LECTURE 5

“ATOM MOVEMENT IN MATERIALS”

Lecture Goals
• To know:-
 What diffusion mechanisms occur:-
 Self-diffusion
 Vacancy or substitutional atom diffusion
 Interstitial diffusion
 What factors influence the flux [J = -D(∆c /∆x) – Fick’s First
Law ] during diffusion:-
 Diffusivity or diffusion coefficient (D)
 Concentration gradient (∆c/∆x)
 What factors influence diffusivity [ D = D0exp(-Q/RT) ]:-
 D0 – a constant for a given diffusion system
Lecture Goals (contd)
 Q – activation energy
 R – gas constant
 T – absolute temperature
 What factors influence Q & hence J:-
 Type of diffusion
 Crystal structure
 Atomic bonding
 Ionic radius
 What types of diffusion occur:-
 Volume diffusion
 Grain boundary diffusion
Lecture Goals (contd)
 Surface diffusion
• To be able to use one solution:
{(cs – cx)/(cs – c0) = erf[x/2(Dt)1/2]} to Fick’s Second Law:
dc/dt = D(d2c/dx2), to:-
 Calculate the concentration of one diffusing species near the
surface of the material, as a function of time & distance
 Design a variety of materials processing techniques
 Grain growth
 Diffusion bonding
 Sintering
1. Diffusion Mechanisms
1.1 Self-diffusion
• Occurs continually in all materials
• Has insignificant effect on materials’ behaviour
Fig.1 shows a nickel (Ni) sheet bonded to a copper (Cu) sheet. Ni
atoms gradually diffuse into Cu & Cu atoms into Ni until the Ni &
Cu atoms are uniformly distributed.
Fig.2 shows the two diffusion mechanisms that have significant
effect on materials’ properties.
1.2 Vacancy or substitutional diffusion
An atom leaves its lattice site to fill a nearby vacancy, thus
creating a new vacancy at the original site, resulting in a
counter-current flow of atoms & vacancies.
• The number of vacancies increases with temperature.
Fig. 1. Diffusion of Copper (Cu) into Nickel (Ni).
Fig. 2. Diffusion mechanisms in materials: (a) vacancy or substitutional
atom diffusion (b) interstitial diffusion.
1. Diffusion Mechanisms (contd)
1.3 Interstitial diffusion
• No vacancies are required for this diffusion mechanism
• Because there are many more interstitial sites than vacancies,
interstitial diffusion must be more rapid than vacancy diffusion.
Note 1: Key Definitions
 Diffusion – the movement of atoms within a material.
 Self-diffusion – the random movement of atoms within a pure
material – that is, even when no concentration gradient is
present.
 Vacancy diffusion – diffusion of atoms involving an atom
leaving a regular lattice site to fill a vacancy in a crystal. This
process creates a new vacancy & the process contintues.
Note 1: Key Definitions (contd)
 Interstitial diffusion – diffusion of small atoms from one
interstitial site to another in the crystal structure.
2. Activation Energy for Diffusion
Fig.3 schematically compares the energies required (activation
energies) to force an atom in a low-energy, relatively stable
site, to a new site; for vacancy & interstitial diffusion.
• Heat supplies the atom with the activation energy
• Generally, more energy is required for a substitutional atom
than for an interstitial atom (Table 1).
Note 2: Key Definition
 Activation energy for diffusion – energy required to move an
atom from one lattice site to another.
Fig. 3. Comparison of activation energies for substitutional (vacancy) and
interstitial diffusion.
Table 1. Diffusion data for selected materials.
3. Rate of Diffusion (Fick’s First Law)
Fig.4 schematically shows flux (J) during diffusion:-
J = -D(∆c/∆x) ……………………………………………………………….(1)
where J – flux (atom.m-2.s-1), D – diffusivity or diffusion
coefficient (m2.s-1), ∆c/∆x – concentration gradient
(atoms.m-3.m-1).
3.1 Factors influencing flux
3.1.1 Concentration gradient ∆c/∆x (Fig.5) – shows how the
composition of the material (∆c) varies with distance (∆x).
What gives rise to the concentration gradient?
• When two materials of different composition are in contact
• When a gas or liquid is in contact with a solid material
Fig. 4. Flux during diffusion.
Fig. 5. Illustration of the concentration gradient.
3.1 Factors influencing flux (contd)
• When non-equilibrium structures are produced in a material
due to processing
3.1.2 Diffusivity D
D = D0exp(-Q/RT) ………………………………………………………..(2)
where D0 – a constant for a given diffusion system (Table 1),
Q – activation energy (J.mol-1) for a given diffusion system
(Table 1), R – gas constant (8.314 J.mol-1.K-1), T – absolute
temperature (K).
Fig.6 shows the temperature dependence of D for selected
materials.
Why are the heat treatment of metals & the processing of
ceramics done at high temperatures?
Fig. 6. The steeper the D vs 1/T plot the higher the Q.
3.1 Factors influencing flux (contd)
• Because when the temperature of a material increases, the
diffusion coefficient & hence the flux increases.
• Because at temperatures below about 0.4 times the absolute
melting temperature of the material, diffusion is very low.
3.1.3 Activation energy Q – a small activation energy Q increases
the diffusion coefficient (D) & hence flux (J).
Two factors influence Q:-
• Type of diffusion (Table 2)
Because of the surrounding atoms, movement of atoms from
one lattice or interstitial site to another through the crystal, in
volume diffusion, is associated with a large Q.
Table 2. The effect of the type of diffusion for thorium in tungsten and
for self diffusion in silver.
3.1 Factors influencing flux (contd)
Because atoms can easily squeeze through the disordered
grain boundary, Q is low for grain boundary diffusion.
Because there is even less constraint on the diffusing atoms at
the surface, Q is even lower for surface diffusion.
• Structure of the material
 Crystal structure
Q is typically lower for atoms diffusing through open crystal
structures than for close-packed crystal structures.
 Atomic bonding
Q is typically lower for diffusion of atoms in materials with a
low melting temperature (Fig.7).
Fig. 7. The higher the melting point, the higher the Q for self diffusion.
3.1 Factors influencing flux (contd)
Because of the high strength of their atomic bonds, covalently
bonded materials, such as carbon (C) & silicon (Si), have
unusually high Q (Table 1).
In ionic materials, a diffusing ion only enters a site having the
same charge. To reach that site, the ion must squeeze past a
region of opposite charge & move a relatively long distance
(Fig.8). Hence, Q for ionic materials, such as ceramics, are
high & flux is lower than for metals.
 Ionic radius
Being smaller in size, cations often have lower Q than anions.
The Q for diffusion of Cl- is about twice that for diffusion of
Na+.
Fig. 8. Diffusion in ionic compounds. Anions can only enter other anion
sites.
Note 3: Key Definitions
 Fick’s First Law – the equation relating the flux of atoms by
diffusion to the diffusion coefficient & the concentration
gradient.
 Diffusivity or diffusion coefficient – a temperature-dependent
coefficient related to the rate at which atoms diffuse.
Diffusivity depends on temperature (T) & activation energy
(Q).
 Concentration gradient – the rate of change of composition
with distance in a non-uniform material, expressed as
atoms .m-3.m-1 or at%m-1.
 Volume diffusion – diffusion of atoms through the interior of
grains.
Note 3: Key Definitions (contd)
 Grain boundary diffusion – diffusion of atoms along grain
boundaries. This is faster than volume diffusion, because the atoms
are less closely packed in grain boundaries.
 Surface diffusion – diffusion of atoms along surfaces, such as cracks
or particle surfaces.
4. Composition Profile (Fick’s Second Law)
Fig.9 illustrates the concentrations (cs, c0, cx), featuring in a solution
(3) to Fick’s second law [dc/dt = D(d2c/dx2), for given boundary
conditions.
(cs – cx)/(cs – c0) = erf[x/2(Dt)1/2] ……………………………………….(3)
where cs – a constant concentration of the diffusing atoms at the
surface of the material, c0 – the initial uniform concentration of the
diffusing atoms in the material, cx – the concentration
Fig. 9. Diffusion of atoms into the surface of a material according to
Fick’s second law.
4. Composition Profile (Fick’s Second Law) (contd)
of the diffusing atoms at a location x below the surface after
time t. The error function erf can be evaluated from Table 3.
Use of (3) to calculate the concentration of one diffusing
species near the surface of the material as a function of time
& distance requires that D remains constant & cs & c0 remain
unchanged. The requirement that there be a constant
composition at the interface is realizable in a process such as
carburizing of steel, in which carbon is continuously supplied
to the steel surface. However, in many cases the surface
concentration gradually changes during diffusion, leading to
inter-diffusion of atoms (Fig.1), & (3) is no longer valid.
Table 3. Error function for Fick’s law.
Note 4: Key Definitions
 Fick’s Second Law – the partial differential equation that
describes the rate at which atoms are redistributed in a
material by diffusion.
 Inter-diffusion – diffusion of different atoms in opposite
directions. Inter-diffusion may eventually produce equilibrium
concentration of atoms within the material.
Inter-diffusion can cause difficulties. Under what
circumstances can inter-diffusion cause difficulties?
In tiny integrated circuits, gold (Au) is welded to aluminium (Al)
to provide an external lead for the circuit. During operation of
the circuit, the Al atoms diffuse faster into the Au than Au
atoms diffuse into the Al, resulting in more total atoms being
on the original Au side than on the original Al
Note 4: Key Definitions (contd)
side. The physical location of original interface moves towards
the Al side of the diffusion couple, along with any foreign
particles originally trapped at the interface (Kirkendall effect).
Coalescence of vacancies involved in the diffusion may lead to
formation of voids. Growth of the voids weakens the Au-Al
connection, a process associated with discolouring of the area
around the connection (purple plague).
Exposure of the weld to hydrogen (H), which dissolves in the
Al, filling the vacancies, prevents self-diffusion of the Al
atoms, inhibiting the diffusion of the Al atoms into the Au,
which embrittles the weld.
 Kirkendall effect – physical movement of an interface due to
unequal rates of diffusion of the atoms within a material.
Note 4: Key Definitions (contd)
 Purple plague – formation of voids in Au-Al welds due to
unequal rates of diffusion of the two atoms; eventually, failure
of the weld can occur.
5. Diffusion & Materials Processing
5.1 Materials processing by grain growth
Fig.10 illustrates diffusion of atoms across the grain boundary,
leading to the growth of some grains at the expense of others.
Grain growth is promoted by:-
• High temperatures
• Low Q
5.2 Diffusion bonding
Fig.11 illustrates diffusion bonding:-
Fig. 10. Grain growth occurs as atoms diffuse across the grain boundary
from one grain to another.
Fig. 11. Diffusion bonding.
5. Diffusion & Materials Processing (contd)
(a) High temperature & pressure are required to force the two
surfaces together, flattening the surface, fragmenting
impurities & producing a high atom-to-atom contact area.
(b) High temperature & pressure are required for diffusion of
atoms along grain boundaries to the remaining voids. The
atoms condense & reduce the size of any voids in the
interface. Because grain boundary is rapid, (b) may occur
very quickly. Eventually, however, grain growth isolates the
remaining voids from the grain boundaries.
(c) Volume diffusion, which is comparatively slow, is required for
the elimination of the remaining voids.
Diffusion bonding is used for joining:-
• reactive metals such as Titanium (Ti)
5. Diffusion & Materials Processing (contd)
• dissimilar metals & materials
• ceramics
5.3 Sintering
Fig.12 illustrates the process of sintering . In order to reduce
the particle surface energy, atoms diffuse to the points of
contact, bonding the particles together & eventually causing
the pore space between the bonded particles to shrink. Over
time, sintering may lead to the elimination of pore spaces,
increasing the density of the material.
The rate of sintering is determined by: the original size of the
particles, activation energy (Q) & diffusion coefficient (D) for
diffusion, temperature (T).
Fig. 12. Sintering.
5. Diffusion & Materials Processing (contd)
Sintering is used in the:-
• Manufacture of ceramics
• Production of metallic products by powder metallurgy
• Production of many composite materials
Note 5: Key Definitions
 Grain growth – movement of grain boundaries by diffusion in
order to reduce the amount of grain boundary area. As a
result, small grains shrink & disappear & other grains become
larger.
 Diffusion bonding – a joining technique in which two surfaces
are pressed together at high pressures & temperatures.
Diffusion of atoms to the interface fills in voids & produces a
strong bond.
5. Diffusion & Materials Processing (contd)
 Sintering – a high-temperature treatment used to join small
particles together.
 Powder metallurgy – a method of producing metallic parts:
tiny metal powder are compacted into shape, which is then
heated to allow diffusion & sintering to join the powders into
a solid mass.