HEAT TREATMENT

AND SURFACE Evolution of

HARDENING Microstructure in
(MSE 671A) Engineering Materials
Engineering
Components Components
Where Surface Matters
 CLASSIFICATION OF ENGINEERING MATERIALS
BOHR ATOM BONDING ATOMIC AGGREGATE

1
n=3 2

IONIC BONDING COVALENT METALLIC

electron H
CH4
+ Coulombic - H
C
H

Attraction
Ceramics (Ionic/Covalent, Non-D)
Non-directional bonding
Very large bond energy
large Tm, large E, small a
H
Polymers (Covalent/Ionic, D) Metals (Metallic, Non-D)
Secondary bonding dominates Variable bond energy
small Tm, small E, large a moderate Tm, E, and a
 Evolution of Macro/Microstructure
MACROSTRUCTURE MICROSTRUCTURE

Nucleation and Growth

process (1st order)
Diffusive transformation
liquid to solid
Three zones: Chilled,
columnar-dendritic,
equi-axed zone
Crystalline aggregate
Macro-defects
Crystal Defects
 MATERIAL PROCESSING

Melting/Casting
Laser Processing

win

Powder Processing Compaction Extrusion Drawing

 Non-equilibrium Processing

RSP: Melt Spinning ECAP/ECAE

Mechanical Alloying/Milling
Thermodynamic Constraint : Equilibrium

Random

Clustering

Ordered
Kinetic Constraint : Diffusivity

100%

0
Concentration Profiles

Q
Diffusivity D Do exp - d
=
RT
 Periodic and Aperiodic Basic
Aggregate of Atoms Crystallography

(a) Scattering by an atom

Comparative X-ray scattering by (i)
(b) Diffraction by a crystal crystalline solid, (ii) amorphous solid or
liquid and (iii) mono-atomic gases
 The fourteen
Crystal Bravais lattices
or Bravais Lattices Common Bravais Lattices of
Metallic Materials

FCC

BCC

HCP
 Unit Cells of Compound Crystals

NaCl (AB) CsCl (AB) ZnS (AB)

BaTiO3 (ABX3) Diamond (C)

CaF2 (AB2)
 Silicate (SiO44-) Structure Network of Tetrahedron

Amorphous Crystalline
 POLYMER CHAIN
COPOLYMER
Linear
Branched Random

Alternate

Cross-linked Networked Block

Graft
 Spherullite

Chain
folding

Unit Cell

Nucleation and
Growth of
Spherullite
Phase Rule:
For a system of P phases and C components composition terms:
Degree of freedom, F = (C - 1) P + 2 (T , P) = C + 2 P

Stability criteria: DG = DH - TDS

Regular Solution: Solutions that follow
HM = XA XB = Nav z XA XB (= RT XA XB)
G = XAGA + XBGB + XAXB + RT (XA ln XA + XB ln XB)
GM = XA XB + RT (X ln XA + XB ln XB)

Chemical potential:
dG'
A =
dn A T, P,
 Phase Diagram and Gibbs Energy Diagram
Scope: Definition, Utility, Classification, Types, Information, Lever rule
1. Isomorphous
 Case I: < O Case II: > O

GM is made further negative. GM is made positive in a given

A-B bonds preferred leading XB range for large A-A, B-B
to formation of intermetallic bonds preferred leading to
phase/compound spinodal decomposition
2. Influnce of DH on Phase Diagrams and Aggregate

Case I: Positive DH
HM > O
A -A or B-B bonding
is preferred
Hs< H1

Case II: Negative DH

HM < O
A B bonding
is preferred
Hs> H1
 Liquid to Solid Phase Transformation
Melting is a usual route for developing
metals and alloys because: (a) solubility
is usually unrestricted in liquid state, (b)
mixing is faster due to convection and
faster diffusion, (c) homogeneity in
composition is easy to achieve, and (d)
subsequent processing (casting,
shaping, joining, etc) is easier from
molten state
Solidification:
Solidification (from liquid state) Melting
(Non-crystalline Crystalline) (Crystalline Non-Crystalline)
Applications:
Ingot casting, foundry casting, continuous casting, single crystal growth, direct
solidification, zone refining, fusion welding

Nucleation
Homogeneous Heterogeneous
(Everywhere probable, Large DT) (Probable at specific sites, Small DT)
Melting and Casting Industrial Practice
Thermodynamics of Homo versus Hetero-Nucleation
Heterogeneous

When
= 100, S() ~ 10-4
= 300, S() ~ 0.02
LDT = 900, S() ~ 0.5
DGV =
Tm Homogeneous
r* f (MS) but r* = f (DT)
DG*het << DG*hom
Kinetics of Homo versus Heterogeneous Nucleation

Heterogeneous nucleation
starts earlier (lower DT)
but enjoys similar kinetics
 Interface Stability/Morphology due to Heat Flow Direction
I. Heat flow into solid (conduction):
Planar Front Solidification

(a) (b) (c)

II. Heat flow into liquid (convection):

Non-Planar Front
Solidification
 Conditions and Mechanism for
Dendritic Growth

As DTo = Tc Tr

r = rmin when DTr = DTo = Tm T, which is Therefore,

equivalent to: r* = 2Tm/(LvDTo) DTr To(r*/r)
Columnar to Dendritic Morphology
Iron-Cementite Diagram
 Moving Boundary phase transformations in steel
Upper Bainite Lower Bainite

Widmanstatten

Eutectoid

Eutectic

Massive
The Kinetic Diagrams TTT and CCT

Pearlite Bainite

Plate
Martensite

Lath
Microstructure