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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

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

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

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

orientations are joined to develop a grain

boundary in the middle.

Suppose tracer A* atoms are deposited on the

surface

considered, with unit length in z direction

∂J

Flux going out of the slab is J y + dy + 2 J x

∂y

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

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

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.

Type B region

Type C region

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

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