Phase Transformations:
Nucleation Theory
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Today’s topics:
• Phase transformations: general context
• Continuous vs. discontinuous transformations
• Nucleation
•Interplay between surface and volumetric energy
terms
•Effect of coherency strain energy on nucleation in
solids
•Heterogeneous nucleation at surfaces and grain
boundaries
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Transformations: General Aspects
• Transformations occur in systems that are
not in equilibrium, e.g., precipitation can
result from cooling a single phase to a
temperature where it is supersaturated.
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Transformations: General Aspects, cont’d
• Systems away from equilibrium behave in
fundamentally different ways, depending on whether
they are in a unstable or in an metastable state.
Consider binary solution, initially homogeneous,
that undergoes an infinitesimal composition
variation such that half the solution increases X by
ΔX and half decreases by ΔX
At X, the homogeneous
solution is metastable;
At Y, the homogeneous
solution is unstable
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Transformations: General Aspects, cont’d
• Nucleation occurs in metastable systems and it
involves the energetics and kinetics of the formation
of a stable cluster that, once formed, can grow
continuously to macroscopic size.
• The construction
shown gives the driving
force for nucleation
of β phase from a super
saturated solution at Xα
(“tangent-to-curve” con
struction.)
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Transformations: General Aspects, cont’d
• The extra free energy associated with the
nucleus/matrix interface serves as a barrier to
nucleation.
• The excess free energy per unit area, γ, is defined as
the work to create a unit area of interface:
#"E &
% ( =)
$ "A 'S,V ,Ni
• In fluid systems, γ is numerically equal to the force
per unit length acting along the perimeter of the
interface, in!the plane of the interface
F
"=
L
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!
Transformations: General Aspects, cont’d
• In crystalline solids, structure of the nucleus/matrix
interface plays a role in determining its energy.
Because of the low value of γ, new phases often start
out as coherent at the nucleation stage.
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Transformations: General Aspects, cont’d
• In crystalline solids, the molar volumes of the
nucleus and matrix phases can differ, and this may
arise in elastic strain energy that also acts to impede
nucleation.
• The elastic strain energy is hard to model. It
depends on the transformation strain (shape
change), the nucleus shape, elastic constants of the
nucleus and matrix, etc.
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Nucleation: critical size and free energy
• The free energy change of forming a nucleus of
volume V and surface area A is
"G = ("gB + "g# )V + $A
• For a spherical nucleus in the absence of strain
energy
! 4 3
"G = ("gB ) #r + $ 4 #r 2
3
"#G 2& 16 '& 3
= 0 $ rc = % and #Gc = 2
! "r #g B 3( B)
#g
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!
Nucleation: kinetics
• Number of particles vs. time for a precipitation
process typically looks like
Region I is called the transient nucleation regime
Region II is the steady-state nucleation regime
Region III shows decreased nucleation at lower "fB
Revion IV is the coarsening regime
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Nucleation: kinetics
• In the steady-state nucleation regime, the steady-
state nucleation rate J is the number of nuclei
forming per unit volume per second
% $Gc (
J = Z"c N exp'# *
& kT )
Z is the Zeldovich non-equilibrium factor, ~ 0.1
βc is!a transport coeff. to bring atoms to nucleus
N is the number of sites available for nucleation
• ΔGc plays a critical role in determining the nucleation
rate
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Nucleation: kinetics
• ΔGc plays a critical role in determining the nucleation
rate
% $Gc (
J = Z"c N exp'# *
& kT )
Taking reasonable values for the parameters in this
relation, and making an educated guess about what
the !
minimum detectable nucleation rate would be,
gives a useful criterion for when nucleation by a
particular mechanism is possible:
"Gc # ~ 76kT
If this condition is not met, nucleation will take so
long as to be effectively unobservable.
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! 12
Homogeneous vs. heterogeneous
nucleation
• Homogeneous nucleation can occur anywhere in a
system; if there are N atoms or molecules, the
number of sites available is N.
• Special sites in the material such as surfaces,
internal interfaces, dislocations, etc. can act to
“catalyze” nucleation by effectively lowering ΔGc.
• Although ΔGc is smaller for heterogeneous
nucleation, the number of heterogeneous sites
available it is small compared to the total number of
sites in the material that could be sites for
homogeneous nucleation. Thus, homogeneous and
heterogeneous nucleation compete with each other.
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Heterogeneous nucleation at surfaces
"R 3
V=
3
( )
2 # 3cos$ + cos 3 $
A = 2 "R 2 (1# cos$ )
B
' 4 "R 3 * 3
2 2 # 3cos $ + cos $
%G = ) %gB + 4 "R & ,
( 3 + 4
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!
Heterogeneous nucleation at surfaces,
cont’d
% 16 #$ 3 ( 2 + 3cos, + cos 3 , homog
% 2 + 3cos , + cos 3 (
,
"Gc = ' 2*
= "Gc ' *
& 3"gB ) 4 & 4 )
• Effects of contact angle θ; limiting values of 0 and π
!
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