PHYSICAL METALLURGY II

Diffusion
M. Khodaei
 2
Contents
1. Diffusion
 Atomic Mechanisms of Diffusion
 Interstitial Diffusion
 Interstitial Diffusion as a Random Jump Process
 Effect of Temperature—Thermal Activation
 Steady-State Diffusion
 Nonsteady-State Diffusion
 Solutions to the Diffusion Equation

 Substitutional Diffusion
 Self-Diffusion
 Vacancy Diffusion
 Diffusion in Substitutional Alloys

 High-Diffusivity Paths
 3
Introduction
 Many reactions and processes that are important in the treatment of materials rely on
the transfer of mass either within a specific solid (ordinarily on a microscopic level)
or from a liquid, a gas, or another solid phase. This is necessarily accomplished by
diffusion.
 Materials of all types are often heat-treated to improve their properties. The phenomena
that occur during a heat treatment almost always involve atomic diffusion.
 The study of phase transformations concerns those mechanisms by which a system
attempts to reach equilibrium state and how long it takes. One of the most
fundamental processes that controls the rate at which many transformations occur is the
diffusion of atoms.
 So, the study of diffusion in solid materials is very important.
 4
Introduction
 Diffusion in solids: the phenomenon of mass transport by atomic
motion within a specific solid.

 Example: Diffusion couple, which is formed by joining bars of two different

metals together so that there is intimate contact between the two faces. This
couple is heated for an extended period at an elevated temperature (but below
the melting temperature of both metals) and cooled to room temperature.

Initial condition

Heat for a while at an elevated temperature

After diffusion
 5
Introduction

High temperature
For a long while

Initial condition After diffusion

 This result indicates that copper atoms have migrated or diffused into
the nickel, and that nickel has diffused into copper. The process by
which atoms of one metal diffuse into another is termed inter-
diffusion, or impurity diffusion.

 In almost all cases, there is a net drift or transport of atoms from high-
to low-concentration regions.
 Diffusion also occurs for pure metals, but all atoms exchanging
positions are of the same type; this is termed self-diffusion. Of course,
self-diffusion is not normally subject to observation by noting
compositional changes.
 6
Diffusion (Thermodynamic point of view)
 The reason why diffusion occurs is always so as to produce a decrease in Gibbs
free energy
 Example: Two blocks of the same A-B solid solution, but with different
compositions, are welded together and held at a temperature high enough for long-
range diffusion to occur.
 1st case
 The molar free energy of each part of the alloy will be given by G1 and G2,
and initially the total free energy of the welded block will be G3.
 However, if diffusion occurs, the free energy will decrease towards G4 (the free energy
of a homogeneous alloy)
 A decrease in free energy is produced by A and B atoms diffusing away from the regions
of high concentration to that of low concentration, i.e. down the concentration gradients.
 7
Diffusion (Thermodynamic point of view)
 The reason why diffusion occurs is always so as to produce a decrease in
Gibbs free energy
 Example: Two blocks of the same A-B solid solution, but with different
compositions, are welded together and held at a temperature high enough for
long-range diffusion to occur.
 2nd case (In alloy systems that contain a miscibility gap)
 the A and B atoms would diffuse towards the regions of high concentration, i.e. up
the concentration gradients. However, this is still the most natural process as it
reduces the free energy from G3 towards G4 again.
 8
Diffusion (Thermodynamic point of view)
 chemical potential gradient

 The A and B atoms are diffusing from regions where the chemical potential is high to
regions where it is low, i.e. down the chemical potential gradient in both cases.
 9
Diffusion (Thermodynamic point of view)
 So
 Gibbs free energy:
 diffusion always occurs to produce a decrease in Gibbs free energy.
 Chemical Concentration:
 In some cases, solute atoms diffuse from high concentration regions toward the low
concentration regions (Down the concentration gradient).
 In some cases, solute atoms diffuse from low concentration regions toward the high
concentration regions (Up the concentration gradient).
 Chemical potential:
 the solute atoms are diffusing from regions where the chemical potential is high to
regions where it is low, i.e. down the chemical potential gradient in both cases.

 NOTES:
 In practice the first case mentioned above is far more common than the second case, and it
is usually assumed that diffusion occurs down concentration gradients.
 However, since case 1 above is mainly encountered in practice and because concentration
differences are much easier to measure than chemical potential differences, it is
nevertheless more convenient to relate diffusion to concentration gradients.
 10
Atomic Mechanisms of Diffusion
 From an atomic perspective, diffusion is just the stepwise migration of atoms from
lattice site to lattice site. In fact, the atoms in solid materials are in constant motion,
rapidly changing positions.
 There are two common mechanisms for in crystalline solids
 Substitutional atoms usually diffuse by a vacancy mechanism
 Interstitial atoms migrate by forcing their way between the larger atoms, i.e. interstitially.

 In both Substitutional and Interstitial diffusion mechanisms, an atom to make

such a move, two conditions must be met:
1. There must be an empty adjacent site (WHAT KIND OF EMPTY ADJACENT SITES?!)
2. The atom must have sufficient energy to break bonds with its neighbor atoms and then
cause some lattice distortion during the displacement. (HOW TO PREPARE THIS
ENERGY?!)
 11
Atomic Mechanisms of Diffusion
 For an atom to make such a move, two conditions must be met:
1. There must be an empty adjacent site (WHAT KIND OF EMPTY ADJACENT SITES?!)
2. The atom must have sufficient energy to break bonds with its neighbor atoms and then
cause some lattice distortion during the displacement. (HOW TO PREPARE THIS
ENERGY?!)
 12
Atomic Mechanisms of Diffusion
 The energy needed for atomic migration is atomic vibrational in nature
(thermal energy).
 At a specific temperature, some small fraction of the total number of atoms is
capable of diffusive motion, by virtue of the magnitudes of their vibrational
energies. This fraction increases with rising temperature.
 13
Atomic Mechanisms of Diffusion
 In substitutional solution one mechanism involves the interchange of an atom
from a normal lattice position to an adjacent vacant lattice site or vacancy.
This mechanism is aptly termed substitutional diffusion (vacancy).
 14
Atomic Mechanisms of Diffusion
 This process necessitates the presence of vacancies, and the extent to which vacancy
diffusion can occur is a function of the number of these defects that are present.
significant concentrations of vacancies may exist in metals at elevated temperatures.
 What about two conditions?
1. Empty adjacent site: VACANCY, the concentrations of vacancies is too low and this condition
is a limiting factor.
2. Sufficient energy to break the bans: thermal vibrational energy, this condition is also a limiting
factor (JUST some portion of atoms have enough energy)

Electron microscopy of sulfur

vacancies in a monolayer of
molybdenum disulfide.
 15
Atomic Mechanisms of Diffusion
 The second type of diffusion involves atoms that migrate from an interstitial position to a
neighboring one that is empty (adjacent empty interstitial site).
 This mechanism is found for diffusion of impurities such as hydrogen, carbon, nitrogen,
which have atoms that are small enough to fit into the interstitial positions.
 Host or substitutional impurity atoms rarely form interstitials and do not normally diffuse
via this mechanism.
 16
Atomic Mechanisms of Diffusion
 The second type of diffusion involves atoms that migrate from an interstitial position to a
neighboring one that is empty (adjacent empty interstitial site).
 This mechanism is found for diffusion of impurities such as hydrogen, carbon, nitrogen,
which have atoms that are small enough to fit into the interstitial positions.
 Host or substitutional impurity atoms rarely form interstitials and do not normally diffuse
via this mechanism.
 17
Atomic Mechanisms of Diffusion
 What about two conditions?
1. Empty adjacent site: Adjacent empty interstitial site, there are more empty interstitial
positions than vacancies and this condition is not a limiting factor.
2. Sufficient energy to break the bans: thermal vibrational energy, this condition is a limiting
factor (JUST some portion of atoms have enough energy)

 In most metal alloys, interstitial diffusion occurs much more rapidly than diffusion by
the vacancy mode, because the interstitial atoms are smaller and thus more mobile.
Furthermore, there are more empty interstitial positions than vacancies; hence, the
probability of interstitial atomic movement is greater than for vacancy diffusion.
 18
Interstitial Diffusion
Interstitial Diffusion as a random Jump Process
 Consider first a simple model: A dilute interstitial solid solution where the parent atoms
are arranged on a simple cubic lattice and the solute B atoms fit perfectly into the
interstices without causing any distortion of the parent lattice.

 If the concentration of B varies in x

direction, the B atoms can diffuse
throughout the material until their
concentration is the same everywhere.

 How this diffusion is related to the

random jump characteristics of the
interstitial atoms.
 19
Interstitial Diffusion
Interstitial Diffusion as a random Jump Process
 consider the exchange of atoms between two adjacent atomic planes such as (1) and
(2)
 Assume that on average an interstitial atom jumps ΓB times per second and that each jump
is in a random direction.
 Atom jumping to every one of the six adjacent sites (1 / 6 to +x direction)

 If plane (1) contains n1 B-atoms per m2 the number of atoms that will jump from plane (1) to
(2) in 1 s (J) will be given by:

 And jump from plane (2) to (1)

 20
Interstitial Diffusion
Interstitial Diffusion as a random Jump Process
 Since n1 > n2 there will be a net flux of atoms from left to right given by

 where n1 and n2 are related to the concentration of B in the lattice.

 If the separation of planes (1) and (2) is α the concentration of B at the position of plane (1) is

 Likewise

 Therefore
 21
Interstitial Diffusion
Interstitial Diffusion as a random Jump Process
 It can be seen that

 So

 The equation may be rewrite as Fick’s first law

 22
Interstitial Diffusion
effect of Temperature—Thermal Activation
 Jump process for an interstitial atom

(a) in equilibrium position, (b) at the position of maximum lattice distortion, (c) Variation of the
free energy of the lattice as a function of the position of interstitial.

 BUT, How to prepare the energy??

 23
Interstitial Diffusion
effect of Temperature—Thermal Activation
 The distributions of particles with the number of ways each distribution can be
produced according to Maxwell-Boltzmann statistics where each particle is
presumed to be distinguishable energy level
 24
Interstitial Diffusion
effect of Temperature—Thermal Activation
 Due to the thermal energy of the solid all the atoms will be vibrating about their
rest positions.
 Occasionally a particularly violent oscillation of an interstitial atom, or some
chance coincidence of the movements of the matrix and interstitial atoms, will
result in a jump.

 The diffusion coefficient is closely related to the frequency of such jumps, Γ, it

is of interest to know the factors controlling Γ and the effect of raising the
temperature of the system.

 In order to move an interstitial atom to an adjacent interstice the atoms of the

parent lattice must be forced apart into higher energy positions.
 The work that must be done to accomplish this process causes an increase in the
free energy of the system by ΔGm (m refers to migration).
 ΔGm is known as the activation energy for the migration of the interstitial atom.
 25
Interstitial Diffusion
effect of Temperature—Thermal Activation
 On average, the fraction of atoms with an energy of ΔG or more than the mean
energy is given by exp(−∆G / RT).
 If the interstitial atom is vibrating with a mean frequency ν in the x direction it
makes ν attempts per second to jump into the next site and the fraction of these
attempts that are successful is given by exp(−∆G / RT)
 Now the atom is randomly vibrating in three-dimensional space, and if it is
surrounded by z sites to which it can jump the jump frequency is given by

 This can be simplified to an Arrhenius-type equation, that is

 26
Interstitial Diffusion
effect of Temperature—Thermal Activation

 Top Equation is found to agree with experimental measurements of diffusion coefficients

in substitutional as well as interstitial diffusion.
 In the case of interstitial diffusion it has been shown that the activation enthalpy Q is
only dependent on the activation energy barrier to the movement of interstitial atoms
from one site to another.
 Example: The diffusion of various interstitials in bcc-Fe

 Diffusion increases as the size of the interstitial atom decreases. (The atomic diameters
decrease in the order C, N, H.)
 27
Interstitial Diffusion
effect of Temperature—Thermal Activation
 Graphical representation of D as a function of temperature

 So,
 28
Interstitial Diffusion
Steady-State Diffusion
 The simplest type of diffusion to deal with is when a steady state exists, that is when
the concentration at every point does not change with time.

 Example: consider a thin-walled pressure vessel containing hydrogen. The

concentration of hydrogen at the inner surface of the vessel will be maintained at a
level CH depending on the pressure in the vessel, while the concentration at the outer
surface is reduced to zero by the escape of hydrogen to the surroundings.

 A steady state will eventually be reached when the concentration everywhere reaches
an unchanged value.
 29
Interstitial Diffusion
Steady-State Diffusion
 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 reaches a state wherein 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.
 30
Interstitial Diffusion
Steady-State Diffusion
 The concentration gradient is the slope at a particular point on this curve. In the present
treatment, the concentration profile is assumed to be linear.

 One another practical example of steady-state diffusion is found in the purification of

hydrogen gas. One side of a thin sheet of palladium metal is exposed to the impure gas
composed of hydrogen and other gaseous species such as nitrogen, oxygen, and water
vapor. The hydrogen selectively diffuses through the sheet to the opposite side, which is
maintained at a constant and lower hydrogen pressure.
 31
Interstitial Diffusion
Nonsteady-State Diffusion (Fick’s 2nd law)
 Most practical diffusion situations are nonsteady-state ones—that is, the diffusion flux
and the concentration gradient at some particular point in a solid vary with time, with a
net accumulation or depletion of the diffusing species resulting.

t=0

t>0
 32
Interstitial Diffusion
Nonsteady-State Diffusion (Fick’s 2nd law)
 In order to calculate how the concentration of B at any point varies with time consider a
narrow slice of material with an area A and a thickness δx

 The mass entering the slice in δt equals

 and the mass exiting

 The change in impurity mass

 33
Interstitial Diffusion
Nonsteady-State Diffusion (Fick’s 2nd law)
 By rearranging of the equation

and dividing both side by δx

Or

 For small δx and δt

Fick’s Second law

And finally
 34
Interstitial Diffusion
Nonsteady-State Diffusion (Fick’s 2nd law)
 Under conditions of nonsteady-state the partial differential equation

 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), the Equation
simplifies to

 Solutions to this expression (concentration in terms of both position and time) are possible
when physically meaningful boundary conditions are specified.
 For 3D problem in a same manner
 35
Interstitial Diffusion
Nonsteady-State Diffusion (Fick’s 2nd law)
 Graphical interpretation of is the curvature of the CB versus x curve.
 If the concentration profile appears as shown in the below Fig., it has a positive curvature
everywhere and the concentration at all points on such a curve will increase with time.

Positive
 When the curvature is negative then CB decreases with time.

Negative
 36
Interstitial Diffusion
Solutions to the Diffusion equation – Homogenization
 It is often of interest to be able to calculate the time taken for an inhomogeneous alloy to
reach complete homogeneity, as for example in the elimination of segregation in
castings.
 Example: segregation of alloying elements on grain boundaries

X
X
 37
Interstitial Diffusion
Solutions to the Diffusion equation – Homogenization
 The simplest composition variation that can be solved mathematically is if CB varies
sinusoidally with distance in one dimension

 At time t = 0 the concentration profile is given by

 where is the mean composition, and β0 is the amplitude of the initial concentration
profile.
 38
Interstitial Diffusion
Solutions to the Diffusion equation – Homogenization
 To predict the distribution of concentration of the alloying element during
homogenization, we must consider the governing equation, boundary
conditions and initial conditions

 By solving the problem

 where τ is a constant called the relaxation time and is given by

 Thus the amplitude of the concentration profile after a time t is given by C

 at x = l/2, i.e.
 39
Interstitial Diffusion
Solutions to the Diffusion equation – Homogenization
 In other words, the amplitude of the concentration profile decreases exponentially
with time and after a sufficiently long time approaches zero.
 After a time t = τ then β=β0/ e that is, the amplitude has decreased to 1 / 2.72 of its value
at t = 0.
 After a time t = 2τ the amplitude is reduced by a total of 1/e2 and …
Time τ 2τ 3τ --- nτ

Amplitude β 0/ e β 0/ e 2 β 0/ e 3 β 0/ e n
 40
Interstitial Diffusion
Solutions to the Diffusion equation – Semi-infinite solution x
 Example: The Carburization of Steel t=0
 The aim of carburization is to increase the carbon concentration in the surface layers of
a steel product in order to achieve a harder wear-resistant surface. This is usually done
by holding the steel in a gas mixture containing CH4 and/or CO at a temperature where
it is austenitic.
 An analytical expression for these profiles can be obtained by solving Fick’s second law
using the boundary conditions. The specimen is considered to be infinitely long.

 By solving the problem

 or
 41
Interstitial Diffusion
Solutions to the Diffusion equation – Semi-infinite solution
 The erf function is shown graphically as below

 Carbon concentration
 42
Interstitial Diffusion
Solutions to the Diffusion equation – Semi-infinite solution
 Note that since erf (0.5) ≈ 0.5 then
if suppose

so

then

 So, the depth at which the carbon concentration is midway between Cs and C0 is given by

 The thickness of the carburized

 layer ( √ Dt) is called penetration depth
 43
Interstitial Diffusion
Solutions to the Diffusion equation – Semi-infinite solution
 There are other situations in which the solution to the diffusion equation is in semi-infinite
condition.
 Example: decarburization of steel
 During decarburization of steel the surface concentration is reduced to a very low value
and carbon diffuses out of the specimen.

 The carbon profile is then given by

 44
Interstitial Diffusion
Solutions to the Diffusion equation – Semi-infinite solution
 Example: Junction
 Another example arises if two semi-infinite specimens of different compositions C1
and C2 are joined together and annealed. The profiles in this case are shown below

 The concentration profile is then given by

 45
Substitutional Diffusion
 Diffusion in dilute interstitial alloys was relatively simple because the diffusing atoms are
always surrounded by ‘vacant’ sites to which they can jump whenever they have enough
energy to overcome the energy barrier for migration.
 In substitutional diffusion, however, an atom can only jump if there happens to be a
vacant site at one of the adjacent lattice positions.
 The simplest case of substitutional diffusion is the self-diffusion of atoms in a pure metal.
 46
Substitutional Diffusion
Self-Diffusion
 The simplest case of substitutional diffusion is the self-diffusion of atoms in a pure metal where
the host atoms are diffusing in the self lattice.
 How to measure the rate of self-diffusion?
 The rate of self-diffusion can be measured experimentally by introducing a few radioactive A atoms (A*)
into pure A and measuring the rate at which penetration occurs at various temperatures.
 Since A* and A atoms are chemically identical their jump frequencies are also almost identical.

 Example:
 47
Substitutional Diffusion
Self-Diffusion
 Since A* and A atoms are chemically identical their jump frequencies are also almost
identical. Thus the diffusion coefficient can be related to the jump frequency by below
Equation

 How to calculate the Jumping frequency 

 An atom next to a vacancy attempt to jumping by frequency of thermal vibrating frequency 
 This atom can make a jump provided it has enough thermal energy to overcome the activation
energy barrier to migration, ΔGm. Therefore the probability that any attempt at jumping will be
successful is given by exp(−∆Gm/RT)
 However, most of the time the adjacent site will not be vacant and the jump will not be possible. The
probability that an adjacent site is vacant is given by zXv where z is the number of nearest
neighbors and Xv is the probability that any one site is vacant, which is just the mole fraction of
vacancies in the metal.
 Combining all these probabilities gives the probability of a successful jump as
 48
Substitutional Diffusion
Self-Diffusion
 If the vacancies are in thermodynamic equilibrium, Xv = Xev as given by

 Combining these last equations gives

 so

 This equation can be written more concisely as

 49
Substitutional Diffusion
Self-Diffusion
 The equation of diffusion coefficient for self-diffusion is the same as was obtained for
interstitial diffusion except that the activation energy for self-diffusion has an extra term
(ΔHv). This is because self-diffusion requires the presence of vacancies whose
concentration depends on ΔHv.

 It can be seen that for a given crystal structure and bond type Q/RTm is roughly
constant; that is, the activation enthalpy for self-diffusion, Q, is roughly proportional to
the equilibrium melting temperature, Tm.
 50
Substitutional Diffusion
Self-Diffusion
 An immediate consequence of these correlations is that the diffusion coefficients of all
materials with a given crystal structure and bond type will be approximately the same at the
same fraction of their melting temperature, i.e. D(T/Tm) = constant.
 BUT WHY?
 Increasing the interatomic bond strength makes the process of melting more difficult; that is, T m is
raised.
 It also makes diffusion more difficult by increasing ΔHv and ΔHm.
 51
Substitutional Diffusion
Vacancy Diffusion
 The jumping of atoms into vacant sites can equally well be considered as the jumping of vacancies
onto atom sites.

Jumping of
an atom into
a vacant site
Jumping of a
vacancy onto
an atom site

 If excess vacancies are introduced into the lattice they will diffuse at a rate which depends on the
jump frequency.
 However, a vacancy is always surrounded by sites to which it can jump and it is thus analogous to
an interstitial atom.
 Therefore a vacancy can be considered to have its own diffusion coefficient given by
 52
Substitutional Diffusion
Vacancy Diffusion
 The jumping of atoms into vacant sites can equally well be considered as the jumping of vacancies
onto atom sites.

Jumping of
an atom into
a vacant site
Jumping of a
vacancy onto
an atom site

 By analogy with the rate Equation of intestinal diffusion

 and by comparing Equations

 53
Substitutional Diffusion
Diffusion in Substitutional Alloys
 During self-diffusion all atoms are chemically identical. Thus the probability of finding a
vacancy adjacent to any atom and the probability that the atom will make a jump into the
vacancy is equal for all atoms. This leads to a simple relationship between jump frequency and
diffusion coefficient.
 In binary substitutional alloys, however, the situation is more complex. In general, the rate at
which solvent (A) and solute (B) atoms can move into a vacant site is not equal and each atomic
species must be given its own intrinsic diffusion coefficient DA or DB
 DA and DB are defend such that Fick’s first law applies to diffusion relative to the lattice, that is

 where JA and JB are the fluxes of A and B atoms across a given lattice plane.
 In the case of interstitial diffusion because the lattice planes of the parent atoms were unaffected
by the diffusion process. It will be seen, however, that the situation is different in the case of
substitutional diffusion.
 54
Substitutional Diffusion
Diffusion in Substitutional Alloys
 Consider the inter diffusion of A and B atoms in a diffusion couple that is made by welding together
blocks of pure A and B. If the couple is annealed at a high enough temperature, a concentration
profile will develop

 If we make the simplifying assumption that the total number of atoms per unit volume is a
constant, C0, independent of composition, then

 so
 55
Substitutional Diffusion
Diffusion in Substitutional Alloys
 Hence at a given position the concentration gradients driving the diffusion of A and B atoms
are equal but opposite, and the fluxes of A and B relative to the lattice can be written as

 for the case DA > DB, i.e. |JA| > |JB|

 56
Substitutional Diffusion
Diffusion in Substitutional Alloys
 In the vacancy mechanisms the jumping of an atom into a vacant site can equally well be
regarded as the jumping of the vacancy onto the atom.
 In other words, if there is a net flux of atoms in one direction there is an equal flux of
vacancies in the opposite direction.
 Thus there is a flux of vacancies −JA due to the migration of A atoms plus a flux of vacancies
−JB due to the diffusion of B atoms.
 57
Substitutional Diffusion
Diffusion in Substitutional Alloys
 In order to maintain the vacancy concentration everywhere near equilibrium
 vacancies must be created on the B-rich side and
 destroyed on the A-rich side.

 The rate at which vacancies are created or destroyed at any point is given by
 58
Substitutional Diffusion
Diffusion in Substitutional Alloys
 How to create or destroy the vacancies?
 Jogged edge dislocations can provide a convenient source or sink for vacancies
 Destroying the vacancies

before After

 Vacancies can be absorbed by the extra half-plane of the edge dislocation shrinking
 59
Substitutional Diffusion
Diffusion in Substitutional Alloys
 How to create or destroy the vacancies?
 Jogged edge dislocations can provide a convenient source or sink for vacancies
 Creating the vacancies

before After

 Vacancies can be emitted from the extra half-plane of the edge dislocation growth
 60
Substitutional Diffusion
Diffusion in Substitutional Alloys
 This means that extra atomic planes will be introduced on the B-rich side while whole
planes of atoms will be ‘eaten’ away on the A-rich side.

 Consequently the lattice planes in the middle of the couple will be shifted to the left.
 61
Substitutional Diffusion
Diffusion in Substitutional Alloys - Kirkendall effect
 In order to show the movement of the lattice at a given point in the couple, insoluble wires are
inserted at the interface before welding the two blocks together. These wires remain in effect
‘fixed’ to the lattice planes.
 The displacement of inert wires during diffusion was first observed by Smigelskas and
Kirkendall in 1947 and is usually known as the Kirkendall effect.
 In this experiment a block of α-brass (Cu-30wt% Zn) was wound with molybdenum wire and
encapsulated in a block of pure Cu.

 After annealing at a high temperature it was found that the separation of the markers (w) had
decreased. This is because DZn > DCu and the zinc atoms diffuse out of the central block faster
than they are replaced by copper atoms diffusing in the opposite direction.
 Similar effects have since been demonstrated in many other alloy systems. In general it is found
that in any given couple, atoms with the lower melting point possess a higher D
 62
Substitutional Diffusion
Diffusion in Substitutional Alloys
Vacancies are not necessarily all annihilated at dislocations, but can also be absorbed by internal
boundaries and free surfaces.
However, those not absorbed at dislocations mainly agglomerate to form holes or voids in the
lattice. Void nucleation is difficult because it requires the creation of a new surface and it is generally
believed that voids are heterogeneously nucleated at impurity particles.

The experimental result of Kirkendall porosity in Cu-NiAl

diffusion couple
 63
Substitutional Diffusion
Diffusion in Substitutional Alloys
Example: Kirkendall effect in nanomaterial synthesis

 Nanoshell

 Nano copper oxide

 Nanotube
 64
Substitutional Diffusion
Diffusion in Substitutional Alloys
 The velocity at which any given lattice plane moves, v, can be related to the flux of
vacancies crossing it.
 If the plane has an area A, during a small time interval δt, the plane will sweep out a volume
of Avδt containing Av δt C0 atoms.
 This number of atoms is removed by the total number of vacancies crossing the plane in the
same time interval, i.e. J A δt, giving

 Thus

 where the mole fraction of A, XA = CA/C0

 65
Substitutional Diffusion
Diffusion in Substitutional Alloys
 Consider a thin slice of material δx thick at a fixed distance x from one end of the couple
which is outside the diffusion zone.
 If consider the total flux of A atoms entering and leaving

 Using the same arguments as were used to derive the 2nd Fick’s law, we can show that

 The total flux of A atoms across a stationary plane with respect to the specimen is the sum
of two contributions:
1. a diffusive flux − DA ∂CA/ ∂x due to diffusion relative to the lattice, and
2. a flux υCA due to the velocity of the lattice in which diffusion is occurring.

 Therefore:
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Substitutional Diffusion
Diffusion in Substitutional Alloys
 By combining this equation we obtain the equivalent of Fick’s first law for the flux relative
to the specimen ends:

 by defining an inter-diffusion coefficient as

 Likewise

 i.e.
Fick’s Second law
for Substitutional
Diffusion
 By substituting J’A into , we have

 These equations were first derived by Darken and are usually known as Darken’s equations
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Substitutional Diffusion
Diffusion in Substitutional Alloys
 In concentrated alloys the experimentally determined values of inter-diffusion
coefficient, DA and DB are also found to show the same form of temperature dependence
as all other diffusivities, so that
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Substitutional Diffusion
High-Diffusivity Paths
 In this section diffusion along dislocations, interfaces, grain boundaries and free
surfaces will be discussed.
 All of these defects are associated with a more open structure and it has been shown
experimentally that the jump frequency for atoms migrating along these defects is
higher than that for diffusion in the lattice.
 It will become apparent that under certain circumstances diffusion along these defects
can be the dominant diffusion path.
 It is found experimentally that diffusion along grain boundaries and free surfaces can be
described by

 In general, at any temperature the magnitudes of Db and Ds relative to the diffusivity

through defect-free lattice D1, are such that

 This mainly reflects the relative ease with which atoms can migrate along free
surfaces, interior boundaries and through the lattice.
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Substitutional Diffusion
High-Diffusivity Paths
 Surface diffusion can play an important role in many metallurgical phenomena, but in an
average metallic specimen the total grain boundary area is much greater than the
surface area so that grain boundary diffusion is usually most important.
 The effect of grain boundary diffusion can be illustrated by considering a diffusion couple
made by welding together two metals, A and B.

 A atoms diffusing along the boundary will be able to penetrate much deeper than atoms
which only diffuse through the lattice.
 In addition, as the concentration of solute builds up in the boundaries atoms will also
diffuse from the boundary into the lattice.
 Points in the lattice close to grain boundaries can receive solute via the high conductivity
path much more rapidly than if the boundaries were absent.
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Substitutional Diffusion
High-Diffusivity Paths - Grain boundary diffusion
 For simplicity let us take a case of steady-state diffusion through a sheet of material in which
the grain boundaries are perpendicular to the sheet

 Assuming that the concentration gradients in the lattice

and along the boundary are identical, the fluxes of solute
through the lattice Jl and along the boundary Jb will be
given by

 If the grain boundary has an effective thickness δ and

the grain size is d, the material diffusing through the
element during t is

 so
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Substitutional Diffusion
High-Diffusivity Paths - Grain boundary diffusion
 Then

 Or

 Thus the apparent diffusion coefficient in this case

 Or

 It can be seen that the relative importance of lattice and grain boundary diffusion depends on
the ratio Dbδ/D1d. When Dbδ > D1d diffusion through the lattice can be ignored in
comparison to grain boundary diffusion.
 The effective width of a grain boundary is ∼0.5 nm. Grain sizes on the other hand can vary
from ∼1 to 1000 µm and the effectiveness of the grain boundaries will vary accordingly.
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Substitutional Diffusion
High-Diffusivity Paths - Grain boundary diffusion
 The relative magnitudes of Dbδ and D1d are most sensitive to temperature.

 Note that although Db > Dl, at all temperatures the difference increases as temperature
decreases.
 This is because the activation energy for diffusion along grain boundaries (Qb) is lower
than that for lattice diffusion (Ql). BUT WHY?
 For example, in fcc metals it is generally found that Qb ~ 0.5 Ql.
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Substitutional Diffusion
High-Diffusivity Paths - Grain boundary diffusion
 The relative magnitudes of Dbδ and D1d are most sensitive to temperature.

 This means that when the grain boundary diffusivity is scaled by the factor δ/d, the grain
boundary contribution to the total, or apparent, diffusion coefficient is negligible in
comparison to the lattice diffusivity at high temperatures, but dominates at low temperatures.
 In general it is found that grain boundary diffusion becomes important below about 0.75-0.8
Tm, where Tm is the equilibrium melting temperature in Kelvin.
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Substitutional Diffusion
High-Diffusivity Paths - Diffusion along Dislocations
 If grain boundary diffusion is compared to the conduction of heat through a material made
of sheets of aluminum in a plastic matrix, the analogy for diffusion along dislocations
would be aluminum wires in a plastic matrix. The dislocations effectively act as pipes
along which atoms can diffuse with a diffusion coefficient Dp.

 The contribution of dislocations to the total diffusive flux through a metal will of course
depend on the relative cross-sectional areas of pipe and matrix.

 where g is the cross-sectional area of ‘pipe’ per unit area of matrix.

 At high temperatures diffusion through the lattice is rapid and gDp/D1 is very small so that
the dislocation contribution to the total flux of atoms is negligible. However, since the
activation energy for pipe diffusion is less than for lattice diffusion, D 1 decreases much
more rapidly than Dp with decreasing temperature, and at low temperatures gDp/D1 can
become so large that the apparent diffusivity is entirely due to diffusion along dislocations.
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