Introduction

Diffusion is defined as, random movement of atoms/ molecules in solid, liquid and
gas. For example dissolution of ink in water and smoke in air
It can also defined as, Diffusion is a process of mass transport by atomic
movement under the influence of thermal energy and a concentration gradient.
To comprehend many materials related phenomenon one must understand
diffusion.

Role of Diffusion

Oxidation Creep

Sintering Aging

Doping Carburizing

Many More...!
Materials Joining : Diffusion Bonding
 Diffusion Phenomena
Mass flow process by which species change their position relative to their
neighbors.
Driven by thermal energy and a gradient
Thermal energy → thermal vibrations → Atomic jumps
Atoms move from higher to lower concentration region. If this movement is from
one element to another e.g. Cu to Ni, then it is termed as Inter-diffusion. If the
movement is within similar atoms as in pure metals, it is termed self-diffusion.

Gradient

Electric Stress

Magnetic Chemical potential

 Diffusion Mechanism
Diffusion of atoms involves movement in steps from one lattice site to the another.
An empty adjacent site and breaking of bonds with the neighbor atoms are the two
necessary conditions for this.

Vacancy Mechanism

This mechanism involves movement of atoms (we are interested in substitutional

atoms) from a regular lattice site to an adjacent vacancy. Since vacancy and atoms
exchange position, the vacancy flux is in the opposite direction.
 Diffusion Mechanism
Interstitial Mechanism

This mechanism Involves migration of atoms from one interstitial site to a

neighboring empty interstitial site.
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.
This mechanism is more prevalent for impurity such a hydrogen, carbon, nitrogen,
oxygen which are small enough to fit into an interstitial position.

Interstitial
Interstitial
atom
atom
 Diffusion Mechanism
Atom Interchange Mechanism
It is possible for movement to take place by a direct interchange between two
adjacent atoms or by a four –atom ring interchange.
However, these would probably occur only under special conditions, since the
physical problem of squeezing between closely packed neighboring atoms would
increase the barrier for diffusion.
Note: The rate of diffusion is much greater in a rapidly cooled alloy than in the
same alloy slow cooled. The difference is due to the larger number of vacancies
retained in the alloy by fast cooling.
 Kirkendall effect
If the diffusion rates of two metals A and B into each other are different, the
boundary between them shifts and moves towards the faster diffusing metal.

This is known as kirkendall effect. Named after the inventor Ernest Kirkendall
(1914-2005). It can be demonstrated experimentally by placing an inert marker at
the interface

A B

Materials A and B welded together with inert Marker

marker and given a diffusion anneal motion
Usually the lower melting component diffuses
faster (say B)

Inert Marker – thin rod of a high melting material which is

basically insoluble in A & B
 Kirkendall effect
Zn diffuses faster into Cu than Cu in Zn. A diffusion couple of Cu and Zn will lead
to formation of a growing layer of Cu-Zn alloy (Brass).

Same will happen in a Cu-Ni couple as copper diffuses faster in nickel than nickel
in copper.
Since this takes place by vacancy mechanism, pores will form in cu (of the Cu-Ni
couple as the vacancy flux in the opposite direction (towards Cu) will condense to
form pores.
 steady and non-steady state diffusion
Diffusional processes can be either steady-state or non-steady-state. These two
types of diffusion processes are distinguished by use of a parameter called flux.
It is defined as net number of atoms crossing a unit area perpendicular to a given
direction per unit time. For steady-state diffusion, flux is constant with time,
whereas for non-steady-state diffusion, flux varies with time.
A schematic view of concentration gradient with distance for both steady-state and
non-steady-state diffusion processes are shown below.

Flux (J) (restricted definition) → Flow / area / time [Atoms / m2 / s]

Steady state diffusion Non-Steady state diffusion
C1 C1
Concentration →

Concentration →
D ≠ f(c)
Steady state
D = f(c)
J ≠ f(x,t) t1
t2
C2 t3
Non-steady state C2
J = f(x,t)
Distance, x → Distance, x →
steady and non-steady state diffusion
Steady State : Concentration profile not changing with time.

Concentration ‘C’ in the box

J (left) J (right) doesn’t change with time

Steady State
X J(x) Left = J(x) Right

Non--Steady State : Concentration profile changes with time.

Non

dx
Concentration accumulating
in the box
J (left) J (right)

Non-Steady State
J(x) Left ≠J(x) Right
 Fick’s I law
Steady-state diffusion is described by Fick’s first law which states that flux, J, is
proportional to the concentration gradient.
The constant of proportionality is called diffusion coefficient (diffusivity), D
(cm2/sec). diffusivity is characteristic of the system and depends on the nature of
the diffusing species, the matrix in which it is diffusing, and the temperature at
which diffusion occurs.
Thus under steady-state flow, the flux is independent of time and remains the same
at any cross-sectional plane along the diffusion direction. for the one-dimensional
case, Fick’s first law is given by

J ≡ atoms / area / time ∝ concentration gradient

dc dc 1 dn dc
J∝ J = −D J= = −D

Steady state
dx dx A dt dx

J ≠ f(x,t)
No. of atoms crossing Concentration gradient
dn dc
= − DA
area A per unit time
Diffusion coefficient/ Cross-sectional area
diffusivity dt dx The minus sign in the equation means that
diffusion occurs down the concentration gradient
 Fick’s I law
In Ficks I law, minus sign comes from the fact that matter flows down the concentration
gradient. It is not necessarily true in all the cases.
Matter may also diffuse up the concentration gradient, which is called uphill diffusion.
Fick’s first law can directly be applied in the case of
steady state, as shown in the example below.
Steady state means that there will not be any change in
the composition profile with time.
If we pass carburizing gas through the pipe as shown in
the figure and decarburizing gas outside the pipe, a
steady composition profile may develop.
Concentration gradient can be calculated following:
dc C − C0 C − Ci
=− i =− 0
dx d d

From this, one can calculate the flux from the known
diffusion coefficients of carbon or the diffusion
coefficient from the flux determined.
 The steady-state diffusion is found in the purification of hydrogen gas.
Solved Compute the number of kilograms of hydrogen that pass per hour through a
Example -1 6-mm-thick sheet of palladium having an area of 0.25 m2 at 600°C. Assume a
diffusion coefficient of 1.7 × 10-8 m2 / s, that the concentrations at the high-
and low-pressure sides of the plate are 2.0 and 0.4 kg of hydrogen per cubic
meter of palladium, and that steady-state conditions have been attained.

This Problem calls for the mass of hydrogen, per hour, that diffuses through a pd sheet.

From the Fick’s I law:

∆c
M = JAt = − DAt
∆x

−8  0.4 − 2.0kg / m 3 
= −(1.7 × 10 m / s )(0.25m )(3600 s / h) 
2 2
−3 
 6 × 10 s 

= 4.1×10 −3 kg / h
 A sheet of BCC iron 2 mm thick was exposed to a carburizing gas atmosphere on one
Solved side and a decarburizing atmosphere on the other side at 675ºC. After having reached
Example -2 steady state, the iron was quickly cooled to room temperature. The carbon
concentrations at the two surfaces of the sheet were determined to be 0.015 and 0.0068
wt%. Compute the diffusion coefficient if the diffusion flux is 7.36 × 10-9 kg/m2-s
(Hint : convert the concentrations from weight percent to kilograms of carbon per
cubic meter of iron.
This problem calls for computation of the diffusion coefficient for a steady-state diffusion
situation. Let us first convert the carbon concentrations from weight percent to kilograms
carbon per meter cubed using below equation.
For 0.015 wt% C    
 C   0.015 
C 'C =  C
× 10 
3 C 'C =  × 10 3  = 1.18kgC / m 3
C C 0.015 99.985
 C+ C   + 
 ρ C ρ Fe   2.25 7.87 

Similarly, for 0.0068 wt% C  

 0.0068 
C '' C = ×103  = 0.535kgC / m3
0.0068 99.9932
 + 
 2 . 25 7 .87 

X − XB  − 2 × 10 −3 m 
D = −J A −9
= −(7.36 × 10 Kg / m − s ) 2
3
C A − CB 1.18 Kg / m − 0.535 Kg / m 
3

= 2.3 ×10−11 m 2 / s
 Fick’s II law
Most interesting cases of diffusion are non-steady-state processes since the
concentration at a given position changes with time, and thus the flux changes with
time.
This is the case when the diffusion flux depends on time, which means that a type
of atoms accumulates in a region or depleted from a region (which may cause them
to accumulate in another region). Fick’s second law characterizes these processes,
which is expressed as:
 Atoms 1    Atoms 
∆x  m 3 s .m  =  m 2 s  ≡ [J ]
Accumulati on = J x − J x + ∆x     

 ∂J   ∂c   ∂J 
Jx Jx+∆x Accumulation = J x −  J x + ∆x   ∆x = J x −  J x + ∆x 
 ∂x   ∂t   ∂x 
Non-steady state

 ∂c  ∂  ∂c   ∂c  ∂  ∂c   ∂c  ∂J
  = D    = −  −    ∆ = − ∆x
J = f(x,t)

D x
 ∂t  ∂x  ∂x   ∂t  ∂x  ∂x   ∂t  ∂x

 ∂c  ∂ 2c
 =D 2 Fick’s II law
 ∂t  ∂x
 Solutions to Fick’s II law
 ∂c  ∂ 2c
 =D 2
 ∂t  ∂x
Solution to the above expression is possible when meaningful boundary conditions
are specified. One common set of boundary conditions can be written as:
For t = 0, C = Co at 0 ≤ x ≤∞
Cs
For t > 0, C = Cs at x = 0

Concentration →
C = Co at x = ∞
Cs - Co
Cx
C ( x, t ) − C o  x 
= 1 − erf   Cx - Co
C s − Co  2 Dt  Co

Distance, x →
Where Cx represents the concentration at depth x after time t. The term erf stands for Gaussian
error function. Corresponding error function values for a variable are usually found from
standard mathematical tables. The above equation demonstrates the relationship between
concentration, position, and time. Thus the equation can be used to explain many practical
industrial problems like corrosion resistance of duralumin, carburization and decarburization of
steel, doping of semi conductors etc.
 Summary on Fick’s II law

Process Solution
 x  Cs = Surface concentration
Carburisation C = CS − (C S − C0 )erf  
 2 Dt  C0 = Bulk concentration

 x 
Decarburisation C = C0 erf   C0 =Initial Bulk concentration
 2 Dt 

 C + C2   C1 − C2   x  C1 = Concentration of steel 1
Diffusion couple C = 1 − erf   C2 = Concentration of steel 2
 2   2   2 Dt 

 πx   t Cmean = Mean concentration

C = Cmean + β 0 sin   exp −  β0 = Initial concentration amplitude
Homogenisation λ  τ λ = half wavelength
t = relaxation time
 An FCC iron–carbon alloy initially containing 0.55 wt% C is exposed to an
Solved oxygen-rich and virtually carbon-free atmosphere at 1325 K (1052ºC).
Example - 3 Under these circumstances the carbon diffuses from the alloy and reacts at
the surface with the oxygen in the atmosphere; that is, the carbon
concentration at the surface position is maintained essentially at 0 wt% C.
(This process of carbon depletion is termed decarburization.) At what
position will the carbon concentration be 0.25 wt% after a 10-h treatment?
The value of D at 1325 K is 4.3 × 10-11 m2/s.

This problem asks that we determine the position at which the carbon concentration is 0.25 wt%
after a 10-h heat treatment at 1325 K when Co = 0.55 wt% C.
C x − Co 0.25 − 0.55  x 
= = 0.5455 = 1 − erf  
C s − Co 0 − 0.55  2 Dt  Z Erf (Z)

 x  0.40 0.4284
erf   = 0.4545
 2 Dt  Z 0.4545
Using tabulation of error function values and linear interpretation
0.45 0.4755
Z − 0.40 0.4545 − 0.4284
= Z = 0.4277
0.45 − 0.40 0.4755 − 0.4284

 x 
  = 0.4277 x = 2(0.4277) Dt = (0.8554) (3.6 × 10 4 s )(4.3 × 10 −11 m 2 / s )
 2 Dt 
= 1.06 ×10 −3 m = 1.06mm
 Solved Nitrogen from a gaseous phase is to be diffused into pure iron at 675ºC. If
Example - 4 the surface concentration is maintained at 0.2 wt% N, what will be the
concentration 2 mm from the surface after 25 h? The diffusion coefficient
for nitrogen in iron at 675ºC is 1.9× 10-11 m2/s .
This problem asks us to compute the nitrogen concentration Cx at the 2 mm position after a 25
h diffusion time, when diffusion is non steady-state.
C x − Co C x − 0  x 
= = 1 − erf  
Cs − Co 0.2 − 0  2 Dt 

 2 × 10 −3
m 
= 1 − erf   = 1 − erf (0.765)
 2 (1.9 × 10 −11 m 2 / s )(25h)(3600 s / h) 
 

Using tabulation of error function values and linear interpretation Z Erf (Z)

0.750 0.7112
0.765 − 0.750 y − 0.7112 y = erf (0.765) = 0.7205
=
0.800 − 0.750 0.7421 − 0.7112 0.765 y

Cx − 0 0.800 0.7421
= 1.0 − 0.7205
0.2 − 0

C x = 0.056wt % N
 Factors affecting Diffusion
Ease of a diffusion process is characterized by the parameter D, diffusivity. The value
of diffusivity for a particular system depends on many factors as many mechanisms
could be operative.

Diffusing species
If the diffusing species is able to occupy interstitial sites, then it can easily diffuse
through the parent matrix. On the other hand if the size of substitutional species is
almost equal to that of parent atomic size, substitutional diffusion would be easier.
Thus size of diffusing species will have great influence on diffusivity of the system.

Lattice structure
Diffusion is faster in open lattices or in open directions than in closed directions.

Presence of defects

As mentioned in earlier section, defects like dislocations, grain boundaries act as

short-circuit paths for diffusing species, where the activation energy is diffusion is
less. Thus the presence of defects enhances the diffusivity of diffusing species.
 Factors affecting Diffusion
Temperature

energy to move and can do so more quickly.

diffusion also increases. This is because the atoms have more
Faster Diffusion Rates: As temperature increases, the rate of

Where:

the Arrhenius equation:

Diffusion Coefficient: The diffusion coefficient

barriers more easily.

temperatures provide the necessary energy to overcome these
other, which involves overcoming an energy barrier. Higher
Activation Energy: Diffusion requires atoms to move past each

barriers that impede their diffusion.

This increased movement helps atoms overcome the energy
kinetic energy of atoms, causing them to vibrate more vigorously.
Increased Atomic Vibrations: Higher temperatures increase the
is the absolute temperature.

is the gas constant.

is the activation energy for diffusion.

is the pre-exponential factor.

increases with temperature. This relationship is often described by

Temperature has a most profound influence on the diffusivity and diffusion rates. It
is known that there is a barrier to diffusion created by neighboring atoms those
need to move to let the diffusing atom pass. Thus, atomic vibrations created by
temperature assist diffusion.
Empirical analysis of the system resulted in an Arrhenius type of relationship
between diffusivity and temperature.
 Q 
− 
D = D0 e  kT 

Where D0 is a pre-exponential constant, Q is the activation energy for diffusion, R

is gas constant (Boltzmann’s constant) and T is absolute temperature.
From the above equation it can be inferred that large activation energy means
relatively small diffusion coefficient. It can also be observed that there exists a
linear proportional relation between (lnD) and (1/T). Thus by plotting and
considering the intercepts, values of Q and D0 can be found experimentally (see in
next slide for clear understanding).
 Diffusion paths with lesser resistance
Experimentally determined activation energies for diffusion…!

Qsurface < Qgrain boundary < Qpipe < Qlattice

Lower activation energy automatically implies higher diffusivity

Core of dislocation lines offer paths of lower resistance PIPE DIFFUSION

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

Log (D) →
self-diffusion of Ag → Single Polycrystal
crystal vs. polycrystal

Single
Qgrain boundary = 110 kJ /mole crystal

QLattice = 192 kJ /mole 1/T →

← Increasing Temperature
 Solved Using the following diffusion data, compute the value of D for the
Example - 5 diffusion of magnesium in aluminum at 400ºC.
Do(Mg in Al) =1.2 × 10-4 m2/s Qd=131 KJ/mol

This problem asks us to compute the magnitude of D for the diffusion of Mg in Al at

400ºC (673K).

−4  131,000 J / mol 
D = (1.2 × 10 m / s ) exp −
2

 (8.31J / mol − k )( 673k ) 

= 8.1×10 −15 m 2 / s
 Solved At what temperature will the difusion coefficient for the diffusion of
Example - 6 zinc in copper have a value of 2.6 × 10-16 m2/s
Do =2.4 × 10-5 m2/s Qd=189 KJ/mol

We are asked to calculate the temperature at which the diffusion coefficient for the
diffusion of Zn in Cu has a value of 2.6 × 10-16 m2/s. Solving for T from below
equation
Qd
T =−
R (ln Do − ln D )

By using the given data we can get

 189,000 J / mol 
T = − −16 −5 
 (8.31J / mol − k )[ln(2.6 × 10 m 2
/ s ) − ln( 2.4 × 10 m 2
/ s ) 

= 901K = 6280 C
 Solved The diffusion coefficients for nickel in iron are given at two
Example - 7 temperatures:
At 1473K 2.2 × 10-15 m2/s
At 1673K 4.8 × 10-14 m2/s
a) Determine the values of Do and the activation energy Qd.
b) What is the magnitude of D at 1300ºC (1573K)

Qd
T =− From this equation we can compute two simultaneous
R (ln Do − ln D ) equations they are

ln D1 − ln D2
Q 1 Q 1 Qd = − R
ln D1 = ln D0 − d { } ln D2 = ln D0 − d { } 1 1
−
R T1 R T2 T1 T2

[ln(2.2 × 10 −15 ) − ln(4.8 × 10 −14 )

Qd = −(8.314 J / mol − K )
1 1
−
1473 K 1673 K

= 315,700 J / mol
  Qd 
Now we can solve Do from this equation  − 
D0 = D1 e  RT1 

−15  315,700 J / mol 

= (2.2 ×10 2
m / s ) exp 
 (8.31J / mol − k )(1473k ) 

= 3.5 ×10 −4 m 2 / s

(b) Using these values of Do and Qd, D at 1573K is just

−4  315,700 J / mol 
D = (3.5 ×10 m / s ) exp −2

 (8.31J / mol − k )(1573k ) 

= 1.1× 10 −14 m 2 / s
 Summary
Diffusion Faster for Diffusion Slower for
Open crystal structures Close packed structures
Lower melting temperature materials. Higher melting temperature materials
Smaller diffusing atoms Larger diffusing atoms
Cations Anions
Materials with secondary bonding Materials with covalent bonding
Lower density materials Higher density materials