Diffusion Solid

"War is a matter of vital importance to the State;

the province of life or death; the road to survival or ruin.
It is mandatory that it be thoroughly studied."
Sun Tzu,"The Art of War“ ( approximately 250 BC)
 Diffusion
Part1. Constitutional effects
Diffusion is the phenomenon of spontaneous material transport by atomic motion.
Diffusion is classified according to
a) conditions: self-diffusion, diffusion from surface, interdiffusion, fast path
diffusion etc.
b) mechanism: interstitial, substitutional;

Part 2.
Non-constitutional effects. Kirkendall effect. Einstein equation.
General Note.
Diffusion is a flux of matter in which the atoms or molecules of a certain type
move differently (rate, amount etc) with respect to the atoms/molecules of
other type.
 Please note the difference from gas or liquid flow, in this case ALL
components move in the same way.
 The definition: “Diffusion is the movement of molecules from a high
concentration to a low concentration” is wrong because there are cases when
diffusion process does just opposite.
 Flux of matter can be caused not only by the difference in concentration of
the atom that diffuses, but also the difference in concentration of other atoms
and or gradient of physical parameters ( temperature, pressure, electric or
magnetic field).
INHOMOGENEOUS DISTRIBUTION OF ONE COMPONENT MAY
CAUSE DIFFUSION OF OTHER COMPONENTS.

Example: If two pieces of steel with 0.4%

carbon, one containing 3.8% silicon and
the other with no silicon, are joined, it
might be expected that the carbon would
remain homogeneously distributed.
However, the chemical potential of
carbon is higher in the silicon-containing
steel, and having a high mobility, the
carbon diffuses into the silicon-free steel.
General thermodynamic considerations lead to a formula for the flux ( amount
of matter through a unit area per unit of time): Fick’s law

C
J  D D- is a diffusion coefficient
x

C is the concentration of the diffusion species.

x is a coordinate

The sign of the diffusion coefficient (direction of the flux) depends on the conditions of
the system. IT CAN BE BOTH POSITIVE AND NEGATIVE ( uphill diffusion, for
instance during phase separation)
Ci  2Ci
  Di
In the systems, in which D is independent on concentration t x 2
Examples of solutions:
1. A fixed quantity of solute (B) is plated onto a semi-infinite bar

Boundary conditions: C ( x,0)  0 and  C ( x, t )dx  B
0

B  x2 
Solution: C ( x, t )  exp  
Dt  4 Dt 

This case is realized if a thin film of diffusant is

deposited on a surface.
Example 2. Interdiffusion of ONE component
and diffusion from constant source.
Boundary conditions: C ( x  0, t )  Cs and C ( x, t  0)  C0

 x2 
Solution: C ( x, t )  Cs  (Cs  C0 ) erf   
C A  CB  4 Dt 
Cs 
2
x
Reminder : erf  x    exp(u 2 )du
0

Notice that the surface concentration remains fixed.

In the case of interdiffusion of TWO components concentration profiles may be very
different!
In ideal case the point of constant concentration propagates with a rate of (4Dt) -½
If there is a way to trace a point of constant concentration then diffusion coefficient
can be determined explicitly.
x2 2
x /(4Dt)=
C ( x, t )  const    const 1.0 1
4 Dt 2

Concentration
x2 4
8
16
32
0.5
64
The slope is 4D

0 2 4 6 8 10
x Depth
t
This method can be used to measure diffusion coefficient by measuring experimentally :
1 x 2
D
4 t
 Microscopic Mechanisms of Diffusion
Phenomenological description does not give dependence of the diffusion
coefficient on any physical parameters.

Consider two adjacent planes in the crystal one can get that D 
 
U
Ne kT
6
N sites N sites
with n1 with n2
atoms
v is the number of jumps per second
atoms
U is the energy barrier separating two sites

a N is the number of atoms per plane

U

Energy profile
1 2

In ideal case diffusion coefficient exponentially depends on temperature.

 Examples

Plot of the logarithm of the diffusion coefficient versus the reciprocal of

absolute temperature for several metals.
 Mechanisms of Diffusion
Diffusion is the stepwise migration of atoms from lattice site to lattice site.
For an atom to make such a move, two conditions must be met:
1. there must be an empty adjacent site, and
2. the atom must have sufficient energy to break bonds with its neighbor
atoms and then cause some lattice distortion during the displacement.

1. Self-diffusion: there is no gradient of chemical potential:

a) Interstitial b) Vacancy b) Kick-out
 Important.
 During self-diffusion there is no change of chemical potential.
 Realization of each of the mechanisms depends on
 Type of intrinsic defects that prevails in the solid
 Activation energy for each of the mechanisms, if more than
one may be realized.
 Presence of other defects (vacancies).
Realization of vacancy or kick-out diffusion is possible only at the
temperatures with sufficient concentration of vacancies. Therefore,
prevailing mechanism may change with temperature.
 In general, EVERY component in solid undergoes self-diffusion, however,
if a solid contains more than one component, the ratio between self-diffusion
coefficient depends on the type of bonding:
Solids with covalent bonding typically have very low self-
diffusion coefficients.
Solids with ionic bonding may have very different self-diffusion
coefficients for anion and cation.
 Metals and metal alloys usually show fast self-diffusion.
 Q

D  D0 e RT
 Diffusion of impurities.
a) Interstitial b) Vacancy b) Kick-out

Important.
 The diffusion mechanism of an impurity depends on many factors:
type of the solution: interstitial or substitutional;
size of the diffusant and size of the host sites;
temperature;
presence of other impurities;
electronic structure of the host: metal, dielectric or
semiconductor.
 Important.
Special cases:
There are materials where structural properties allow ultra-fast ion
movement: superionics. In these materials ( for example AgRb3I4 one of the
ions is much smaller than the available sites and there are far more available
sites than ions.
Diffusion in polymers and glasses can be described by “randomly opening
path” theory. Temperature dependence of diffusion coefficient in these
materials is very complicated and time to time activation energy may
become negative=> Diffusion coefficient may decrease with temperature.
Diffusion coefficient in anisotropic solids is a strong function of direction.
Example: diffusion coefficient of Li and other alkaline metals in graphite
along and across the layers may differ by 4 orders of magnitude.
 Diffusion in presence of electric field: Electromigration.

Ionic and charged in impurities in solids can drift in electric field. As a

first approximation one can assume that the flux of ions is proportional to
electric field and concentration, i.e., one can use a concept of mobility. In
this idealized case the flux of ions is given:
J i  g i Ci E )1(
where gi is mobility of
ions, Ci is the
concentration of ions and
Diffusion coefficient and mobility are linked E is electric field.
E
Thus mobility is Dez
gi 
kT
(Nernst) Einstein equation

Electromigration Diffusion
 Limitations.

 Electrical mobility and diffusion coefficient are linked to each other.

 Nernst-Einstein equation is valid whenever the following conditions are
met:
The system is not far from equilibrium, i.e., gradient of potential
and concentration are small
The diffusion species follow Boltzmann statistics, i.e., they do not
interact with the host and with each other.
Important: Nernst-Einstein equation is applicable to electrons in some
semiconductors.
 Nernst-Einstein equation is not valid for systems with strong
interactions.
 Comments

Nernst-Einstein equation is a low electric field approximation! It implies

that the energy acquired by ion during one jump is mush smaller than the
activation energy. =>
Systems with very low activation energy do not obey Nernst –
Einstein equation.
Application of a sufficiently high electric field may significantly
increase mobility. This electric field is, in fact, comparable with crystal
field, the electric field between ions in crystal.
Materials with fast-path diffusion may have different electric
fields for each path at which non-linear dependence between mobility and
diffusion coefficient becomes noticeable.
 Thermal diffusion
If a homogeneous alloy is placed in a temperature gradient, one of the elements will diffuse under the
influence of the temperature difference. This is known as the Sorét effect, and again shows an
example of diffusion occurring without a composition gradient. In the presence of temperature
gradients we cannot use Gibbs free energies to define equilibrium conditions, so chemical potential
arguments can not be used.
T1 < T2
Thermal diffusion in ionic solids with only one
1 ≠ 2 atom mobile leads to thermo-electric voltage,
similar to Seebeck effect in electronic
conductors.

In practice thermal diffusion (also

called thermomigration) can occur
both down and up the temperature
gradient.
Carbon in austenite thermomigrates up a temperature gradient, because the activation
energy in this case is required mainly for preparing the destination site. As the carbon
moves, two Fe atoms have to separate to create room for the C atom. This occurs more
easily at a higher temperature, so the carbon moves preferentially to the hotter region.
 Strain field induced diffusion
The presence of strain in the material can have a significant effect on the
chemical potential of a solute. For example, in the case of an interstitial solute
such as carbon in iron, a tensile strain will increase the space available for the
interstitial and so reduce the chemical potential.

The impurities that expand the lattice drift toward dilated regions and
impurities that cause contraction of the lattice drift towards compressed
regions.