DIFFUSION

Diffusion is relative flow of one material into another (Mass flow process by
which species change their position relative to their neighbours).
Diffusion of a species occurs from a region of high concentration to low
concentration (usually). More accurately, diffusion occurs down the chemical
potential () gradient.
To comprehend many materials related phenomenon (as in the figure below) one must
understand Diffusion.
The focus of the current chapter is solid state diffusion in crystalline materials.
Roles of Diffusion

Oxidation Creep
Metals Some mechanisms
Sintering Aging
Precipitates

Doping Carburizing
Semiconductors Steels

Many more Material Joining

Diffusion bonding
 Optimization of the Diff usion Bonding Parameters for
6063 Aluminum Alloy

The results showed that the interface thickness is

decreased with increasing bonding temperature and

pressure which can be attributed to the diffusion of the

atoms and continuous metallic bond formation at the

joint interface during the bonding process.

Diffusion refers to the process by which molecules intermingle as a result of their
kinetic energy of random motion.
Consider two containers of gas A and B separated by a partition. The molecules
of both gases are in constant motion and make numerous collisions with the
partition.
Diffusion mechanisms
Vacancy diffusion
Interstitial diffusion
Impurities

The mathematics of diffusion

Steady-state diffusion (Ficks first law)
Non-steady-State Diffusion (Ficks second
law)

Factors that influence diffusion

Diffusing species
Temperature
Microstructure
 When a perfume bottle is opened at one end of a room, its smell reaches the other
end via the diffusion of the molecules of the perfume.
If we consider an experimental setup as below (with Ar and H 2 on different sides
of a chamber separated by a movable piston), H 2 will diffuse faster towards the
left (as compared to Ar). As obvious, this will lead to the motion of movable
piston in the direction of the slower moving species.
This experiment can be used to understand the Kirkendall effect.

H2 diffusion direction

Ar H2

Movable piston
Piston motion
with an orifice
Piston moves in the
direction of the slower
moving species

Ar diffusion direction
Kirkendall effect
o Let us consider two materials A and B welded together with Inert marker and given a
diffusion anneal (i.e. heated for diffusion to take place).
o Usually the lower melting component diffuses faster (say B). This will lead to the shift in
the marker position to the right.
o This is called the Kirkendall effect.

Example W Mg

A B

Direction of
marker motion

Inert Marker is basically a thin rod of a high melting material, which is insoluble in A & B
Diffusion
Mass flow process by which species change their position relative to their
neighbours.
Diffusion is driven by thermal energy and a gradient (usually in chemical
potential). Gradients in other physical quantities can also lead to diffusion (as in
the figure below). In this chapter we will essentially restrict ourselves to
concentration gradients.
Usually, concentration gradients imply chemical potential gradients; but there are
exceptions to this rule. Hence, sometimes diffusion occurs uphill in
concentration gradients, but downhill in chemical potential gradients.
Thermal energy leads to thermal vibrations of atoms, leading to atomic jumps
In the absence of a gradient, atoms will still randomly jump about, without any
net flow of matter.
Concentration / Chemical potential

Electric
Gradient
Magnetic
Stress
 Flux (J) (restricted definition) Flow / area / time [Atoms / m2 / s]

Flow direction

Area (A)

1 dn
J
A dt
Ficks I law As we shall see the law is actually an equation

Flux (J) of atoms* is flow per unit area per unit time Flow/area/time [Atoms/m2/s].
(This is a restricted definition).

Assume that only B is moving into A.

Assume steady state conditions J f(x,t) (No accumulation of matter).
Flux is proportional to the concentration gradient. The constant of proportionality is the
Diffusivity (D). Diffusivity is a function of the composition of the material and the
temperature.
The negative sign implies that diffusion occurs down the concentration gradient

dc dc
J J D Ficks first law (equation)
dx dx
1 dn dc
J D
A dt dx Flow direction
A
dn dc
DA dc dJ
dt dx x x
dt dx
Continuity equation
* Could be other species as well
 dc
J D
dx

Diffusion coefficient/ Diffusivity

No. of atoms dn dc
crossing area A DA Cross-sectional area
per unit time dt dx Concentration gradient

ve sign implies matter transport is down the concentration gradient

Flow direction

A
As a first approximation assume D f(t)
 Steady and non-steady state diffusion D f(c)
Steady state
Under steady state conditions J f(x,t) D = f(c)
dc J Diffusion
0
dt x x t D f(c)
Substituting for flux from Ficks first law Non-steady state
J c J = f(x,t)
D = f(c)
D 0 If D is constant
x x 2c Slope of c-x plot is constant under steady state
D 2 0 conditions
If D is NOT constant x
c
D constant
x
If D increases with concentration then slope (of c-x plot)
decreases with c
If D decreases with c then slope increases with c
1st law 2nd law

x
x1 x2 x3
Ficks II law

The equation as below is often referred to as the Ficks II law (though clearly this is an
equation and not a law).
The equation is a second order PDE requiring one initial condition and two boundary
conditions to solve.
In the form of the equation below D is the diffusivity and is assumed constant (i.e is not a
function of concentration).

c 2
c
D 2
t x
 If Jx is the flux arriving at plane A and Jx+x is the flux leaving plane B. Then the
Accumulation of matter is given by: (Jx Jx+x). 2nd law

x
Accumulation J x J x x

J A B
Accumulation J x J x x
x Jx Jx+x

c J Atoms 1 Atoms
m 3 s .m m 2 s J

x J x J x x

t x

c J c c
x x D Ficks first law
t x t x x

c c D f(x) c 2c
D D 2 x1x2x3
t x x t x
 c 2c
D 2
t x

RHS is the curvature of the c vs x curve

c
c

x x

LHS is the change is concentration with time

+ve curvature c as t ve curvature c as t

Temperature dependence of diffusivity

a) Diffusivity depends exponentially on temperature.

b) This dependence has important consequences with regard to material behaviour
at elevated temperatures. Processes like precipitate coarsening, oxidation, creep
etc. occur at very high rates at elevated temperatures.

Q D = diffusion co efficient
D0= diffusion co efficient at temp T =
D D0 e kT K= gas const
T= abs temperature in K
Q = activation energy
Arrhenius type

Approximate formula for depth of penetration

x Dt
ATOMIC MODELS OF DIFFUSION
The diffusion of two important types of species needs to be distinguished:
(i) species sitting in a lattice site
(ii) species in a interstitial void

1. Interstitial Mechanism

Usually the solubility of interstitial atoms (e.g. carbon in steel) is small. This implies that
most of the interstitial sites are vacant. Hence, if an interstitial species wants to jump, most
likely the neighboring site will be vacant and jump of the atomic species can take place.
Light interstitial atoms like hydrogen can diffuse very fast. For a correct description of
diffusion of hydrogen anharmonic and quantum (under barrier) effects may be very
important (especially at low temperatures).
Interstitial Diffusion

Hm
1 2

1 2

At T > 0 K vibration of the atoms provides the energy to overcome the energy
barrier Hm (enthalpy of motion)
frequency of vibrations, number of successful jumps / time

H m

' e kT
2. Vacancy Mechanism

For an atom in a lattice site (and often we are interested in substitutional atoms) jump to a
neighbouring lattice site can take place if it is vacant. Hence, vacancy concentration plays
an important role in the diffusion of species at lattice sites via the vacancy mechanism.
Vacancy clusters and defect complexes can alter this simple picture of diffusion involving
vacancies
Substitutional Diffusion

Probability for a jump

(probability that the site is vacant).(probability that the atom has sufficient energy)
Hm enthalpy of motion of atom
frequency of successful jumps

H f H m H f H m

' e kT
e kT
' e kT

H f H m

D 2 e kT

Where, is the jump distance

Interstitial Diffusion

H m H m
kT
D e 2 kT of the form
D D0 e

D (C in FCC Fe at 1000C) = 3 1011 m2/s

Substitutional Diffusion

H f H m H f H m

of the form kT
D e 2 kT D D0 e

D (Ni in FCC Fe at 1000C) = 2 1016 m2/s

Diffusion Paths with Lesser Resistance

Experimentally determined activation energies for diffusion

Qsurface < Qgrain boundary < Qlattice

Lower activation energy automatically implies higher diffusivity

Diffusivity for a given path along with the available cross-section for
the path will determine the diffusion rate for that path
 Comparison of Diffusivity for self-diffusion of Ag
single crystal vs polycrystal

Schematic
Qgrain boundary = 110 kJ /mole
QLattice = 192 kJ /mole
Log (D)

Polycrystal

Single
crystal
1/T
Increasing Temperature
Applications based on Ficks II law Carburization of steel
Surface is often the most important part of the component, which is prone to degradation.
Surface hardening of steel components like gears is done by carburizing or nitriding.
Pack carburizing solid carbon powder used as C source.
Gas carburizing Methane gas CH4 (g) 2H2 (g) + C (diffuses into steel).

C(+x, 0) = C1
C(0, t) = CS

A = CS
B = CS C1
 Solved A 0.2% carbon steel needs to be surface carburized such that the concentration
Example of carbon at 0.2 mm depth is 1%. The carburizing medium imposes a surface
concentration of carbon of 1.4% and the process is carried out at 900C
(where, Fe is in FCC form).
Data: D0 (C in -Fe) 0.7 10 4 m 2 / s Q 157 kJ / mole

The solution to the Fick second law: C ( x, t ) A B erf x

(1)
2 Dt

x
C ( x, t ) CS (CS -C0 ) erf
2 Dt

C ( x, t ) CS x
= erf
C0 CS 2 Dt

1 2 10-4
erf (2)
3 2 Dt
1
 1.4
1 2 10-4
From equation (2) erf
1.2 3 2 Dt
1

1.0
t 2 10-4
erf 1 (0.3333) 0.309

0.8 2 7.14 10 12
t1
%C

0.6 t = t1 = 14580s 2
1 104
t1 12 14580 s
0.4 t = 1000s
t = 7000s 7.14 10 0.33
t =0
0.2

0.2 0.4 0.6 0.8 1.0 1.2 1.4

x (in mm from surface)
Approximate formula for depth of penetration
x Dt
C ( x, t ) CS x c( x, t ) C0 x


= erf C C 1 erf
C 0 C S 2 Dt S 0 2 Dt

Let the distance at which

[(C(x,t)C0)/(CSC0)] = be called x1/2
(which is an effective penetration depth)
x1 2 1
1 x1 2 erf
1 erf 2 Dt 2
2 2 Dt

1 1 x1 2 1
erf
2 2 2 Dt 2

x penetration Dt

The depth at which C(x) is nearly C0 is (i.e. the distance beyond which is un-penetrated):
x
0 1 erf Erf(u) ~ 1 when u ~ 2
2 Dt
x
2 x 4 Dt
2 Dt
End
Diffusion in ionic materials

Ionic materials are not close packed

Ionic crystals may contain connected void pathways for rapid diffusion
These pathways could include ions in a sublattice (which could get disordered)
and hence the transport is very selective
alumina compounds show cationic conduction
Fluorite like oxides are anionic conductors
Due to high diffusivity of ions in these materials they are called superionic
conductors. They are characterized by:
High value of D along with small temperature dependence of D
Small values of D0
Order disorder transition in conducting sublattice has been cited as one of the
mechanisms for this behaviour
Calculated and experimental activation energies for vacancy Diffusion

Element Hf Hm Hf + Hm Q

Au 97 80 177 174

Ag 95 79 174 184
 c = atoms / volume
c=1/3
concentration gradient dc/dx = (1 / 3)/ = 1 / 4
Flux = No of atoms / area / time = / area = / 2

J ' 4
D 2 ' 2
1 2 (dc / dx)

H m

D 2 e kT

Q
On comparison
with D D0 e kT

Vacant site

D0 2

3. Interstitialcy Mechanism

Exchange of interstitial atom with a regular host atom (ejected from its regular
site and occupies an interstitial site)
Requires comparatively low activation energies and can provide a pathway for
fast diffusion
Interstitial halogen centres in alkali halides and silver interstitials in silver halides

Steady state diffusion

C1 D f(c)
Concentration

C2
D = f(c)