Lecture 39 & 40 Diffusion (contd.

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Summary of last class: Fick’s First Law

Concentration, C
B atoms Slope = dc/dx
Area A

Distance, x

1 %& %*
!= = −)
$ %' %+

2
Summary of last class Fick’s Second Law (changing flux with x and t)

!" ! &"
=% &
!# !'

1
• ( ', # = * − ,. ./0
& 23 C

where A and B are constants dependent on t2

the particular scenario.
t1
And
x
1/& 23
' 2
./0 = 6 exp −<& =<
2 %# 5 7

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Steady and Unsteady State Diffusion

Steady State Diffusion: Flux does not Unsteady State Diffusion: Flux
change with time and distance changes with time and distance
Concentration, C

Slope = dc/dx Slope = dc/dx

C
t2
t1
Distance, x x

Both Fick’s Laws apply to both Steady & Unsteady State Diffusion
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Diffusivity & Temperature

• Experimental D data for different temperatures.

ln (D)

• It is found that
) ln (Do)
! = !# . exp − Slope = −(Q/R)
*+
where Q is named an activation energy for
diffusion (its physical significance will be discussed
later).

• Can be re-written as
ln(D) = ln(Do) − (Q/RT) 1/T

• Experimental data plotted as in the schematic on

the right.
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Some diffusion data

Self-diffusion where A (or B) atoms diffuse

in a matrix of the same atoms, e.g. Cu in
Cu.

Note that C in Fe (∝) has a much lower

activation energy than Fe in Fe (∝).

More about mechanisms later.

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Another example - carburizing of steels

• https://www.youtube.com/watch?time_continue=22&v=tEQoZvrR6qM
&feature=emb_logo 7
Analysis of Carburizing: Estimation of case depth (or carburizing time!)

• Boundary conditions:
C(x, 0) = C1 x>0
C(0, t) = Cs
"
! ", $ = & − (. *+, Block of steel with initial
2 .$ carbon content C1
Carburizing atmosphere
• Hence, A = Cs and B = Cs−C1 Carbon content Cs

• We know D from expt.

• We know our target C concentration. Carburizing
C concentration
• We set carburizing time, t. atmosphere
• From standard error function tables, the Cs
Steel
carburizing depth, x, readily estimated! t = t1
t=0 C1
• Or, we can insist for a given depth x that
has the carbon concentration C and we
can estimate the time that is required! 0 Distance, x

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How does diffusion actually occur?

• J = −D.(dc/dx)

!" !& "

=% &
!# !'

• The equations tell us that concentration changes with time and

distance.
• But how do atoms actually move around?

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 Interstitial Mechanism

• Smaller atoms occupy voids

(interstices) in crystal structures.
• They can jump to neighbouring
interstices, given sufficient
energy to push through the host
atoms.

Host atom
Interstitial atom

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But are neighbouring sites vacant?

• Yes!
• Consider steel with C sitting in octahedral sites in austenite (FCC).
• We recall there are 4 octahedral sites in an FCC cell of 4 atoms.
• Thus, 1 interstitial site per atom!
• Say we have a 2 wt.% C steel, i.e. 9 atomic % C. And 91 atomic% Fe.
• Hence, 91 interstitial sites available and only 9 occupied!
• So, availability of vacant sites is not an issue.

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So is there any barrier to Interstitial Diffusion

• Motion of an atom through the lattice

involves “pushing” other atoms a bit,
characterized by the enthalpy ∆Hm.
• Probability of an atom having enough
thermal energy to overcome the barrier
∆Hm is exp(− ∆Hm/RT).

Host atom

Interstitial atom

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 Substitutional Diffusion

CA CA

CB
CB
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Vacancy Mechanism

• But a vacancy needs to first

exist next to the atom
attempting a jump.
• n/N = exp(−∆Hf/kT).
• So, here the migration energy is
negligible, but energy is needed
to first create a vacancy (unlike
interstitial diffusion).

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Origin of Activation Energy for Diffusion
• Energy needed to push through surrounding solute (host) atoms (∆Hm)
(This is predominant in Interstitial diffusion, since vacant sites available)

• Energy needed to create an adjacent vacancy (∆Hf). The jump itself is

relatively easy (an additional term in substitutional diffusion).

So how does this relate to the experimentally found diffusion coefficient and the
activation energy Q for substitutional diffusion?
2
! = !# . exp −
34

Answer: Q = ∆Hf + ∆Hm

AND

) ∆Hf ∆01
! = !# . exp − = !# . ,-. − . ,-. −
*+ *+ *+

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Factors affecting diffusion

• Shows that temperature is

a major factor.
• Atomic size is another
factor – smaller atoms
diffuse faster!
• See C in Fe versus Fe in
Fe!

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Diffusion Paths

More free an atom, higher the
diffusion coefficient.
Qs < QGB < QL
Surface Diffusion
Lattice Diffusion
GB Diffusion

Q
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Diffusion Paths

DGB > DL

At low temperatures, bulk

(lattice) diffusion is slower.
GBs provide high diffusivity
paths.

At higher temperatures, lattice

diffusion accelerates, reducing
the difference between the two.

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Summary

We have addressed
• The driving force for diffusion.
• Physical laws of diffusion
• Factors affecting diffusion.
• Some applications in the real-world.

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Phase Transformations
• Phase Diagrams tell the equilibrium phases.
• How fast do phases transform? For example, does a liquid
instantaneously transform to solid on cooling?
• These “kinetic” issues are addressed by the study of phase
transformations.

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 Let’s take the case of freezing

• Undercooling is defined as the

(∆GV)1
temperature below the
melting point, Tm (∆T = Tm− T).

Free Energy, G
• Driving force ∆GV increases
with the undercooling.
Solid (S)
• No driving force above the
melting point. Liquid (L)
T1 Tm

Temperature

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Nucleation rate, growth rate and the overall transformation

• Nucleation rate: The number

of nuclei forming per unit
volume per unit time, I (Units: A
nuclei m−3 s−1) Solid Liquid (L)
• Growth rate: The rate at which
nuclei that are formed grow with
time (G = dr/dt) (Units: m s−1) .
• Overall Transformation Rate: r
The volume fraction of product
phase (f) formed as a function
of time, dx/dt (Units: s−1).

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Overall transformation rate, df/dt for various temperatures
Balance between
thermodynamic driving Tm
force and atomic mobility!

Growth rate peaks earlier

than the nucleation rate. "
dx/dt

Temperature
The overall transformation
rate depends on both,
!
nucleation and growth
rates.

Hence dx/dt peaks at an

intermediate temperature
between the nucleation and
growth rates. Various rates 23
 Time-Temperature-Transformation Diagrams (TTT) for solidification

Tm
• The curves approach Start
the melting point 100 %
T3
asymptotically. Temperature, T Finish
• They cannot cross
the melting line since tNose
no solidification can T2
50 %
occur above Tm.

T1

1%

Time, t 24
Summary

• We have looked at Diffusion & just a bit of what phase transformations are.
• This completes the course “Fundamentals of Engineering Materials”.
• All topics have now been covered.
• Good Luck with your further studies!

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