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Grain boundary diffusion

Diffusion
direction

d
 For the sake of explanation let us consider rectangular grains of width d and
grain boundary of width δ.
dC
 Flux because of lattice diffusion J l = − Dl
dx
dC
 Flux because of grain boundary diffusion J g = − Dg
dx
 The effective flux can be written as (δ<<d)
dJ l + δJ g dJ l + δJ g  δ  dC dC
J eff = ≈ = − Dl + Dg  = − Deff
d +δ d  d  dx dx

 It can be written as Deff = (1 − g ) Dl + gD g


g is the fraction of grain boundary area
g 2 > g1
Since activation energy for grain
boundary diffusion is always less than
Dg
the activation energy for lattice
Deff
diffusion, Dg > Dl . Diffusion rate through
Deff2 grain boundary is always higher.
1
Deff
Contribution from grain boundary is
actually the diffusion rate multiplied by
Dl g 2 Dg fraction of grain boundary area .
g1 Dg

1/T

 There will be a sharp change in the slope when diffusion process transforms
from mainly lattice diffusion controlled to the diffusion process mainly controlled
by grain boundary diffusion.
 Transformation temperature will depend on the relative area of grain boundary
Note: In practical examples, materials are generally polycrystalline and we always
measure effective diffusion coefficient only, not separately, lattice or grain
boundary diffusion coefficients.
 There could be mainly three different situations because of difference between the
lattice and the grain boundary diffusion.

 If grains are relatively smaller or there is not much difference in the diffusion rates,
diffusion length in the grain boundary and the lattice will not be much. This is Type A
diffusion.
Diffusing species
Dl t
Dl t
Dg t Dg t
d
Dg t

 In type A kinetics, diffusion length because of lattice diffusion Dl t is much higher


than grain width, d. We can write Dl t >> d

 Diffusion coefficient in type A is expressed in terms of effective diffusion


coefficient. In two dimensional case, we can write Deff = gDg + (1 − g )Dl , where, g is the
total cross sectional area of grain boundary
 If grains are relatively bigger or there is reasonable difference in the diffusion rates,
diffusion length in the grain boundary and the lattice will be reasonable. This is Type
B diffusion.
 Type B kinetics is observed, when grain boundary spacing is larger compared to the
diffusion length by lattice diffusion. On average, it will meet the condition 100δ < Dl t < d / 20

 If grains are very big or there is very high difference in the diffusion rates, in
relatively small time, diffusion of elements will happen through the grain boundary only.
This is Type C diffusion.

 Type C kinetics is found, when diffusion length because of lattice diffusion is much
smaller than the grain boundary width. That means when 20 Dl t < δ

Note: Type A and C obey Fick’s law and parabolic growth is found (that maximum is
diffusion length is proportional to t 1/ 2 ). However, type B does not follow Fick’s law and
maximum diffusion length is found to be proportional to t 1/ 4 .

 In type A the overall flux is mainly because of the lattice diffusion, since the grain
boundary area will be much smaller than the lattice. Similarly in type C, the diffusion is
mainly from grain boundary diffusion. So in these processes, we actually measure the
lattice or grain boundary diffusion directly.

 However, in type B, both lattice and grain boundary diffusion can have reasonable
contribution and we need to develop the treatment to determine the diffusion rates
from different contributions.
Determination of grain boundary diffusion coefficient

 Imagine that two crystals of A with different


orientations are joined to develop a grain
boundary in the middle.
 Suppose tracer A* atoms are deposited on the
surface

 Two dimensional (x, y) system should be


considered, with unit length in z direction

 Flux coming inside the slab is Jy

 ∂J 
 Flux going out of the slab is  J y + dy  + 2 J x
 ∂y 

 So the rate of change in concentration can be


written as
∂ C A* 1   ∂J y  
= δ 
  yJ − J y − dy 
 − 2 dyJ x
∂t 1x dY x t   ∂ y  
∂J y 2
=− − Jx
∂y δ

Philosophical Magazine 45 (1954) 1225–1236 and Transactions of the Faraday Society 57 (1961) 1191–1199
∂C Al * ∂C Ag*
J x = − Dl J y = − Dg
∂x ∂y
 Inside the grain boundary

∂ 2C Ag* 2 Dl  ∂C A* 
l
∂C A*
= Dg + 
∂t ∂y 2 δ  ∂x 
 x =δ / 2
 Outside the grain boundary

∂ C Al * ∂ 2 C Al *
= Dl
∂t ∂x 2

 Whipple solved these as

5/ 3
 d ln CA*  D 
1/ 2
 1 
 = 0.66 l   
6/ 5 
( )
 d y   t  δ D 
 g 

 Note that following this equation, we actually measure δDg , since the thickness
of the grain boundary is unknown
 The relation derived can only be used
when
Dg >> Dl
 This condition can be understood from
the relation
 Dg  δ 
β =  
 Dl  2 Dl t 
 The parameter β gives the idea about
penetration

 Suppose for example, we consider δ =0.4


nm, Dl=10-15 m2/s, t = 105 s (28 hrs) and β = 1,
then we find
Dg / Dl = 5x104
Temperature range to find different types of diffusion
 1  2
ln I R = ln − y
 4 D A* t
 πD A* t
 l  l

1/ 2
y  d ln I A* 
5/ 3
 DlA
*
  1 
= 0.66   
 6/5 
( )
d y 
 t



 δD A 
 g 
*

 
 1  y2
ln I R = ln − *
 πDgA t  4 DgA t
*

 

 If experiments are done at very high temperature, then only A type will be found
in the sample.
 At intermediate temperature, type A and B can be found.
 At even lower temperature type B and type C can be found.
 At very low temperature only grain boundary diffusion that is type C can be found
because of lack of vacancies for lattice diffusion.
 Note again that in type B region we measure δDg, whereas, in region of type C, we
measure Dg
 Lattice diffusion coefficient, Dl is first measured in type A. This is further used to
measure grain boundary diffusion δDg in type B.

 Dg can be measured in type C directly.

Type A region Type B region


Type B region
Type C region

Diffusion coefficient in Type B Diffusion coefficient in Type C


region is measured region is measured
5/3 1/ 2
 1   
 DlA   1  x2
*
 d ln I A*   
 6/5 
= 0.66  ln I R = ln −
 d ( )
x 
 t



 δD A*
 g


 πDgA t

*


4 D A*
g t

Acta Mat. 55 (2007) 5910