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Objective
Bioex.

MicrostructureProperties:II
TheKJMAEquation

Notation
Assump
tions

27-302
Lecture 5
Fall, 2002
Prof. A. D. Rollett

Derivation
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MaterialsTetrahedron
Processing
Performance

Objective
Bioex.
Notation
Assump
tions
Derivation
Plots

Microstructure

Properties

Objective
Bioex.
Notation
Assump
tions

Objective
The objective of this lecture is to introduce
the concept of phase transformation kinetics
as described by the Kolmogorov-JohnsonMehl-Avrami equation.
Part of the motivation for this lecture is to
prepare the class for a Lab on the
crystallization of glass-ceramics.

Derivation
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References

Objective
Bioex.

Notation

Assump
tions

Derivation
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Phase transformations in metals and alloys, D.A. Porter, & K.E.

Easterling,Chapman & Hall, 0-412-45030-5, 669.94 P84P2: page 289.
Kolmogorov, A. (1937). A statistical theory for the recrystallization of
metals. Akad. nauk SSSR, Izv., Ser. Matem. 1: 355.
Johnson, W. and R. Mehl (1939). Reaction kinetics in processes of
nucleation and growth. Trans AIME 135: 416.
Avrami, M. (1939). Kinetics of Phase Change. I: General Theory. J.
Chem. Phys. 7: 1103.
Avrami, M. (1940). Kinetics of Phase Change. II: Transformation-Time
relations for random distribution of nuclei. J. Chem. Phys. 8: 212.
Avrami, M. (1941). Kinetics of Phase Change. III: Granulation, Phase
Change an Microstructures. J. Chem. Phys. 9: 177.
Anderson, W. and R. Mehl (1945). Recrystallization of Al in terms of the
rate of nucleation and growth. Trans. AIME 161: 140.

Objective
Bioex.
Notation
Assump
tions
Derivation

TransformationKinetics
The kinetics of transformation are typically
described by a standard equation known as
the Kolmogorov-Johnson-Mehl-Avrami
equation, named after the individuals who
derived it.
The characteristic of the kinetics is that of
the S-curve, i.e. slow at first, then
accelerating, then decelerating.

Plots

= 1exp{kt }

Transformationkineticsareuniversal

Objective
Bioex.
Notation

The kinetics of transformation are universal.

Consider this example of the kinetics of cell growth.
High-Throughput Assay System for the Discovery Of
Anti-Bacterial Drugs

J. Bruce Pitner, 2Mark R. Timmins, 2Maurice Kashdan, 3Mandar Nagar, and 3David T. Stitt,
BD Technologies 21 Davis Drive, Research Triangle Park, NC 27709, 2BD Biosciences, Two Oak Park,
Bedford, MA 01730, 3BD Biosciences, 250 Schilling Circle, Cockeysville, MD 21030; Presented at AAPS
- New Orleans, LA November, 1999
1
1

Assump
tions
Derivation
Plots

Cellculturegrowthkinetics

Objective
Bioex.
Notation
Assump
tions
Derivation
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NotetheScurvekinetics

Objective
Bioex.
Notation

Derivations
First, a remark on derivations.
The objective of a derivation is to build a
(mathematical) bridge between basic concepts
(axioms in math) and a result (generally, an
equation, with parameters or variables
corresponding to physical quantities).

Assump
tions
Derivation
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Transformationtypes
Continuous nucleation:
nuclei added
during transformation.

Objective
Bioex.

Site Saturated:
all nuclei present
at t=0.

Notation
Assump
tions
Derivation
Plots

Cellular:
recrystallization,
for example.
Kinetics same as for
site saturated case.

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Objective
Bioex.
Notation
Assump
tions
Derivation
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KJMAnotation
The central idea in the derivation of the KJMA
equation is to focus on the increment in the (volume)
fraction transformed and to relate it to the current
value of the fraction transformed.
Notation:
f
fraction transformed
t
time
t50% time required for 50% transformation
r
radius
V volume
v growth rate (speed)
incubation/delay time
N rate of nucleation, or, density of nuclei per unit
volume

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Fractiontransformed
The relationship between volume and fraction
transformed is simple.
Fraction transformed = volume / total volume,

Objective

or,

Bioex.
Notation

f = V / Vtotal

Assump
tions
Derivation

Similarly for area (2D), line (1D), etc.

Plots

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KJMA:extendedfraction
To understand the concept of an extended fraction
transformed, imagine that each patch of new phase
can overlap with another one as they grow (ignore
the effect of impingement):

Objective
Bioex.

V2

Notation
Assump
tions
Derivation
Plots

V1

fext=(V1+V2)/Vtotal
f=(V1V2)/Vtotal

Thetruefractiontransformedcountsonlythe
actualvolumetransformed:theextended
fractioncountsallvolumeasifnoimpingement

occurs.

unionof

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Objective
Bioex.
Notation

KJMAderivation:assumption
There is one key assumption in the derivation of the KJMA
equation:
the nuclei are distributed randomly in space.
This assumption allows us to make a quantitative relation
between the true increment in fraction transformed, a fictitious
or extended fraction transformed and the current fraction:
df = dfext (1-f)

Assump
tions

Why does this work? The reason is that the volume that each
patch can grow into is decreased from the total in proportion to
Derivation
the fraction that has already transformed.
Plots

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KJMAderivation
The KJMA derivation is therefore a bridge between
the differential equation just stated and the final
equation that we use.

Objective
Bioex.
Notation
Assump
tions
Derivation
Plots

df=dfext(1f)

= 1exp{kt }

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Objective
Bioex.
Notation
Assump
tions
Derivation
Plots

KJMAderivation:1
Step 1: define the differential equation (above).
Step 2: describe the growth rate of an individual
patch/region.
Example: 3D, isotropic growth, site saturated
nucleation:
V = 4/3 r3(t) = 4/3 (vt)3
Step 3: multiply the individual volume by the
number density of nuclei, N:
fext = Vi /Vtotal = 4/3 N (vt)3
Step 4: obtain the extended fraction increment:
dfext = V/Vtotal = 4 Nv3 t2 dt

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KJMAderivation:2
Step 5: insert the extended fraction increment into
the differential equation:

Objective
Bioex.
Notation
Assump
tions
Derivation
Plots

df = dfext (1-f)
df = 4 Nv3 t2 dt (1-f)
df/ (1-f) = (4 N v3) t2dt
Step 6: collect the nucleation and growth terms into a
constant (which varies depending on the conditions
of nucleation and growth):
k = 4/3 N v3

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KJMAderivation:3
Step 7: solve the differential equation:
recognize that df = -1 * d(1-f), and that the fraction
transformed is zero at t=0, so that we are dealing
with a logarithmic solution.

Objective

- ln(1 - f ) = k t3

Bioex.
Notation
Assump
tions

Re-arrange to obtain the final result:

Derivation

Plots

generalresult

= 1 exp { kt }
? 4 3 3 ?
= 1 exp ?
Nv t ?
? 3
?

sitesaturated,
3Dgrowth

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Objective
Bioex.
Notation
Assump
tions
Derivation

KJMAsolutions
In general, the k value contains all the temperature
dependent terms because
thermal activation affects
the growth strongly through
boundary/interface mobility,
and because the nucleation
density depends very strongly
on driving force.
See P&E p269:
v = v(T) = v0 exp-(Q/RT)

Plots

In general, the exponent n in the equation is related

to the geometry of the transformation.

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nvalues
Site saturated:
1D growth 1
2D growth 2
3D growth 3

Objective
Bioex.
Notation
Assump
tions

Continuous nucleation, constant nucleation rate:

1D growth 2
2D growth 3
3D growth 4

Derivation CAUTION: you cannot always deduce the geometry of

Plots
transformation from the value of the exponent.

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People

Kolmogorov was a Russian mathematician who work is

much referenced in statistics. He worked out this
relation for the case of continuous nucleation.
Johnson was a graduate student at Carnegie Tech
Objective
under R.F. Mehl as his adviser. He studied
recrystallization in aluminum.
Bioex.
Notation Avrami was a chemist and worked out the most general
approach: his work is known in the chemical
Assump
tions
engineering world.
Derivation Porter & Easterling describe the equation but do not
explain it in detail. Other texts provide more detail.
Plots

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KJMAplots
A very useful way to analyze the kinetics of
transformation (e.g. recrystallization) is to plot the
quantity -ln(1-f) versus time on a double-logarithmic
plot. The slope of the line is then the exponent, n.

Objective
Bioex.

log(ln(1f )) =log(k) +nlog(t)

Notation
Assump
tions
[Humphreys]

Derivation
Plots

n=slope=2

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Measurement
The fraction transformed can be measured in
almost any conceivable way.

Objective
Bioex.
Notation

From micrographs
Hardness
Electrical resistivity
Optical properties
Calorimetry

Assump
tions
Derivation
Plots

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Objective
Bioex.
Notation
Assump
tions

KJMAderivation:diffusion
controlledgrowth
Step 1: define the differential equation (above).
Step 2: describe the growth rate of an individual patch/region.
Example: 3D, isotropic diffusion controlled growth, site saturated
nucleation:
V = 4/3 r3(t) = 4/3 {X0/(Xppt-Xe)}3 ({Dt})3
= 4/3 {X0/(Xppt-Xe)}3 (Dt)1.5
Step 3: multiply the individual volume by the number density of
nuclei, N:
fext = Vi /Vtotal = N 4/3 {X0/(Xppt-Xe)}3 (Dt)1.5

Derivation Step 4: obtain the extended fraction increment:

dfext = V/Vtotal = N 2 {X0/(Xppt-Xe)}3 D1.5 t dt
Plots

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KJMAderivation:diffusion
controlledgrowth
Step 5: insert the extended fraction increment into the
differential equation:
df = dfext (1-f)

Objective
Bioex.
Notation

df = 2 N {X0/(Xppt-Xe)}3 D1.5 t dt (1-f)

df/ (1-f) = 2 N {X0/(Xppt-Xe)}3 D1.5 t dt

Assump
tions

Step 6: collect the nucleation and growth terms into a constant

(which varies depending on the conditions of nucleation and
Derivation
growth):
Plots
k = 4/3 ND1.5 {X0/(Xppt-Xe)}3

KJMAderivation:diffusion
controlledgrowth

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Step 7: solve the differential equation:

recognize that df = -1 * d(1-f), and that the fraction
transformed is zero at t=0, so that we are dealing
with a logarithmic solution.
Objective

- ln(1-f) = 4/3 N {X0/(Xppt-Xe)}3 (Dt)1.5

Bioex.
Notation
Assump
tions
Derivation

Re-arrange to obtain the final result:

generalresult

= 1exp{ktn}

sitesaturated,

4
X0
1.5

= 1exp N
(Dt) 3Ddiffusion

3 X Xe
controlledgrowth

Plots

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Fixedfractiontransformed
If we need to find the time for a fixed fraction
transformed, this is easily accomplished by
manipulation of the basic equation, e.g. for 10%
and 90% transformed.

Objective
Bioex.
Notation

= 1exp{ktn} f = 1exp{ktn}

Assump
tions

0.1=1exp{ktn }

0.9=1exp{ktn }

Derivation

ln0.9 =ktn

ln0.1=ktn

ln0.91/ n

t =
k

ln0.11/n

t =
k

Plots

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Objective
Bioex.
Notation
Assump
tions
Derivation
Plots

TTTDiagrams
What is the connection between KJMA kinetics and
TTT diagrams?
Answer: once you have defined the relevant
quantities in the KJMA equation, i.e. the nucleation
density and the growth rate (and exponent) as a
function of temperature, then you can calculate the
time required to achieve a certain fraction
transformed (previous slide).
Armed with a set of times for a fixed fraction
transformed, draw the locus of points that is a curve
on the TTT diagram. Repeat for each volume
fraction of interest.