Diffusion in the ordered phases

Atomic diffusion mechanism in random solid solution is better

understood, however, it is least understood in the ordered phases.

We shall discuss the complexity of the process considering B2 (NiAl)

and γ (Ni3Al) phases, in which most of the studies till date are
conducted.
 Crystal structure of the B2 phase (stoichiometric composition)

B2

α-sublattice (lets say belongs to Al)

β-sub attice (lets say belongs to Ni)

B2 or the β phase in the Ni-Al system has L1o structure. If Ni occupies the body
center position of the cubic cell then Al occupies the body corner positions.

Similarly as explained, it can also be seen as Al occupying the body center position
and Ni occupying the body corner positions.

Actually two simple cubic cells of Al and Ni penetrate each other.

Phase diagram from P. Nash, Phase Diagrams of Binary Nickel Alloys, Materials Park (Ohio): ASM International (1991) 3-11

It can be seen that the phase has a wide homogeneity range. It deviates both on
Ni and Al rich sides.

Deviation from the stoichiometry is achieved because of the presence of
constitutional defects

Al
Ni

In the Al rich side, there are triple defects (2VNi+NiAl ) . That means two missing Ni
and one additional Ni on Al sublattice. Ni on Al sublattice is called Ni antisite

In the Ni rich side, there are Ni antisites.

Bradley and Taylor, Proc. Royal Soc. A 159 (1937)

 Migration of atoms/vacancy in B2 structure

Al
Ni
NNN VNi

NN

NN (Nearest Neighbor) jump is not possible: because Al will go to Ni sublattice,

which is not allowed unless it is an antisite defect. Vacancy concentration on the
sublattices will change, which is not again allowed, since in equilibrium condition
different sublattices will have particular concentration of vacancies.

Only possibility is NNN (Next Nearest Neighbour) jump to maintain the order,
since direct NNN jump is not possible because of 4 Al atoms which are present in
the middle

Different diffusion mechanisms are proposed following which diffusion is

possible
 6 jump cycle (6JC) mechanism

Proposed by:
Huntington, private communication
Elcock and McCombie Phys. Rev. B 109 (1958) 605
Comments from Divinski and Herzig, Intermetallics, 8 (2000) 1357

Ni, Al and VNi exchange positions 6 times after which NNN jump is
possible

The occurrence of 6JC is limited to the stoichiomtric composition
and below 1100 K (following the model of embedded atom
Al potentials)
VNi
Ni
Contribution is only 30% of the total diffusivity
 Triple defect mechanism

NiAl

VNi

Proposed by Stolwijk, van Al

Gand, Bakker, Phil Mag. A 42 VNi
Ni
(1980) 783

Possible diffusion mechanism in the Al-rich side

After 2 jumps Ni and VNi exchange their position
without destroying triple defect structure

Only Ni atoms migrate in this particular case
Continue……
 Triple defect mechanism
NiAl

VNi

Al
VNi Proposed by Stolwijk, van Gand, Bakker, Phil Mag. A 42 (1980) 783
Ni

Possible diffusion mechanism in the Al-rich side

After 4 jumps Ni, Al and VNi exchange their position without destroying triple defect
structure

Ni and Al atoms migrate together.
 Anti structure bridge (ASB) mechanism

VNi

Antisite atoms make a bridge to facilitate diffusion

Proposed by: Kao and Chang, Intermetallics,1 (1993) 237

Possible diffusion mechanism in the Ni-rich side

Antisite Ni atoms make a bridge to facilitate diffusion

Al
Ni
 Crystal structure and constitutional defects in the Ni3Al phase

Stoichiometric
composition

AlNi
NiAl
Al
Ni

Al-rich(by Al Ni-rich(by Ni
antisites) antisites)

Ni3Al phase has L12 structure, in which Al occupies body corner positions and
Ni occupies the face center positions.

This phase deviates from the stoichiometric composition because of the

presence of antisite defects.
Aoki and Izumi, Phys. Stat. Sol. 32 (1975) 657

When there are no defects present in the crystal, each Ni atom is surrounded
by 8 Ni and 4 Al atoms, whereas, each Al atom is surrounded by 12 Ni atoms.

So Ni can diffuse through its own sublattice, if vacancies are present.

On the other hand Al cannot diffuse if it does not have any antisite defect.
Because otherwise it cannot exchange position with vacancies on the Ni
sublattice.

However, experimental results indicate significant diffusion of Al.
 Defect concentrations calculated in Ni3Al

AlNi NiA
AlNi NiA
AlNi NiA
l
l
l VNi
VNi

VNi VAl

VAl

VAl

1200 K 1400 K 1600 K

Following theoretical analysis of Numakura et al., antisite defects are always
present.

Concentration of vacancy on the Ni sublattice is much higher than vacancy on the
Al sublattice.

This indicates that diffusion mainly happens because of vacancies on the Ni
sublattice only.
Numakura et al. Phil. Mag. 77 (1998) 887

Diffusion of Ni occurs by exchanging position of atoms and vacancies on its
own sublattice .

Presence of Ni antisites increases the diffusion rate.

Diffusion of Al occurs because of vacancy on the Ni sublattice and Al antisite

defects.

Numakura et al. Phil. Mag. 77 (1998) 887