Lecture 4

Lecture 4
Diffusion in Solids
20 January 2023
16
Similarity with other physical Laws
Parameter Heat Flow Charge Flow Mass Flow

Flux Heat Flux Q Charge Flux j Mass Flux, J
(J m−2 s−1 ) (A m−2 = C m−2 s−1) (mol m−2 s−1 or kg m−2 s−1 )
Gradient Temperature gradient Electric Potential Gradient, Concentration Gradient,
dT/dx dV/dx dC/dx
Law Fourier’s Law Ohm’s Law Fick’s First Law
Q = − K. dT/dx j = − 𝝈. dV/dx J = − D. dC/dx
Material Thermal conductivity, Electrical conductivity, Diffusion Coefficient
Property K (W m−1 K−1) 𝝈 (s m−1, Ω−1 m−1) D (m2 s−1)
Year of 1807 1827 1855
Discovery
17
Diffusivity & Temperature
• Experimental D data for different temperatures.

ln (D)
• It is found that
ln (Do)
Slope = −(Q/R)
where Q is named an activation energy for

diffusion (its physical significance will be discussed
later).
• Can be re-written as
1/T
ln(D) = ln(Do) − (Q/RT)
• Experimental data plotted as in the schematic on

the right.
18
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.
19
A special case of steady-state diffusion
• Even if dc/dx is not a straight
Concentration of diffusing species

line, the flux may be equal at
all distances. dC/dx constant
• In this case, the product

dC/dx varies
D.dc/dx must be constant for
all x.
Distance
20
21
A more common situation – unsteady-state diffusion
• The concentration gradient

changes with distance.
• But D does not change so
Concentration of diffusing species

as to compensate for the
(dC/dx)1 > (dC/dx)2
change in dc/dx.
• So what does it mean for (dC/dx)1
the diffusion flux?
• As J = −D(dC/dx), the flux
(dC/dx)2
also must vary with
distance.
Distance
22
23
Volume = A Δx
Area A
Jx ∆x Jx+Δx
Which means, there is net
accumulation of the diffusing
C
species in a volume element
AΔx !
x x+∆x
J
Jx
Jx+Δx
x x+∆x
24
• Material entering ΔV at x in a time interval Δt is
25
Converting mass change to concentration change.
Concentration = mass/volume
26
Fick’s second law
• Thus, the change in flux across a

volume element results in..
• An accumulation of the diffusing

species.
• And hence, a change in the

concentration of the diffusing
species in the volume element.
• Fick’s 2nd law relates the change

in concentration with time to the
change in concentration with
distance.
𝝏𝟐 𝑪
• Curvature is defined as 𝝏𝒙𝟐 .
• Thus change in concentration
with time is related to curvature.
27
28
Both Fick’s Laws apply to both Steady & Unsteady State Diffusion
Steady State Diffusion: Concentration- Unsteady State Diffusion: :
distance profile does not change with time Concentration-distance profile changes
with time
Concentration, C
Slope = dc/dx
Distance, x
𝑑𝑐
𝐹𝑖𝑟𝑠𝑡 𝐿𝑎𝑤 𝐽 = −𝐷
𝑑𝑥
29
Solution is given as
𝜕𝐶 𝜕 𝐶
=𝐷
𝜕𝑡 𝜕𝑥
where A and B are constants dependent on the particular scenario.
And
30
More about the error function
• Bell shaped distribution.

• For η ranging from 0 to ∞, )
the area under the curve is
√π/2.
• For η ranging from 0 to −∞,
the area under the curve is
−√π/2. 𝑥
• Thus, 0 𝜂=
2 𝐷𝑡
erf (0) = 0
/
erf (∞) = 1
erf (−∞) = −1
31
32
Another example - carburizing of steels
• https://www.youtube.com/watch?time_continue=22&v=tEQoZvrR6qM&feature=emb_logo
33
Analysis of Carburizing: Estimation of case depth (or carburizing time!)
• Boundary conditions:
C(x, 0) = C1 x>0
C(0, t) = Cs
𝑥
𝑐 𝑥, 𝑡 = 𝐴 − 𝐵. 𝑒𝑟𝑓 Block of steel with initial
2 𝐷𝑡 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
35

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Parameter Heat Flow Charge Flow Mass Flow

• Experimental D data for different temperatures.

where Q is named an activation energy for

• Experimental data plotted as in the schematic on

Self-diffusion where A (or B) atoms diffuse

Note that C in Fe ( ) has a much lower

More about mechanisms later.

• Even if dc/dx is not a straight

Concentration of diffusing species

• In this case, the product

• The concentration gradient

Concentration of diffusing species

• Thus, the change in flux across a

• An accumulation of the diffusing

• And hence, a change in the

• Fick’s 2nd law relates the change

where A and B are constants dependent on the particular scenario.

• Bell shaped distribution.

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