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Solid State Diffusional Transformations

The document discusses diffusional transformations in solids that occur via thermally activated atomic movements. It describes different types of phase transformations such as precipitation, eutectoid, ordering, massive, and polymorphic. It then focuses on the mechanisms of homogeneous and heterogeneous nucleation during diffusional transformations. Homogeneous nucleation requires overcoming a large energy barrier, so heterogeneous nucleation is more common, occurring at defects like dislocations and grain boundaries. Precipitation in age-hardening alloys is used as an example, where transition phases like GP zones form initially before the equilibrium phase.

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25 views30 pages

Solid State Diffusional Transformations

The document discusses diffusional transformations in solids that occur via thermally activated atomic movements. It describes different types of phase transformations such as precipitation, eutectoid, ordering, massive, and polymorphic. It then focuses on the mechanisms of homogeneous and heterogeneous nucleation during diffusional transformations. Homogeneous nucleation requires overcoming a large energy barrier, so heterogeneous nucleation is more common, occurring at defects like dislocations and grain boundaries. Precipitation in age-hardening alloys is used as an example, where transition phases like GP zones form initially before the equilibrium phase.

Uploaded by

zain
Copyright
© All Rights Reserved
We take content rights seriously. If you suspect this is your content, claim it here.
Available Formats
Download as PDF, TXT or read online on Scribd

Diffusional

Transformations
SOLID STATE
Introduction

 Phase transformations in solids – by


thermally activated atomic
movements
 Different types of transformations –
divided into following groups
 Precipitation
 Eutectoid
 Ordering
 Massive
 polymorphic
Introduction…

 Precipitation
α’  α + β
 Eutectoid
α+β
 Ordering
α (disordered)  α’ (ordered)
 Massive
βα
 Polymorphic
Single component system
Homogeneous Nucleation…
G  VGV  A  VGS

 Equation similar to that derived for solidification


 For liquid-solid interface,  is roughly the same for all
interfaces

 Nucleation in solids
  varies
 very low for coherent interfaces
 high for incoherent interfaces
 A term should be replaced by a summation over all surfaces
of the nucleus, i.e.

 i Ai
Homogeneous Nucleation…
 Ignoring variation of  and Effect of the misfit
assuming spherical nucleus strain energy is to
reduce the effective
G   r GV  GS   4r 2
4 3 driving force for
3 transformation.

 Differentiation yields

2
r 
*

GV  GS

16 3
G 
*

3(GV  GS ) 2
Homogeneous Nucleation…
 Concentration of  G *

critical-sized nuclei C  C0 exp  
* hom

 kT 
C0 is the number of atoms per unit volume

 If each nucleus made supercritical


at a rate f per second, then Nucleation
Rate N hom  fC *

 This depends on surface area of the


nucleus & the rate of diffusion
Gm is activation energy for atomic
 Gm   G *
 migration
N hom  C0 exp    exp   
 kT   kT 
 is a factor that include
vibrational frequency of atoms
and area of critical nucleus
Driving Force for Precipitation

 Alloy X0 is solution treated at


T1 and cooled rapidly to T2
 Supersaturated with B – will try
to ppt β

 After complete
transformation, the free-
energy will decrease by ΔG0
 ΔG0 is the total driving force for
transformation
Driving Force for Precipitation
 If small amount of material with
nucleus composition (XBβ) is
removed from the α phase
 Then total free energy of the system
will decrease by ΔG1 (per mole of β
removed)

G1   A X A   B X B
ΔG1 is represented by point P

 Atoms are then rearranged into β


crystal structure
 Per mole of β formed

   
G2   A X A   B X B
ΔG2 is represented by point Q

 Driving force for Nucleation

Gn  G2  G1


Homogeneous Nucleation…
 Volume free energy
decrease associated with
nucleation event is
therefore,

Gn
GV 
Vm
 For dilute solutions

GV  X
where
X  X 0  X e
Homogeneous Nucleation…
Homogeneous Nucleation…
G  VGV  A  VGS

 Assumed – nuclei are spherical with


equilibrium composition & structure
 However, in practice, nucleation will be
dominated by whatever nucleus has minimum
activation energy barrier.
 Most effective is to form nucleus with smallest
total interfacial energy
 This will mostly dominate nucleation

 Incoherent nuclei have very high


energy – virtually impossible
Homogeneous Nucleation…
G  VGV  A  VGS

 Coherent nuclei with orientation


relationship with matrix – reduced
energy
 Coherent nuclei – high strain energy
 Lowering of interfacial energy compensates for
the increase in the strain energy
Interface Coherency
Interface
Coherency
Incoherent Interface
Homogeneous Nucleation…

 Homogeneous nucleation can occur


in very few systems
 e.g. Cu-Co system
 Both are FCC with only 2% difference in lattice
parameter
 Very low coherency strains

 Ni-Superalloys
 Precipitation of Ni3Al

 Most other examples are limited to metastable


phases (usually GP zones)
Heterogeneous Nucleation
 Nucleation is mostly heterogeneous
 Suitable nucleation sites
 Defects like excess vacancies, dislocations,
grain boundaries, stacking faults, inclusions
and free surfaces
 Creation of a nucleus results in the destruction
of a defect – some free energy (ΔGd) will be
released
 This will reduce the activation energy barrier

Ghet  V GV  GS   A  Gd


Nucleation on GBs
 Optimum embryo shape would be one that
minimize total interfacial free energy

Misfit strains
ignored

 
cos   G  VGV  A   A 
2 

Gd
Nucleation on GBs… cos  
 
2 

 Critical radius of the


spherical caps
2 
r 
*

GV
 Activation energy
barrier

Ghet
* *
 *  S  
Vhet
Ghom Vhom
*

where

S    2  cos  1  cos  


1 2

2
Nucleation on GBs…
 If matrix and precipitate are
sufficiently compatible
 Low energy (coherent) facets can be formed
 Nucleus may have orientation relationship with
one of the grains
Rate of Heterogeneous Nucleation

 In order of decreasing
G*
 Homogeneous sites
 Vacancies
 Dislocations
 Stacking faults Overall rate of
 Grain boundaries / transformation
interphase boundaries
also depends on
Free surfaces

the relative
concentration of
these sites
Rate of Heterogeneous Nucleation…
 If concentration
of heterogeneous  Gm   G * 
N het  C1 exp    exp   
sites is C1 per unit  kT   kT 
volume, then Nuclei m-3 s-1
Rate of Heterogeneous
Nucleation…
 Relative magnitudes N het C1  Ghom
*
 Ghet
*

of heterogeneous  exp  
and homogeneous N hom C0  kT 
volume nucleation
rates Although G* is always
 (Differences in  smallest for heterogeneous
and Gm are not so nucleation , the factor C1/C0
important and so must also be taken into
ignored.) account
i.e. the number of atoms on the
heterogeneous sites relative to
the number of atoms within
the matrix
N het C1  Ghom
*
 Ghet
*

 exp  
N hom C0  kT 

 At small driving forces,


heterogeneous nucleation is always
dominant
 At large driving forces, homogeneous
nucleation may also occur because of
the C1/C0 ratio
Precipitation in Age-Hardening
Alloys
 Al-4Cu (1.7
at%) alloy
 α-phase
 θ-phase
Precipitation in Age-Hardening
Alloys – Transition Phases
 GP zones
 Fully coherent
 Very low interfacial energy
 Two atomic layers thick
 10 nm diameter
Precipitation in Age-Hardening
Alloys – Transition Phases…
 GP zones are
formed as first
ppt during low
temperature
aging of many
technologically
important alloys.
Precipitation in Age-Hardening
Alloys – Transition Phases…
 Precipitation  o  1  GPzones   2   "  3   '   4  
process
 θ” are fully Go  G1  G2  G3  G4
coherent plate-
like ppts
 Visible through
coherency-strain
fields
 Orientation
relationship with
the matrix

001 " 001


100 " 100
Precipitation in Age-
Hardening Alloys

 Activation
energy
barrier

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