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APL 102
C2
Concentration →

Cavg
↑t

A B
C1
x →

Diffusion in Crystalline Solids

Concepts: diffusion couple; diffusivity; extrinsic and intrinsic diffusion; case hardening

Lecture 25
 Recap
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Diffusion – Mass flow process by which species change their position relative
to their neighbors.
Diffusion driven by: Thermal energy and concentration gradient

Mathematical models to describe diffusion

Flux (J) proportional to 100%
dn dc
Fick’s Ist law in 1D:   DA concentration gradient.
dt dx Flux (J) →Flow/area/time 0
Concentration Profiles
Steady state diffusion: J ≠ f(x,t) [Atoms/m2/s]

x
 c   2c
Fick’s IInd law:    D 2
 t  x
Jx Jx+x Non steady state diffusion: J = f(x,t)
 Solution to Fick’s Second Law
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 c   2c  x 
 D 2 c( x, t )  A  B erf  
 t  x  2 Dt 


erf   
2
    exp  u 2 du
0

Exp( u2) → Area

0  u →
 Properties of Error function
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 Erf ( ) = 1
 Erf (-) = -1
 Erf (0) = 0
 Erf (-x) = -Erf (x)

If required we can provide error function table

 Error function table
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Question for thought

How to experimentally determine the D?

 Diffusion couple
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Cu-Zn & pure Cu welded together and heated to high temperature

t2 > t1 | c(x,t1) t1 > 0 | c(x,t1) t = 0 | c(x,0)
C2
Concentration →

Cavg Cavg (at junction) = ??

↑t
Constant (≠f(t))
A B
C1
x →

 C(+x, 0) = C1  A = (C1 + C2)/2 Profile of concentration can be

 C(x, 0) = C2  B = (C2 – C1)/2 deduced at any time of interest for one T
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Question for thought

Why temperature is critical for diffusion process?

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Dependence of D on T and C (Concentration):

Experimentally and theoretically
 Diffusion and temperature
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 Diffusivity increases with T

pre-exponential [m2/s] (see Table 5.2, Callister 6e)
activation energy
 Q  [J/mol],[eV/mol]
diffusivity D  Do exp  d  (see Table 5.2, Callister 6e)
 RT 
gas constant [8.31J/mol-K]

What type of equation is this?

What sort of graph/plot needed to obtain

the activation energy and diffusivity?
 Diffusion and temperature
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 Experimental Data:
1500
1000

600

300
T(C) D has exponential dependence on T
10-8 Recall: Vacancy does also!
C
in

D (m2/s) Ci Dinterstitial >> Dsubstitutional

-

n
Fe

- Fe
C in -Fe Cu in Cu
C in -Fe Al in Al
10-14 Fe in -Fe
Zn

Fe in -Fe
Fe

in Cun -

Al
Cu in Fe
F

Zn in Cu
in
in
ei e

Al
 -F

10-20
Cu

0.5 1.0 1.5 2.0 1000K/T

 D0 and Q values
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 Diffusion and temperature
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log D

Bulk Diffusivity

Grain Boundary
Diffusivity
TC 1/T
 At low temperature, grain boundary diffusion dominates
 At higher temperatures, bulk diffusion dominates
 Blue line depicts the overall behaviour
 Diffusion and temperature
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Intrinsic Extrinsic (due to

(due to bulk extrinsic defects
log D

or intrinsic created by impurities)

defects)

TC 1/T
In ionic solids such as NaCl,
 At low temperatures, diffusion due to high extrinsic defect concentration (due to impurities
such as CaCl2) dominates
 At higher temperatures, bulk defects outnumber the defects due to impurities and bulk
diffusion dominates.
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Atomistic mechanisms of Diffusion

What kind of atomic diffusion

mechanisms are possible?
 Interstitial diffusion
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1. Interstitial Mechanism

e.g. C in Fe

Thermal energy provides oscillations for atoms to jump in all directions, it

is the gradient in concentration that decides the direction
 Substitutional diffusion
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2. Vacancy Mechanism

e.g. B or P in Si

 Applies to substitutional impurities

 Atoms exchange with vacancies 3. Direct interchange
 Rate depends on:
-- number of vacancies 4. Ring mechanism
-- activation energy to exchange
 Other Diffusion Processes
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 Grain Boundary Diffusion

 Defect Diffusion
 Surface Diffusion

Qsurface< Qgb < Qlattice

 Diffusion Application
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 Surface is often the most important part of the component, which is prone to degradation

 Surface hardening of steel components like gears is done by carburizing or nitriding

Diffuse carbon atoms into the host

iron atoms at the surface
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Question for thought

How does the C or N atom diffuse in the iron (Fe)

crystal?

Interstitial diffusion, Example is a case hardened gear

 Diffusion Application
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 Doping Silicon with P for n-type semiconductors:

 Process:
1. Deposit P rich layers on surface

silicon

2. Heat it
3. Result: Doped semiconductor P regions.

silicon
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Question for thought

Do the phase change or transformation always happen

through diffusion process?

No. Diffusionless transformations do happen

Example: Martensitic transformation
 Announcement
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 Quiz 1 Exam Schedule:

Date: 27th September (Tomorrow)
Locations: LH – 108 (Monday’s and Tuesday’s group)
LH – 111 (Thursday’s and Friday’s group)
Time: 5:30 pm – 5:50 pm

 Minor II Syllabus: After minor I topics (i.e. from Thermodynamics) to

tomorrow’s (27th September) lecture topic (Deformation behaviour)

 Minor II Exam Schedule:

Date: 06th October (Friday)
Location: LH – 121 & LH – 310
Time: 2:30 pm – 3:30 pm