Diffusional Transformations

1-phase

Many-phases

C0 Fixed bulk composition

 '  metastablesupersaturated solid solution
Precipitation  '  

Eutectoid    

Diffusional
Ordering  (disordered )   '(ordered )
Transformations

Original phase decomposes to one or

Massive   more new phases which have the same
composition as the parent phase but
different crystal structures

Polymorphic  crystal 1   crystal  2

Precipitation  '    

Eutectoid System
Eutectic System

Peritectic System
Eutectoid    
Ordering  (disordered )   '(ordered )
Massive  
Polymorphic  crystal 1   crystal  2
Precipitation of Ferrite from Austenite

 Fe-0.15wt% C → partially allowed to transform to Ferrite a various T below A3

 Ferrite
40s

910oC A3
Acm
a 800oC
A3
b 750oC
723oC 150s
A1
9s
c 650oC 2s

T
d 550oC

0.15 % 0.8 %
Wt% C →
800oC
Ferrite nucleates on Austenite grain boundaries and
grows with a blocky appearance
→ Grain Boundary Allotriomorphs Small T

Curved interfaces → incoherent

Faceted interfaces → semicoherent

150s

750oC 40s
Larger undercooling – Ferrite grows as plates from GB
→ Widmannstätten side-plates Large T
Irrational habit planes

Ferrite can also nucleate within the  grains

heterogeneously at inclusions and dislocations
→ equiaxed at low undercoolings and plate-like at higher
undercoolings
650oC 9s
Widmannstätten side-plates → become finer with larger
undercooling

550oC 2s
Very Large undercooling – Ferrite grows as needles GB
→ Widmannstätten needles
Cellular Precipitation (Discontinuous Precipitation)
 Grain boundary precipitation may also occur by cellular precipitation
(apart from Allotriomorphs, Widmannstätten side plates & needles)
 Main Feature → boundary moves with the tip of the precipitates
 The mechanism by which GB ppt. develops into cellular precipitation is system specific
 Called discontinuous precipitation as the composition of the matrix changes
discontinuously as the cell front passes
 (Continuous precipitation- not cellular- occurs throughout the matrix and the matrix
composition changes continuously with time

 ' (higher solute concentration)   (lower solute concentration)  

 ' (higher solute concentration)   (lower solute concentration)  

Partitioning of the solute ahead of

the moving front by GB diffusion
 Original position of GB
New position of GB
Grain-II

Grain-I
Eutectoid Transformations Pearlite in Fe-C alloys     Fe3C
Nucleation at GB

Low undercooling (below A1)

Small number of nuclei form which grow without interference

Large undercooling (below A1)

High nucleation rate → Site saturation along GB
 Orientation Relation: Kurdyumov-Sachs
Branching mechanism

Proeutectoid cementite

Orientation Relation:
Kurdyumov-Sachs

(100)C (111)
Pearlite colony (010)C (110)

(001)C (112)
 The development of Pearlitic microstructure requires cooperative growth of
Ferrite and Cementite
 If this cooperation is not established then the resulting microstructure is non-
lamellar → Degenerate Pearlite
Massive Transformation
Cu-Zn System


Massive Transformations
 The type of transformation that occurs in cooling (e.g. Cu-38 at% Zn alloy)
depends on the cooling rate
 Slow cooling → transformation at small undercoolings  equiaxed 
 Faster cooling → transformation at lower T  Widmannstätten  needles
 Even faster cooling (brine quench) → no time for diffusion  Transformation
of  → without change in composition (MASSIVE TRANSFORMATION)
  richer in Cu  growth of  requires long-range diffusion of Zn away from
advancing / interface
 MASSIVE Tr.
 Nucleation at GB and rapid growth into 
 Irregular appearance
 No change in composition  Only short range jumps (thermally activated)
across the interface (/) (no long range diffusion required)→ fast growth rate
(thermally activated migration of incoherent interfaces → diffusionless civilian)
 Separate transformation curve (in TTT & CCT diagrams)
 ~ to GB migration during recrystallization → but driving force v.high
 Phase Diffraction
 FCC
- Cu-Zn A2, BCC solid solution
’ B2, CsCl
- Cu5Zn8 D82, -brass
- CuZn3 B2, CsCl
- Cu-Zn A3, Mg, HCP
If Ms below RT → metastable 


Massive


G > G 

G = G

G < G 

Free energy composition curves (schematic) for  and  in the Cu-

Zn system for four temperatures

But, usually observed in single phase region

Massive Tr. can also occur in Fe-C system

V.High cooling rate will

produce Martensite
Martensitic Transformations
Points about Martensitic transformations

 Occur at high supersaturations, without change in composition

 No long range diffusion → Movement of atoms a fraction of the inter-atomic
distance
 Nearest neighbour configuration remains unchanged
 Cooperative movement of a large group of atoms → transformation proceeds at
the speed of sound in the material
 Thermal activation does not play a role in the growth of the martensitic phase
Thermal activation may play a role in the nucleation of martensite
 Usually martensite crystals nucleate and grow across the whole grain (in some
cases this growth is a function of temperature)
 In some cases the transformation occurs over a period of some time (due to
thermally assisted nucleation)
 Martensitic crystals have a specific orientation relationship (OR) with the parent
phase
 Planes of the parent lattice on which Martensitic crystals from → Habit planes
(irrational Indices)
 Interface between Martensite and parent phase → Coherent or Semi-coherent
Effect of plastic deformation on Martensitic transformations

 At a given temperature (between Ms and Mf) the fraction transformed ↑ with plastic
deformation (in some cases elastic stress also has a similar effect)
 With prior plastic deformation the transformation temperature can be increased to Md
Characteristic of Martensitic transformations
 Shape of the Martensite formed → Lenticular (or thin parallel plates)
 Associated with shape change (shear)
 But: Invariant plane strain (observed experimentally) → Interface plane between Martensite and
Parent remains undistorted and unrotated
 This condition requires
 1) Bain distortion → Expansion or contraction of the lattice along certain crystallographic
directions leading to homogenous pure dilation
 2) Secondary Shear Distortion → Slip or twinning
 3) Rigid Body rotation →

Surface deformations caused by the Martensitic plate

 But shear will distort the lattice!

Slip Twinning

Average shape
remains undistorted
How does the motion of dislocations lead to a macroscopic shape change?
(From microscopic slip to macroscopic deformation  a first feel!)

Step formed
Dislocation
when dislocation
formed by
leaves the crystal
pushing in
a plane  
b
Net shape change
 High Magnification shows twinned structure
 Minimum strain energy condition for martensitic transformation leads to
lenticular shape → shape obtained in most martensitic transformations
 Plates formed a given temperature have similar r/c ratio

Lenticular Martensite (Fe-Ni-C)

Schematic of Martensitic Transformation with decreasing temperature

 Forms when Ms is high (at high temperature)
High Magnification shows high dislocation density
(~ 1015 m/m3)

 Second most common martinsitic morphology found in low alloy low carbon
steels
 Thin martensite plates (laths) have dimensions in the range: 0.3 x 4 x 100 
 Habit plane of laths ~ 5 from the (111) plane of austenite
 Laths form clusters, wherein members of a cluster have same habit plane, OR
Lath Martensite and deformed shape

Other martensitic morphologies are variations of lenticular morphology:

 Fe-31% Ni alloy: plates are segmented
 Fe-8%Cr-1%C: sideplates form from main plate
 Martensitic plate may have a midrib with high transformation twin density
 Fe-Ni-C alloys: thin plate martensite (variant of lenticular morphology where sides of the
plate are paralle)
 Fe-Ni-C alloys: butterfly martensite (number of plates grow from a single point in
different directions)
 Single crystals (Au-Cd, Cu-In): under a thermal gradient martensite nucleates at the
colder end of the crystal- single transformation front/interface sweeps across the crystal
with lowering of temperature- with product being a single martensitic plate
 Low C: Lath morphology

Medium C: Plate Fe-Ni: Plate

morphology morphology
Athermal

 Fraction transformed = f(T) only (between Ms and Mf)

 At a given T a certain number of nuclei form which grow at the speed of sound
in the material across the whole grain
 The number of nuclei forming increases with decreasing T  more
transformation
 Ms and Mf temperatures increase with increasing grain size
 %Martensite
Isothermal Transformation diagram for
Martensitic Transformation in Fe-
Isothermal Ni-Mn alloy

 Fraction transformed at a given T (between Ms and Mf) = f(t)

→ observed in some alloys at subzero T
 At the low T thermal activation of growth does not occur (as usual fast)
 “t effect” is due to small thermal activation required for nucleation of Martensitic
plates and autocatalytic effect
 Rate of transformation at a given T ↑ with ↑g grain size (fewer nucleation events
give more transformed fraction)
 %Martensite
Burst

 At some T (Mb) → sudden transformation of a large fraction of parent to

Martensite (often with a acoustic effect-click)
 % transformed during the “burst” → few-over 50%
 The ‘burst’ can be thought of as an extreme form of autocatalytic effect
 Remaining transformation is completed at →  lower T  longer t
 OR: KS
Branching mechanism

Semi-coherent
low energy interface

Incoherent mobile interface

Proeutectoid cementite

(100)C (111)

Pearlite colony
(010)C (110)

(001)C (112)
Cu-Zn System




Massive