■²
• Fine plate size: Hall-Petch type strengthening
• Retained austenite islands contribute to toughness (TRIP effect in some steels)

8. SHAPE MEMORY EFFECT

In non-ferrous alloys (e.g., Ni-Ti "Nitinol", Cu-Zn-Al), martensitic transformation is thermoelastic and fully
reversible:
• One-Way Shape Memory: recovers shape on heating above A_f (austenite finish temperature)
• Two-Way Shape Memory: recovers shape both on heating and cooling
• Superelasticity: large reversible strains (~8%) at constant temperature
• Applications: Medical stents, orthodontic wires, actuators, pipe couplings

9. KEYWORDS
★ Diffusionless / Athermal transformation
★ BCT structure; c/a = 1 + 0.046(%C)
★ M_s and M_f temperatures
★ Lath vs Plate martensite
★ Retained austenite
★ Shape Memory Effect (Nitinol)

10. VIVA QUESTIONS

Q1. Define martensitic transformation and list its characteristics.
Q2. Explain the BCT structure of martensite and how c/a ratio varies with carbon content.
Q3. What is M_s temperature? How do alloying elements affect it? (Andrews equation)
Q4. Distinguish between lath and plate martensite.
Q5. What is retained austenite? How is it eliminated?
Q6. Explain the shape memory effect in Ni-Ti alloys.
Q7. What are the mechanisms responsible for the high hardness of martensite?
 MODULE IV — Heat Treatment of Steels (6 Hrs)

TOPIC 12: TTT (Time-Temperature-Transformation) Diagrams

1. INTRODUCTION
TTT diagrams (also called isothermal transformation diagrams or "C-curves" or "S-curves") show what
microstructure forms when austenite is rapidly cooled to a given temperature and held isothermally. They
are fundamental tools in steel heat treatment design.

2. CONSTRUCTION
• Steel samples austenitized → rapidly quenched to fixed T → held for various times → quenched to RT
→ metallographic examination
• Time for transformation start (1%) and finish (99%) plotted vs temperature
• Results in characteristic C-shaped (sigmoid) curves

3. FEATURES OF TTT DIAGRAM

• Nose of TTT curve (T_nose): ~550°C for eutectoid steel; minimum incubation time (~1–2 s)
• Above nose: pearlite transformation (diffusion-controlled)
• Below nose: bainite transformation
• M_s line: Martensite start (independent of time — horizontal line)
• M_f line: Martensite finish
• Cooling rate must exceed critical cooling rate to miss the nose → martensite

4. EFFECT OF CARBON ON TTT DIAGRAM

• Increasing carbon shifts TTT curve to the right (increases incubation time) — improves hardenability
• Hypoeutectoid steels: proeutectoid ferrite line appears above eutectoid temperature
• Hypereutectoid steels: proeutectoid cementite line appears above eutectoid temperature

5. EFFECT OF ALLOYING ELEMENTS

<b>Element</b> <b>Effect on TTT</b> <b>Effect on M_s</b>

C (↑) Shifts right (most powerful) Lowers M_s strongly

Mn Shifts right Lowers M_s

Ni Shifts right Lowers M_s

Cr Shifts right; separates pearlite and bainite noses Slightly lowers M_s

Mo Strongly shifts right; creates separate bainite bay Slightly lowers M_s

Co Shifts LEFT (reduces hardenability) Raises M_s

Al, Si Retard cementite formation Slightly raises M_s

6. READING TTT CURVES FOR DIFFERENT COOLING RATES

• Very fast quench (water quench): misses nose → 100% martensite
 • Moderate cooling: intersects nose → mixed martensite + bainite or pearlite
• Slow cool (furnace cool): → coarse pearlite
• Interrupted quench (martempering): quench to just above M_s → hold → air cool → martensite
without cracking
• Isothermal anneal: hold in pearlite range → fully pearlitic microstructure

7. LIMITATIONS OF TTT DIAGRAMS

• Valid only for isothermal conditions — not directly applicable to continuous cooling
• Constructed for specific austenitizing temperature and grain size
• Austenite grain size affects position (finer grain → TTT shifted left)
• Composition variations in industrial steels shift curves

8. KEYWORDS
★ Nose temperature ~550°C (eutectoid steel)
★ Critical cooling rate (CCR)
★ M_s and M_f lines
★ Martempering
★ Austempering (hold in bainite range)

9. VIVA QUESTIONS
Q1. What is a TTT diagram? How is it constructed?
Q2. Explain the significance of the "nose" of the TTT curve.
Q3. How do alloying elements affect the TTT diagram?
Q4. What is the critical cooling rate? How is it determined from TTT diagram?
Q5. Distinguish between TTT and CCT diagrams.

TOPIC 13: CCT (Continuous Cooling Transformation) Diagrams

1. INTRODUCTION
In industrial practice, steels are continuously cooled rather than isothermally transformed. CCT diagrams
represent the transformation behaviour under continuous cooling conditions and are more directly
applicable to industrial heat treatment.

2. CONSTRUCTION
• Austenitized samples cooled at different rates; transformation start and finish detected by dilatometry or
calorimetry
• Transformation temperature and time plotted for each cooling rate
• Result superimposed on temperature-time plot

3. COMPARISON: TTT vs CCT

<b>Feature</b> <b>TTT Diagram</b> <b>CCT Diagram</b>

Condition Isothermal (constant T) Continuous cooling (varying T)

Position Reference Shifted RIGHT and DOWN vs TTT

Applicability Theoretical; austempering, martempering Practical (normalizing, annealing, quenching)

Curves shown Transformation start/finish at each T Transformation start/finish for each cooling rate

Martensite Athermal lines Shown at lower T (start/finish shifted)

Bainite Clear bainite bay May be suppressed in high-alloy steels

4. MICROSTRUCTURES ON CCT DIAGRAM

• Very slow cooling (furnace anneal): ferrite + coarse pearlite
• Slow cooling (air cool — normalizing): ferrite + fine pearlite
• Moderate cooling: ferrite + pearlite + bainite (mixed)
• Fast cooling (oil quench): martensite + retained austenite
• Very fast cooling (water quench): 100% martensite

5. VIVA QUESTIONS
Q1. Why are CCT diagrams shifted to the right compared to TTT diagrams?
Q2. What microstructures do you expect at different cooling rates from CCT diagrams?
Q3. What is the practical significance of CCT diagrams over TTT diagrams?

TOPIC 14: Annealing, Normalizing, Hardening & Tempering

1. ANNEALING
Annealing: Heat treatment involving heating to a suitable temperature, soaking, and very slow cooling
(furnace cooling) to produce a soft, ductile, stress-relieved condition.
<b>Type</b> <b>Temperature</b> <b>Purpose</b> <b>Cooling</b>

Full Annealing A■+50°C (hypo) or A■+50°CCoarse

(hyper)pearlite; maximum softness Furnace cool

Process Annealing Below A■ (~550–650°C) Restore ductility after cold work Air cool

Spheroidize Annealing Just below A■ or cycling around

Globular
A■ carbides; best machinability Slow furnace cool

Stress Relief Annealing 150–650°C (below A■) Remove residual stresses Slow cool

Recrystallization Annealing 0.3–0.5 T_m Restore cold-worked microstructure Air cool

2. NORMALIZING
Normalizing: Heating to A■+50°C (or A_cm+50°C for hypereutectoid), soaking, and air cooling to
produce a fine, uniform pearlitic microstructure.
• Produces finer pearlite than full annealing (faster air cooling)
• Results in higher strength and hardness than annealing
• Eliminates banded structures, improves uniformity
• Used for: forgings, castings, rolled products to refine grain and improve machinability
Temperature: A■ + 30–50°C; hold 1 hr/inch of thickness; air cool

3. HARDENING (QUENCH HARDENING)

 Hardening: Heating to the austenitizing temperature, soaking for complete austenitization, and rapid
quenching to produce martensite.
Austenitizing temperature: A■+50°C for hypo-eutectoid; A■+50°C for hyper-eutectoid steels

Quenching Media (in order of severity):

<b>Medium</b> <b>Cooling Rate</b><b>H value</b> <b>Application</b>

Brine (10% NaCl) Fastest ~2.0 Simple shapes; plain carbon steel

Water Fast ~1.0 Plain carbon steels; risk of cracking

Oil (warm ~60°C) Moderate ~0.35 Alloy steels; less distortion/cracking

Air Slow ~0.02 Air-hardening steels (high alloy); minimal distortion

Salt Bath Moderate-slow ~0.3 Martempering; uniform cooling

Polymer (PAG) Adjustable 0.2–2.0 Versatile; environmentally friendly

Quenching Defects:
• Quench cracking: thermal stresses exceed fracture strength (high carbon + water quench)
• Distortion: non-uniform cooling produces shape changes
• Soft spots: insufficient quench rate in thick sections
• Retained austenite: M_f below room temperature

4. TEMPERING
Tempering: Reheating of hardened (martensitic) steel to a temperature below A■, holding, and cooling to
improve toughness and ductility at some sacrifice of hardness.

Stages of Tempering:
<b>Stage</b>
<b>Temperature Range</b> <b>Changes Occurring</b>

Stage 1 100–200°C ε-carbide (Fe■.■C) precipitation from BCT martensite; initial hardness drop

Stage 2 200–300°C Retained austenite transforms to lower bainite/tempered martensite

Stage 3 250–350°C ε-carbide dissolves; cementite (Fe■C) nucleates; martensite loses tetragonality → BCT → BCC

Stage 4 >350°C Cementite spheroidizes and coarsens; ferrite recrystallizes; significant softening

Effect of Tempering Temperature on Properties:

• Hardness: decreases continuously with tempering temperature
• Toughness (CVN impact energy): increases, peaks, then may decrease
• Tempered Martensite Embrittlement (TME): brittleness at 250–350°C (also called 260°C
embrittlement)
• Temper Embrittlement (TE): reversible embrittlement at 350–550°C in alloy steels (Mn, P, Sn, Sb
segregation to grain boundaries)

5. COMPARISON TABLE
<b>Treatment</b> <b>Temperature</b><b>Cooling</b> <b>Microstructure</b> <b>Properties</b>

Full Anneal A■+50°C Furnace Coarse pearlite Softest, most ductile

Normalizing A■+50°C Air Fine pearlite Moderate strength/hardness

Hardening A■+50°C Quench Martensite Maximum hardness

Tempering <A■ Air Tempered martensite Balanced strength+toughness

6. KEYWORDS
★ Austenitizing: A■+50°C (hypo), A■+50°C (hyper)
★ Quenching media: brine > water > oil > air
★ Tempering: 4 stages; improves toughness
★ TME: 250–350°C embrittlement
★ Temper Embrittlement: 350–550°C in alloy steels

7. VIVA QUESTIONS
Q1. What is the purpose of tempering? Explain the stages of tempering.
Q2. Compare the microstructures and properties obtained by full annealing and normalizing.
Q3. What is tempered martensite embrittlement? How does it differ from temper embrittlement?
Q4. What factors determine the choice of quenching medium?
Q5. What temperature is used for hardening hyper-eutectoid steel and why?

TOPIC 15: Hardenability

1. DEFINITION
Hardenability: The ability of a steel to be hardened by quenching — specifically, the depth to which a
steel is hardened when austenitized and quenched. NOT the same as hardness (which is the resistance to
indentation).

2. JOMINY END-QUENCH TEST (STANDARD METHOD)

• Standardized specimen: 25 mm diameter × 100 mm long cylinder
• Austenitized at standard temperature → end-quenched with water jet from one end
• Cooling rate varies from very fast at quenched end to air cooling at the other end
• Hardness measured at intervals from the quenched end → Jominy hardenability curve
• High hardenability steel: hardness remains high far from quenched end
• Low hardenability steel: hardness drops rapidly from quenched end

3. FACTORS AFFECTING HARDENABILITY

<b>Factor</b> <b>Effect on Hardenability</b> <b>Reason</b>

Carbon content (↑) Increases (up to ~0.6%C)Shifts TTT right; increases M_s hardness

Alloying elements (Mn, Cr, Mo, Ni,

Increase
Si) significantly Shift TTT curve right → lower critical cooling rate

Austenite grain size (↑) Increases Fewer nucleation sites → slower transformation

Undissolved carbides Decrease Reduce carbon in austenite; provide nucleation sites

Homogeneity of austenite Inhomogeneous → decreases

Composition variations cause local transformation

4. IDEAL CRITICAL DIAMETER (D_I) AND SEVERITY OF QUENCH (H)

 Ideal Critical Diameter (D_I): The diameter of a steel bar that will just produce 50% martensite at the
centre when quenched in an ideal quench (H = ∞).
Critical Diameter (D_c): The bar diameter that gives 50% martensite at centre with a specific quench of
severity H.
D_c / D_I = f(H) [Grossman chart relates D_c, D_I, and H]
H_water = 1.0, H_oil = 0.35, H_brine = 2.0, H_air = 0.02 (Grossman H values)

5. EFFECT OF ALLOYING ELEMENTS — MULTIPLYING FACTORS

Grossman multiplying factors (f) for alloying elements increase D_I:

<b>Element</b> <b>Effect</b> <b>Mechanism</b>

Carbon Most effective per unit Stabilizes austenite; raises C* for pearlite nucleation

Manganese Strong carbide former; very

Dissolves
effective
in austenite; reduces ferrite nucleation rate

Chromium Strong (forms stable carbides)

Retards pearlite; creates separate bainite bay in TTT

Molybdenum Very strong (strongest per

Creates
%) pronounced bainite bay; reduces CCR dramatically

Nickel Moderate Stabilizes austenite; reduces CCR

Boron (~0.003%) Extremely effective Segregates to grain boundaries; blocks ferrite nucleation

6. INDUSTRIAL SIGNIFICANCE
• Allows selection of steel grade and quench medium for a required hardness depth
• Prevents quench cracking (can use slower quench for same martensite depth with high-hardenability
steel)
• Used in gear, axle, and structural component design for through-hardening or case-hardening
specifications

7. KEYWORDS
★ Hardenability ≠ Hardness
★ Jominy End-Quench Test
★ Ideal Critical Diameter D_I
★ Severity of Quench H
★ Boron effect on hardenability

8. VIVA QUESTIONS
Q1. Define hardenability. How does it differ from hardness?
Q2. Describe the Jominy end-quench test with a neat sketch.
Q3. What is the ideal critical diameter? How is it related to severity of quench?
Q4. Explain the role of alloying elements in improving hardenability.
Q5. Why is boron so effective in improving hardenability even at 0.003%?
 MODULE V — Surface Treatments & Non-Ferrous Alloys (6 Hrs)

TOPIC 16: Surface Heat Treatment Processes

1. INTRODUCTION
Many engineering components (gears, cams, crankshafts) require a hard, wear-resistant surface with a
tough, ductile core. Surface heat treatment achieves this combination without changing the bulk
composition.

2. FLAME HARDENING
Definition: Rapid heating of the steel surface with an oxy-acetylene or oxy-propane flame followed by
immediate quenching with water spray.
• Applicable to steels with 0.3–0.6% C
• Case depth: 1.5–6 mm (controllable by flame speed and intensity)
• Types: Spot, progressive, spinning, and combination methods
• Equipment: simple, portable; no furnace required
• Applications: large gears, rails, machine tool slideways, crankshafts, cams
• Limitations: temperature control difficult; risk of overheating; not suitable for complex shapes

3. INDUCTION HARDENING
Definition: Heating the steel surface by electromagnetic induction (eddy currents + hysteresis losses)
using an AC coil, followed by quenching.
P ∝ f × B² (power generated proportional to frequency and magnetic flux density)
• Skin effect: Current concentration near surface; depth δ ∝ 1/√f
<b>Frequency</b> <b>Case Depth</b> <b>Application</b>

50–60 Hz (mains) 3–6 mm Large components, heavy case

1–10 kHz 1–3 mm Medium gears, cams

100–500 kHz 0.5–1.5 mm Small gears, ball screws

1–2 MHz 0.1–0.5 mm Surface hardening of thin sections

• Fast process (seconds); reproducible; easily automated

• Applications: automotive crankshafts, gears, axle shafts, ball races
• Limitations: complex coil geometry for complex shapes; residual stresses possible

4. CARBURIZING
Definition: A case-hardening process in which carbon is introduced into the surface layer of a low-carbon
steel (0.15–0.25% C) by exposure to a carbonaceous atmosphere at 900–950°C, followed by quenching.
Carburizing reaction: CH■ → 2H■ + [C] (carbon transfers to steel surface)

<b>Type</b> <b>Medium</b> <b>Temperature</b>

<b>Case Depth</b> <b>Features</b>

Pack Carburizing Charcoal + BaCO■ in box 900–950°C 0.5–4 mm Simple; batch process; non-uniform heating

Gas Carburizing CH■, C■H■ or CO atmosphere

900–950°C 0.5–3 mm Most common industrial; precise control
Liquid Carburizing Molten NaCN salt bath 750–950°C 0.1–1.5 mm Fast; thin cases; toxic waste disposal issue

Vacuum Carburizing Hydrocarbons at low pressure

900–1050°C 0.3–3 mm No intergranular oxidation; clean process

Carburizing + Heat Treatment Sequence:

• Carburize at 920°C → direct quench OR cool to RT then reheat to A■+50°C → quench → temper at
150–200°C
• Case: 0.7–1.0% C martensite + retained austenite → HRC 58–62
• Core: low-carbon lath martensite or ferrite + pearlite → tough
• Applications: gears (transmission, differential), pins, cams, chain links

5. NITRIDING
Definition: A case-hardening process in which nitrogen is introduced into the surface of steel at
490–560°C (below A■) using ammonia gas or plasma.
2NH■ → 3H■ + 2[N] (nitrogen absorbed into steel surface)

<b>Feature</b> <b>Nitriding</b> <b>Carburizing</b>

Temperature 490–560°C (below A■) 900–950°C (above A■)

Distortion Very low (no phase change) Moderate to high

Case hardness HV 700–1200 (extremely hard) HRC 58–62

Case depth 0.1–0.6 mm (thinner) 0.5–4 mm

Wear resistance Excellent + corrosion resistance Good

Cost Higher; longer cycle Lower; shorter cycle

Steels used Nitralloy, Cr-Al-Mo steels Low-C steels (0.15–0.25%C)

6. CYANIDING & CARBONITRIDING

• Cyaniding: Immersion in molten NaCN/NaCO■ salt bath at 750–850°C → introduces both C and N →
case depth 0.1–0.5 mm; faster than carburizing
• Carbonitriding: Gas atmosphere containing both CH■ (or propane) and NH■ at 700–900°C → C and
N introduced → better hardenability than carburizing alone

7. COMPARISON TABLE
<b>Process</b><b>Element Added</b>
<b>Temperature</b>
<b>Case Depth</b>
<b>Case Hardness</b>
<b>Key Advantage</b>

Flame Hardening None Surface >A■ 1.5–6 mm 58–65 HRC Portable; large parts

Induction Hardening None Surface >A■ 0.5–6 mm 58–65 HRC Fast; automated

Carburizing Carbon 900–950°C 0.5–4 mm 58–62 HRC Deep case; versatile

Nitriding Nitrogen 490–560°C 0.1–0.6 mm 70–80 HRC [Link] distortion; extreme hardness

Carbonitriding C+N 700–900°C 0.1–0.8 mm 60–65 HRC Better hardenability

8. KEYWORDS
★ Flame & Induction Hardening — no composition change
★ Carburizing: 0.15–0.25%C steel, 900–950°C
 ★ Nitriding: 490–560°C, below A■, no distortion
★ Skin depth in induction: δ ∝ 1/√f

9. VIVA QUESTIONS
Q1. Distinguish between case hardening and through hardening.
Q2. Compare flame hardening and induction hardening.
Q3. Explain gas carburizing. What microstructure is produced in case and core?
Q4. Why is nitriding done below A■? What advantage does this give?
Q5. Compare nitriding and carburizing in terms of temperature, case depth, hardness, and
distortion.

TOPIC 17: Heat Treatment of Non-Ferrous Alloys

1. ALUMINIUM-COPPER (Al-Cu) ALLOYS — AGE HARDENING

Precipitation Hardening / Age Hardening: A heat treatment process involving solid solution treatment,
quenching, and aging to produce a fine dispersion of precipitates that strengthen the alloy.

Three Steps:
• Solution Treatment: Heat to single-phase (α) field (~500–540°C for 2024 Al) → dissolve all Cu into Al
→ uniform supersaturated solid solution
• Quench: Rapid cooling to RT → supersaturated solid solution (SSSS) trapped; no time for precipitation
• Aging: Hold at elevated temperature (artificial aging: 100–200°C) or room temperature (natural aging)
→ precipitate forms

Precipitation Sequence in Al-Cu:

SSSS → GP Zones → θ" → θ' → θ (CuAl■)

<b>Stage</b> <b>Precipitate</b> <b>Coherency</b> <b>Size</b> <b>Hardness Effect</b>

Natural aging GP Zones (Cu-rich discs on {100})

Fully coherent 1–5 nm Increases

Early artificial aging θ" (coherent CuAl■) Fully coherent 5–20 nm Peak hardness

Peak aging θ' (semi-coherent) Semi-coherent 10–100 nm Maximum hardness

Overaging θ (CuAl■) Incoherent >100 nm Decreases (softening)

Strengthening Mechanism:
• Coherent GP zones and θ" create strain fields → dislocations must cut through → high stress needed
(cutting mechanism)
• θ' semi-coherent: dislocations by-pass by Orowan looping mechanism
• θ incoherent: easy Orowan bypass → softening (overaging)
Peak strength when transition from cutting to bypassing mechanism occurs

Applications:
• 2024-T4 (naturally aged): aircraft fuselage, wing skin
• 7075-T6 (Zn-Mg-Cu, artificially aged): highly stressed aircraft structures
• 6061-T6 (Al-Mg-Si): structural applications, bicycle frames
 2. BRASS (Cu-Zn ALLOYS) — HEAT TREATMENT
• Stress Relief Annealing: 200–300°C for 1 hr → removes residual stresses from cold work → prevents
season cracking (SCC in ammonia atmosphere)
• Recrystallization Annealing: 450–750°C → restores ductility after cold working
• Alpha brass (<37% Zn): excellent formability; heat treatment = annealing only (no precipitation
hardening)
• Alpha-Beta brass (37–46% Zn): hot working, not cold working; some heat treatment possible

3. TITANIUM ALLOYS — HEAT TREATMENT

Titanium exists in two allotropic forms: α (HCP, stable below 882°C) and β (BCC, stable above 882°C).

<b>Alloy Type</b> <b>Composition</b> <b>Heat Treatment</b> <b>Properties</b> <b>Applications</b>

α alloys Commercially pure Ti; Ti-5Al-2.5Sn

Annealing only High T strength, weldable
Cryogenic, aerospace airframes

β alloys Ti-13V-11Cr-3Al Solution treat + age High strength High-strength fasteners

α+β alloys Ti-6Al-4V (most common) Solution treat + age + annealBest overall propertiesJet engines, biomedical implants

• Ti-6Al-4V solution treatment: heat to β field (995–1040°C) → quench → β transforms to martensite

(α') → age at 500–600°C → fine α+β precipitates → UTS >1000 MPa

4. NICKEL ALLOYS — HEAT TREATMENT

• Ni superalloys (e.g., Inconel 718, Waspaloy, René 95) rely on γ' (Ni■Al, Ni■Ti) precipitation
• Solution treatment: ~1000–1120°C → dissolve γ' → slow cool or air cool
• Aging: 700–900°C → fine γ' precipitates → high-temperature strength
• Double aging used for bimodal γ' distribution in disk alloys
• Applications: jet engine turbine blades, disks, combustion chambers, nuclear reactors

5. KEYWORDS
★ Age Hardening Steps: Solution Treat → Quench → Age
★ Precipitation Sequence: SSSS → GP Zones → θ" → θ' → θ
★ Peak hardness at θ' (semi-coherent) stage
★ Overaging: incoherent θ → softening
★ Ti allotropes: α(HCP) ↔ β(BCC) at 882°C
★ γ' (Ni■Al) in Ni superalloys

6. VIVA QUESTIONS
Q1. Explain the three steps of age hardening in Al-Cu alloys.
Q2. What is the precipitation sequence in Al-Cu? At what stage is peak hardness obtained?
Q3. Explain the cutting and bypassing (Orowan) mechanisms in age-hardened alloys.
Q4. What is overaging? How does it affect properties?
Q5. What heat treatment is given to Ti-6Al-4V alloy? What microstructure results?
Q6. What is the role of γ' phase in Ni superalloys?

TOPIC 18: Maraging Steel & HSLA Steel

 1. MARAGING STEEL
Maraging Steel: An ultra-high strength steel that derives its strength from martensite + aging (intermetallic
precipitation), NOT from carbon. The name combines "martensite" and "aging."

Composition:
• Fe + 18% Ni + 8–12% Co + 3–5% Mo + Ti + Al; Carbon < 0.03%
• Grades: 18Ni(200), 18Ni(250), 18Ni(300), 18Ni(350) — yield strength in ksi

Heat Treatment:
Austenitize at 820°C → Air cool → soft, tough lath martensite (28–35 HRC)
Age at 480°C for 3–6 hrs → intermetallic precipitates (Ni■Mo, Ni■Ti, Fe■Mo) → UTS 1700–2500
MPa

Strengthening Mechanism:
• Low carbon martensite (very tough, easily machined before aging)
• Fine, coherent intermetallic precipitates (Ni■Mo, Ni■Ti, Fe■Mo) in martensite matrix
• No carbon → no hydrogen embrittlement issues

Advantages over conventional high-strength steels:

<b>Feature</b> <b>Maraging Steel</b> <b>High-C Martensite Steel</b>

YS 1400–2500 MPa 1000–1500 MPa

Toughness (K_IC) High (50–80 MPa√m) Lower

Weldability Excellent Poor (preheat/PWHT required)

Distortion in aging Very low (<0.1%) High on quenching

Machinability (before aging) Good (soft martensite) Poor

Applications:
• Aerospace: rocket motor casings, aircraft undercarriage components
• Die casting: tooling for zinc die casting (thermal fatigue resistance)
• Nuclear: rotor shafts, containment components
• Sports: golf club shafts, fencing swords
• Ordnance: gun barrels, warhead casings

2. HIGH-STRENGTH LOW-ALLOY (HSLA) STEELS

HSLA Steels: Low-carbon steels (0.05–0.15% C) with small additions of microalloying elements (Nb, V,
Ti, typically <0.1% each) that achieve high strength through a combination of strengthening mechanisms
while maintaining good weldability and toughness.

Chemical Composition:
• C: 0.05–0.15%; Mn: 0.5–1.6%; Si: ≤0.5%
• Microalloying elements: Nb (0.02–0.05%), V (0.05–0.15%), Ti (0.01–0.04%)
• Optional: Cr, Ni, Mo, Cu for additional strength or corrosion resistance

Strengthening Mechanisms:
 <b>Mechanism</b> <b>Contribution</b><b>Key Element</b> <b>How It Works</b>

Precipitation Hardening ~100–200 MPa Nb, V, Ti carbides/nitridesFine MC/M(CN) precipitates formed during controlled rolling

Grain Refinement ~100–200 MPa Nb, Ti (grain pinning) Fine austenite grain → fine ferrite → Hall-Petch strengthening

Solid Solution ~50–100 MPa Mn, Si, P Solute atoms strain ferrite lattice

Dislocation Strengthening ~50 MPa Pancaked austenite → increased nucleation sites → fine ferrite
Controlled rolling (warm rolling)

Controlled Rolling (Thermomechanical Processing):

• Deformation in the non-recrystallization zone (800–900°C) → elongated, pancaked austenite grains
• Cooling rate controlled → ASTM ferrite grain size 10–12 (very fine)
• Results in both grain refinement AND precipitation hardening simultaneously

Classification of HSLA Steels:

<b>Type</b> <b>YS (MPa)</b> <b>Key Feature</b> <b>Examples/Standards</b>

Weathering steels 350–450 Cu, Cr, Ni additions; atmospheric corrosion

Cor-Ten
resistance
(ASTM A588)

Microalloyed steels 350–700 Nb, V, Ti; controlled rolling API 5L X65, X80 pipeline steels

Dual-phase steels 500–800 Martensite islands in ferrite DP600, DP800 (automotive)

TRIP steels 600–900 Retained austenite → martensite on deformation

TRIP700, TRIP800 (automotive)

Bainitic HSLA 600–900 Bainitic microstructure Rail steels, ship plate

Applications:
• Structural: bridges, buildings, cranes, offshore platforms (ASTM A572)
• Pipeline: high-pressure natural gas pipelines (API 5L X70, X80)
• Automotive: car body panels, bumpers, chassis (weight reduction 20–30%)
• Shipbuilding: hulls and deck structures
• Rail: high-strength rails for high-speed railways

Advantages of HSLA over Plain Carbon Steel:

<b>Property</b> <b>HSLA Steel</b>
<b>Plain Carbon Steel (equivalent strength)</b> <b>Advantage</b>

C content 0.05–0.15% 0.3–0.5% Better weldability (low CE)

Weight Can reduce 20–30% Heavier section Weight savings; fuel economy

Toughness (CVN) High (even at −40°C) Moderate Better low-temperature service

Weldability Excellent (CE < 0.45%) Limited No preheat needed in most cases

Corrosion resistance Better (weathering grades)

Average Reduced maintenance cost

3. KEYWORDS
★ Maraging: Fe-18Ni + intermetallic precipitates; age at 480°C
★ Maraging grades: 18Ni(200/250/300/350)
★ HSLA: Nb+V+Ti microalloying; grain refinement + precipitation
★ Controlled rolling → pancaked austenite → fine ferrite
★ CE (Carbon Equivalent) = C + Mn/6 + (Cr+Mo+V)/5 + (Ni+Cu)/15
★ TRIP steel: retained austenite → martensite during forming
4. VIVA QUESTIONS
Q1. What is maraging steel? What gives it its ultra-high strength?
Q2. Explain the heat treatment cycle of maraging steel.
Q3. Why is maraging steel preferred over high-carbon steel for aerospace applications?
Q4. Define HSLA steel and list the strengthening mechanisms.
Q5. What is the role of Nb in HSLA steels?
Q6. What is controlled rolling? How does it contribute to the properties of HSLA steels?
Q7. Distinguish between dual-phase and TRIP steels.
 QUICK REVISION — KEY EQUATIONS & FACTS

ESSENTIAL EQUATIONS FOR EXAMS

<b>Equation</b> <b>Meaning</b> <b>Module</b>

∆G = ∆H − T∆S Gibbs free energy; driving force I

r* = −2γ/∆Gv Critical nucleus radius I

∆G* = 16πγ³/(3∆Gv²) Activation energy for homogeneous nucleation

I

∆G_mix = Ω·X_A·X_B + RT(X_A lnX_A + X_B lnX_B) Regular solution free energy of mixing I

S = (r_A − X_A)/(1 − X_A) Long-range order parameter II

D² − D_0² = K·t Parabolic grain growth law II

D_lim = 4r/(3f) Zener limiting grain size (pinning) II

S■ ∝ 1/∆T Pearlite interlamellar spacing III

c/a = 1 + 0.046(%C) Martensite tetragonality III

M_s = 539 − 423(%C) − 30.4(%Mn) − ... Martensite start temperature (Andrews) III/IV

X = 1 − exp(−kt^n) Avrami equation (transformation kinetics) III

CE = C + Mn/6 + (Cr+Mo+V)/5 + (Ni+Cu)/15 Carbon equivalent for weldability V

KEY TEMPERATURES TO REMEMBER (Fe-C SYSTEM)

<b>Symbol</b> <b>Temperature</b> <b>Significance</b>

A■ 727°C Eutectoid (pearlite reaction temperature)

A■ 910°C (pure Fe) to 727°C at 0.77%C

Upper critical temperature (γ/α+γ boundary)

A■ 1394°C γ → δ transition

Eutectic 1147°C at 4.3%C L → γ + Fe■C (ledeburite formation)

T_r (Fe) ~450–550°C Recrystallization temperature of iron

Nose (eutectoid steel) ~550°C Minimum incubation time on TTT

Carburizing 900–950°C Above A■ for gas carburizing

Nitriding 490–560°C Below A■ — no distortion

Maraging aging 480°C × 3–6 hr Intermetallic precipitation in maraging steel

Al-Cu solution treat 500–540°C Single α-phase field

COMMON PREVIOUS-YEAR QUESTION PATTERNS

<b>Question Type</b> <b>Example</b> <b>Module</b>

Define + Explain (2-mark) "Define hardenability. How does it differ from hardness?" IV

Mechanism (8-mark) "Explain the mechanism of martensitic transformation with neat sketch." III

Compare/Distinguish (8-mark)
"Compare TTT and CCT diagrams." IV
 Full answer (16-mark) "Explain the heat treatment stages of age hardening in Al-Cu alloys. Describe
V the precipitation sequenc

Diagram-based "With a neat TTT diagram, explain the microstructures obtained at different IV
cooling rates."

Industrial application "Explain induction hardening with applications." V

Derivation "Derive the expression for critical nucleus radius." I

CONCLUSION
These notes cover the complete MTPC2005 syllabus across all five modules. The subject integrates
thermodynamic principles (free energy, phase diagrams) with kinetic considerations (nucleation, growth,
TTT/CCT diagrams) and practical heat treatment applications. Mastering the Fe-C phase diagram, TTT
diagrams, and the precipitation hardening sequence in Al-Cu alloys are particularly critical for examination
success. Understanding the mechanistic basis of each transformation — not just memorizing facts — will
enable confident answers to 16-mark questions.

End of MTPC2005 Complete Notes | Metallurgical & Materials Engineering