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lecture-diffusion in solids

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 Diffusion in Solids
Diffusion refers to the transport of atoms in a medium along a given
direction, It takes place in solid liquid or gas. It occurs even in the
absence of any external force.

Diffusion processes play a crucial role in many solid-state

phenomena and in the kinetics of microstructural changes during
metallurgical processing and applications.

typical examples include phase transformations :

1. Nucleation.
2. Recrystallization.
3. Oxidation.
4. Creep.
5. Sintering.
6. ionic conductivity.
7. intermixing in thin film devices.
8. Direct technological uses of diffusion include solid electrolytes
for advanced battery and fuel cell applications.
9. Semiconductor chip and microcircuit fabrication.
10. Surface hardening of steels through carburization.

Types of Diffusion :
(i) Self Diffusion : It is the transition of a thermally excited atom from a
site of crystal lattice to an adjacent site or interstice.

(ii) Inter Diffusion : This is observed in binary metal alloys such as the
(Cu-Ni) system.

(iii) Volume Diffusion : This type of diffusion is caused due to atomic

movement in bulk in materials.

(iv) Grain Boundary Diffusion : This type of diffusion is caused due to

atomic movement along the grain boundaries alone.

(v) Surface Diffusion : This type of diffusion is caused due to atomic

movement along the surface of a phase.

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Dr. Edrees Edaan Al Obeidi
 Important definition

Self-Diffusion :
It is the transition of a thermally excited atom from a site of the
crystal lattice to an adjacent site or interstice. If the solid is composed of a
single element (say pure copper), the movement of the atom is called
self-diffusion because in this case the moving atom and the solid are the
same chemical element. The process of self-diffusion is very important
for annealing and creep. Use of radioactive tracers have found to be quite
useful in determining self-diffusion coefficient.

Inter-Diffusion :
It is contrary to self-diffusion and takes place in binary metallic
alloys, e.g. the Cu-Ni system. If nickel had been plated onto the surface
of copper, then atomic diffusion would bring about nickel
homogenization within the copper, after a sufficient time, at elevated
temperatures.

Diffusion mechanisms :
i) Vacancy Mechanism :
This mechanism is a very dominant process for diffusion in FCC,
BCC and HCP metals and solid solution alloy. The activation energy for
this process comprises the energy required to create a vacancy and that
required to move it. In a pure solid, the diffusion by this mechanism is
shown in below.
Diffusion by the vacancy mechanism can occur by atoms moving into
adjacent sites that are vacant.
Concentration changes takes place due to diffusion over a period of
time.
We must note that vacancies are continually being created and
destroyed at the surface, grain boundaries and suitable interior
positions, e.g. dislocations. Obviously, the rate of diffusion increases
rapidly with increasing temperature.

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Dr. Edrees Edaan Al Obeidi
 If a solid is composed of a single element (pure metal) the
movement of thermally excited atom from a site of the crystal lattice to
an adjacent site or interstice is called self diffusion because the moving
atom and the solid are the same chemical-element.

There are two type of vacancy mechanism for atomic diffusion :

1. Pure solid solution
2. Substitutional solid solutions.

(ii) The Interstitial Mechanism :

The interstitial mechanism where an atom changes positions using
an interstitial site does not usually occur in metals for self-diffusion but is
favoured when interstitial impurities are present because of the low
activation energy.
When a solid is composed of two or more elements whose atomic
radii differ significantly, interstitial solutions may occur. The large size
atoms occupy lattice sites where as the smaller size atoms fit into the
voids (called as interstices) created by the large atoms, figure below show
this mechanism.

We must note that an activation energy is associated with

interstitial diffusion because, to arrive at the vacant site, it must squeeze
past neighbouring atoms with energy supplied by the vibrational energy
of the moving atoms.

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Dr. Edrees Edaan Al Obeidi
 The interstitial mechanism process is simpler since the presence of
vacancies is not required for the solute atom to move. This mechanism is
vital for the following cases:
(a) The presence of very small atoms in the interstices of the lattice affect
to a great extent the mechanical properties of metals.
(b) At low temperatures, oxygen, hydrogen and nitrogen can be diffused
in metals easily.

(iii) Interchange Mechanism : In this type of mechanism, the atoms

exchange places through rotation about a mid point. The activation
energy for the process is very high and hence this mechanism is highly
unlikely in most systems.
Two or more adjacent atoms jump past each other and exchange
positions, but the number of sites remains constant, as show in figures
below.

This interchange may be two-atom or four-atom (Zenner ring) for

BCC. Due to the displacement of atoms surrounding the jumping
pairs,interchange mechanism results in severe local distortion. For
jumping of atoms in this case, much more energy is required. In this
mechanism, a number of diffusion couples of different compositions are
produced, which are objectionable. This is also termed as Kirkendall’s
effect.

 Laws of Diffusion:

1. FICK’S FIRST LAW (STEADY-STATE DIFFUSION):

Diffusion can be treated as the mass flow process by which atoms (or
molecules) change their positions relative to their neighbours in a given
phase under the influence of thermal energy and a gradient.

It is necessary to know how fast diffusion occurs, or the rate of

mass transfer. This rate is frequently expressed as a diffusion flux (J),
defined as the mass (number of atoms) (M) diffusing through and
perpendicular to a unit crosssectional area of solid per unit of time.

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Dr. Edrees Edaan Al Obeidi
 𝑁
J= …………..(1)
𝐴𝑡

Where (A) denotes the area across which diffusion is occurring and
(t) is the elapsed diffusion time. In differential form, this expression
becomes

1 𝑑𝑁
J= …………..(2)
𝐴 𝑑𝑡

The units for (J) are kilograms or atoms per meter squared per
second (kg/m2.sec or atoms/m2.sec).
If the diffusion flux does not change with time, a steady-state
condition exists.

The mathematics of steady-state diffusion in a single (x) direction

is relatively simple, in that the flux is proportional to the concentration
gradient, (dC/dx) through the expression:

𝑑𝐶
J = −𝐷 …………..(3)
𝑑𝑥

Or
∆𝑥 2 𝑑𝐶
J=− …………..(4)
2∆𝑡 𝑑𝑥

Substituting Eq.(2) to (3), we get :

𝑑𝑁 𝑑𝐶
= −𝐷𝐴 …………..(5)
𝑑𝑡 𝑑𝑥

Or

This equation is sometimes called Fick’s first law. The constant of

proportionality (D) is called the diffusion coefficient, which is expressed
in (m2/sec).

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Dr. Edrees Edaan Al Obeidi
 The negative sign in this expression indicates that the direction of
diffusion is down the concentration gradient, from a high to a low
concentration.
Fick’s first law may be applied to the diffusion of atoms of a gas
through a thin metal plate for which the concentrations (or pressures) of
the diffusing species on both surfaces of the plate are held constant.

This diffusion process eventually reaches a state where in the

diffusion flux does not change with time—that is, the mass of diffusing
species entering the plate on the high-pressure side is equal to the mass
exiting from the low-pressure surface—such that there is no net
accumulation of diffusing species in the plate. This is an example of what
is termed steady-state diffusion.
When concentration (C) is plotted versus position (or distance)
within the solid (x), the resulting curve is termed the concentration
profile; furthermore, concentration gradient is the slope at a particular
point on this curve.

𝑑𝐶 Δ𝐶 𝐶𝐴 − 𝐶𝐵
𝑐𝑜𝑛𝑐𝑒𝑛𝑡𝑟𝑎𝑡𝑖𝑜𝑛 𝑔𝑟𝑎𝑑𝑖𝑒𝑛𝑡 = = = ……..…..(6)
𝑑𝑥 Δ𝑥 𝑥𝐴 − 𝑥𝐵

For diffusion problems, it is sometimes convenient to express

concentration in terms of mass of diffusing species per unit volume of
solid (kg/m3 or g/cm3).
The driving force for diffusion reactions, according to equation (3)
is the concentration gradient.

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Dr. Edrees Edaan Al Obeidi
 Q : What factors affect the diffusion rate in solid metal crystals?
The diffusion rate in solid metal crystals is affected by five factors:
1. Diffusion mechanism;
2. Temperature of diffusion;
3. Concentration of the diffusion species (concentration gradient);
4. Type of crystal structure; (bcc > fcc)
5. Type of crystal imperfections.

2. FICK’S SECOND LAW (NONSTEADY-STATE DIFFUSION):

Most practical diffusion situations are nonsteady-state that is, the
diffusion flux and the concentration gradient at some particular point in a
solid vary with time. This is illustrated in Figure below, which shows
concentration profiles at three different diffusion times.

𝑑𝐶 𝜕𝐽 𝜕 𝜕𝐶
= − =− (−𝐷 ) ……..…..(7)
𝑑𝑡 𝜕𝑥 𝜕𝑥 𝜕𝑋

known as Fick’s second law, is used. If the diffusion coefficient is

independent of composition (which should be verified for each particular
diffusion situation), Equation (7) simplifies to :
𝑑𝐶 𝜕2 𝐶
= 𝐷 ……..…..(8)
𝑑𝑡 𝜕𝑥 2

One practically important solution is for a semi-infinite solid in which the

surface concentration is held constant. The partial pressure is maintained
at a constant value. Solutions to above expression (concentration in terms
of both position and time) are possible when physically meaningful
boundary conditions are specified as follows :
Initial condition

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Dr. Edrees Edaan Al Obeidi
 For t = 0, C = Co at 0 ≤ x ≤ ∞

Boundary conditions

For t > 0, C = Cs (the constant surface concentration) at x = 0

For t > 0, C = Co at x = ∞

Application of these conditions to Equation (8) yields the solution

𝐶𝑥 −𝐶𝑜 𝑥
= 1 − 𝑒𝑟𝑓 ( ) ……..…..(9)
𝐶𝑠 −𝐶𝑜 2√𝐷𝑡

2 𝑧 2
𝑒𝑟𝑓(𝑧) = ∫ 𝑒 −𝑦 𝑑𝑦
𝜋 0
……..…..(10)
√
𝑥
Where; ( ) has been replaced by the variable (z).
2√𝐷𝑡

(Cx) : represents the concentration at depth (x) after time (t).

(Cs) : represents the concentration element at the surface.
(Co) : represents the initial uniform concentration of element in
Solid.
(x) : distance from surface.
(D) : diffusivity of diffusing solute element.
(t) : time
(erf) : mathematical Gaussian error function.function ca

Note: A bar of solid is considered to be semi-infinite if none of the

diffusing atoms reaches the bar end during the time over which diffusion
takes place. A bar of length ( l ) is considered to be semi-infinite when
( l > 10 √𝐷𝑡 ).

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Dr. Edrees Edaan Al Obeidi
 Suppose that it is desired to achieve some specific concentration of
solute, (C1), in an alloy;

the left-hand side of Equation (9) now becomes:

𝐶1 −𝐶𝑜
= 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡 ……..…..(11)
𝐶𝑠 −𝐶𝑜

the right-hand side of Equation (9) is also a constant, and subsequently:

𝑥
( ) = 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡 ……..…..(12)
2√𝐷𝑡

Or
𝑥2
( ) = 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡 ……..…..(13)
𝐷𝑡

For some diffusion situations where in time and temperature are

variables and in which composition remains constant at some value of (x),
Eq.(13) takes the form:

(𝐷𝑡) = 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡 ……..…..(14)

 FACTORS THAT INFLUENCE DIFFUSION:

1. 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.
2. Temperature :
The temperature dependence of the diffusion coefficients is

𝑄𝑑
D = 𝐷𝑜 𝑒𝑥𝑝 (− ) ……..…..(15)
𝑅𝑇

Where:
Do = a temperature-independent preexponential (m2/s).
Qd = the activation energy for diffusion (J/mol or eV/atom).
R = the gas constant, 8.31 J/mol.K or 8.62 * 10-5 eV/atom.K.
T = absolute temperature (K).

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Dr. Edrees Edaan Al Obeidi
 The activation energy may be thought of as that energy required to
produce the diffusive motion of one mole of atoms.

Taking natural logarithms of Eq.(15) yields:

𝑄 1
𝑙𝑛D = 𝑙𝑛𝐷𝑜 − ( 𝑑 ) ( ) ……..…..(16)
𝑅 𝑇

or, in terms of logarithms to the base 10:

𝑄𝑑 1
𝑙𝑜𝑔D = 𝑙𝑜𝑔𝐷𝑜 − ( )( ) ……..…..(17)
2.3𝑅 𝑇

Because (Do), (Qd), and (R) are all constants, Equation (17) takes on the
form of an equation of a straight line (Y = b + mx).

typical Arrhenius plot of log10 of the reaction rate versus reciprocal absolute
temperature

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Dr. Edrees Edaan Al Obeidi
 3. Lattice structure :
Diffusion is faster in open lattices or in open directions than in
closed directions
4. Presence of defects :
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.

 Diffusion paths in solids:

Diffusion of species in solids also depends on the path that it follows.

In a solid we can think of three distinct paths. Metals are made of several
crystals that meet along grain boundaries. If a species has to move
through this it could either move through the grain, the grain boundary or
the top surface. This is illustrated in Fig below. The diffusivity through
the grain is denoted by (Dg). This is often known as bulk diffusion
coefficient. The diffusivity through the grain boundary is denoted by
(Dgb). The space between atoms because of irregular arrangement is more
at the grain boundary than that within the grains. This is why the mobility
of atoms through the grain boundary is expected to be higher than that
through the grain. The same logic can be extended to the exposed top
surface. There is enough space to accommodate extra atoms at the free
surface if required. Therefore the mobility of the atoms along the free
surface (Ds) is much higher. The relation between the three could be
described as (Ds > Dgb > Dg).

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Dr. Edrees Edaan Al Obeidi
 The Figure also illustrates that the temperature dependence of the
diffusivity through three different paths. The activation energy of surface
diffusion is likely to be the lowest and that for the grain is the highest.
Mathematically this is denoted as (Qg > Qgb > Qs).

 Diffusion as a random walk process:

The process of diffusion is governed by the movement of atoms. In
solids where atoms are closely packed such movements will be difficult
in the absence of vacant sites. At a given temperature several lattice sites
are vacant. If there are several sites around an atom how would an atom
decide where to move ? An obvious option could be a random selection.
Fig below illustrates the difference between a normal and a random walk.

If a species moves through the lattice at a velocity (v), the distance

between its initial and final position after time t is equal to (vt), provided
with an arrow head denote the distance covered in this case. However if
the direction keeps changing randomly the distance between the initial
and final position is much less. This is shown with the help of a shorter
red line with an arrow head.
The distance between the initial and the final position is best
represented as a vector sum of each step (𝑟̅𝑖 ). The final location (𝑅̅𝑖 ) after
(n) steps of movement is given by:

……..…..(18)

The dot product of a vector with itself gives the square of its
magnitude. This is given by:

……..…..(19)

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Dr. Edrees Edaan Al Obeidi
 Each term of the second series in equation (19) denotes dot product
of two vectors. If the angle between the two is (Ɵij), and each step size is
equal to (λ) the equation (19) on simplification becomes:

……..…..(20)

Since the direction of motion is random the magnitude of (cosƟ)

could be both and negative. The sum total value is therefore likely to be
zero. Thus the average distance between the initial and final location in
this case is (𝜆√𝑛) as against (λn) in the case of normal walk. (𝑅̅𝑛 )
represents average root mean square distance. In equation (4), (∆x/∆t)
denotes the average velocity (v) of the diffusing species and (∆x) is the
average step size which equivalent to (λ). The total distance covered by
the species is (nλ). Therefore the time it takes to cover this distance is
(nλ/v). Thus by a little algebraic simplification you get the following
relations:

……..…..(20)

This shows that average random walk distance is equal to (√2𝐷𝑡).

Kirkendall Effect :
When we consider in a binary solution of A and B, the rates at
which A and B diffuse are not necessarily equal. It is observed that,
usually, the lower melting component diffuses much faster than the
other. This lead to certain effects which are interesting and first observed
by Kirkendall.

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Dr. Edrees Edaan Al Obeidi
 Inert markers, i.e. thin rods of a high melting point substance
which is insoluble in the diffusion matrix, are placed at the weld joint of
the couple, prior to the diffusion of anneal. It is found that these markers
shift during the anneal in the same direction as the slower moving
species. The extent of this shift is reported to be proportional to the
square root of the diffusion time. This type of movement reveals that the
net mass flow due to the difference in diffusivities is being compensated
by a bulk flow of matter in the opposite direction within the diffusion
zone. Obviously, lattice planes are created on one side of the diffusion
zone, while they are destroyed on the other side of the diffusion zone, and
the resulting bulk flow carries the markers along. We must note that the
bulk flow occurs relative to the ends of the diffusion couple. It is
interesting to note that it is quite a different phenomenon from the
diffusion process itself. In several cases, one observes porosity on the
lower-melting component side, indicating that the bulk flow does not
fully compensate for the difference in diffusivities of the two species. To
understand the Kirkendall effect, one may consider the analogy of
gaseous interdiffusion. Let us consider that hydrogen and argon at the
same pressure be kept in two chambers interconnected through a tube and
a frictionless piston in the tube separates the gases. When an orifice in the
piston is opened, the gases interdiffuse. Obviously, the lighter hydrogen
will diffuse faster, resulting in a pressure difference that will tend to shift
the piston in the same direction as the slower diffusion argon is moving.

Applications of Diffusion :
Diffusion processes are the basis of crystallization,
recrystallization, phase transformation and saturation of the surface of
alloys by other elements. Few important applications of diffusion are :
(i) Oxidation of metals.
(ii) Doping of semiconductors.
(iii) Joining of materials by diffusion bonding, e.g. welding,
soldering, galvanizing, brazing, and metal cladding.
(iv) Production of strong bodies by sintering, i.e. powder metallurgy
(v) Surface treatment of steels, e.g. case hardening
(vi) Important in heat treatment, e.g. homogenising treatment of
castings, recovery, recrystallization and precipitation of phases.
(vii) Diffusion is fundamental to phase changes, e.g. γ to α-iron.

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Dr. Edrees Edaan Al Obeidi
  Summary
Diffusion FASTER for...
1. open crystal structures
2. lower melting (T) materials
3. materials /secondary bonding
4. cations
5. smaller diffusing atoms
6. lower density materials
‫خالصة‬
Diffusion SLOWER for...
1. close-packed structures
2. higher melting (T) materials
3. materials /covalent bonding
4. anions
5. larger diffusing atoms
6. higher density materials

References :
1. Materials Science and Engineering; an introduction, WILLIAM
D. CALLISTER, JR. and DAVID G. RETHWISCH, John Wiley &
Sons, 2014.
2. Diffusion in solids I, Lecture 15, Kharagpur : Prof. R. N. Ghosh,
Dept of Metallurgical and Materials Engineering.
3. Materials Science, G. K. Narula، K. S. Narula، V. K. Gupta, Tata
McGraw-Hill Education, 2007.
4. Mass Transport–Induced Failure, Milton Ohring, Copyright
2020 Elsevier Journals & Books, book in Reliability and Failure of
Electronic Materials and Devices, printed in 1998.

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Dr. Edrees Edaan Al Obeidi

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