Orientation dependence

Previously, we have not considered orientations in our discussion.

Further during the discussion of random jumps, we simplified the solution

considering the cubic crystal, where we can neglect the orientation dependence.

So let us consider different crystals and show the orientation relationship.

Orientation dependence in a BCC crystal

BCC crystal is shown above, let us now calculate the diffusion rate along <100>
direction.

Suppose there is a vacancy present at the body center.


We have previously derived the relation of self diffusion as
Z
1
s
D = Xv
Z
∑ Γi ∆xi
Z =1
2

In a BCC crystal Z is 8 and vacancy has an equal probability to exchange

position with any of the atoms 1-8.

Since this is a cubic crystal it can be visualized that the activation barrier for
any of the jumps will be the same.

So the jump frequency for any of the exchanges also should be the same. That
means Γi = Γ

Further, since we are considering the jump direction of <100>, the projected jump
length to this direction is a/2. Further we need to consider both the positive and
negative directions.

The effective jump length for exchanging position with atoms 1, 2, 5 and 6 is ∆xi = − a / 2

The effective jump length for exchanging position with atoms at 3, 4, 7 and 8 is ∆xi = a / 2

So the self diffusion in <100> direction can be written as
1  a a 
2 2
s s
Dx = D<100> = X v Γ 4 −  + 4  
8   2   2  
1
= X v Γa 2
4

Note that even to <010> and <001> directions also the diffusion rates will be
the same.

Now let us consider the <110> direction, which is perpendicular to the (110)
plane shown in the figure above.

Note that atoms 2, 4, 6 and 8 are placed on the same plane. So if vacancy
exchanges position with any of these atoms, the effective jump length in the <110>
direction will be zero. Although atom jumps a distance but in terms of diffusion in
this particular <110> direction is zero.

The effective jump length for exchanging with atoms at 1 and 5 is ∆xi = − a / 2

The effective jump length for exchanging position with atoms at 3 and 7 is ∆xi = a / 2

The effective jump length for exchanging position with atoms at 2, 4, 6 and 8 is 0

The activation barrier for all the atoms will be the same, we can consider Γi = Γ

1 
2
2  a 
Dxs = D<s110 > = X v Γ 4(0 ) + 4 ±  
8   2  
1
= X v Γa 2
4

So it can be seen that the diffusion rate to any of the directions <100>, <010>, <001>
and <110> is the same.

In fact it will be the same for any of the directions.

 Orientation dependence in a FCC crystal

Let us now consider a FCC crystal.

For the sake of explanation let us consider two crystals, as shown in the figure
above.

The coordination number of a FCC crystal is 12 and it can be seen that the
vacancy is surrounded by 12 atoms.

Again the jump frequency for any of the exchanges will be the same.

Let us consider the <100> direction first.


Effective jump length to 5, 6, 7 and 8 is ∆x = −a / 2

Effective jump length to 9, 10, 11 and 12 is ∆x = + a / 2

Effective jump length to 1, 2, 3 and 4 is ∆x = 0

The activation barrier for all the atoms will be the same; we can consider Γi = Γ
1   a a 
2 2

So the diffusion coefficient will be Dx = D<100> = X v Γ 4 −  + 4(0) + 4  

s s

12   2   2  
1
= X v Γa 2
6

Now let us consider <111> direction.

For that we need to consider first the

(111) plane.

Suppose, atoms 4 to 9 and the vacancy at the center are located on the same
plane.

So if atoms 1-3 are located on the plane below this plane then atoms 10-12 are
located on the plane above this plane.

a

Interplanar spacing is ∆x = ±
3

Effective jump length to 1, 2 and 3 is ∆x = −a / 3

Effective jump length to 4, 5, 6, 7, 8 and 9 are ∆x = 0

Effective jump length to 10, 11 and 12 are ∆x = a 3

The activation barrier for all the atoms will be the same, we can consider Γi = Γ

1   a   a  
2 2

Dxs = D<s111> = X v Γ 3 −  + 6(0) + 3  

12   3  3  
1
= X v Γa 2
6

So it can be seen that even after changing the orientation the diffusion
coefficient is the same.
 Orientation dependence in body centered tetragonal

Let us compare the jump to <100> and <001> direction.

Effective jump length to x and y direction is a/2 and to z direction is c/2.

However, it can be seen that the actual distance of all the atoms from vacancy
is the same.

Further void size also is the same so that the activation barrier and jump
frequency will be the same for exchanging position of vacancy with any atom

1  a  1
2 2
a
D<100> = D<010> = X V Γ 4 −  + 4   = X V Γa
2

8   2  2  4
Dxs = D ys ≠ Dzs
1  c  1
2 2
c 2
D<001> = X V Γ 4 −  + 4   = X V Γc
8   2   2  4
 Orientation dependence of diffusion in
Face Centered Orthorhombic structure

Here lattice parameters are a, b and c.

Three different jump frequencies should be defined, because void that is

barrier will be different on three different planes parallel to the major axes:
1,2,3,4 – Γ1
5,7,9,11 – Γ2
6,8,10,12 – Γ3

So the diffusion in different directions can be written as

1   a 
2 2 2 2
 a a a 1
Dxs = D<s100> = X v 2Γ2  −  + 2Γ3  −  + 4(0) + 2Γ2   + 2Γ3    Dxs = X v (Γ2 + Γ3 )a 2
12   2   2 2 2  12
5, 7 6, 8 9, 11 10, 12

1   b
2 2 2 2
 1
s s  b b b D ys = X v (Γ1 + Γ3 )b 2
D =D
y < 010 > = X v 2Γ1  −  + 2Γ3  −  + 2Γ1   + 2Γ3   + 4(0) 12
12   2   2 2 2 
1, 4 8, 12 2, 3 6, 10

1  c 
2 2 2 2
c  c  b 1
s
D =D
z
s
< 001> = X v 2Γ1   + 2Γ2   + 2Γ1  −  + 2Γ2  −  + 4(0)  Dzs = X v (Γ1 + Γ2 )c 2
12   2  2  2  2  12
1, 2 5, 9 3, 4 7, 11

So diffusion is anisotropic in this system and we can write

Dxs ≠ Dys ≠ Dzs

 Orientation dependence in Hexagonal closed packed structure

In hexagonal crystal also there are 12 neighbors.

It should be clear that for activation energy and jump frequency for exchanging
position with any of the atoms 1-6 and 7-12 are different.

Let us consider diffusion rates in two different directions, x and y.

 Orientation dependence in Hexagonal closed packed

1  
2 2 2 2
2  a  a a a 2
s
D = XV
x  1
2 Γ (± a ) + 2Γ1 −  + 2 Γ2 −  + 2Γ1  + 2Γ2  + 2 Γ2 (0 ) 
12   2  2 2 2 
1, 4 2, 6 7, 10 5, 3 9, 12 8, 11
1
Dxs = X V a 2 (3Γ1 + Γ2 )
12

1   1
2 2
c  c
6Γi (0) + 3Γ2   + 3Γ2  − 
s 2
D = XV
Z  = X V c Γ2
12  2  2  8
7, 8, 9 10, 11, 12

So the diffusion in hexagonal crystal is also anisotropic and we can write

D xs ≠ D zs