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Chapter 3: Diffusion in solids

Chapter Outline
Diffusion - how do atoms move through solids?
 Diffusion mechanisms
Vacancy diffusion
 Interstitial diffusion
 Impurities
 The mathematics of diffusion
 Steady-state diffusion (Fick’s first law)
 Nonsteady-State Diffusion (Fick’s second law)
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Cont’d
 Factors that influence diffusion:
 Diffusing species
 Host solid
 Temperature
 Microstructure
 Atomic mobility
 Tracer diffusivity in binary alloys
 Diffusion in ternary alloys
 High diffusivity paths
 Diffusion in multi phase binary solutions
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Cont’d

What is diffusion?
 Diffusion: the movement of particles in a solid
from an area of high concentration to an area of
low concentration, resulting in the uniform
distribution of the substance.
 Diffusion is process which is NOT due to the
action of a force, but a result of the random
movements of atoms.
 Heat causes atoms to vibrate.
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Mechanisms of diffusion
Interdiffusion: In an alloy, atoms tend to migrate
from regions of high conc. to regions of low conc.
After some time
Initially

Cu Ni Cu Ni

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Cont’d

Before After
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Cont’d
 Self-diffusion: In an elemental solid, atoms also
migrate.
Label some atoms After some time
C
C

A D
A
D
B
B

All atoms exchanging positions are of same type no compositional


Diffusion in pure metal changes

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Cont’d
 Atoms in solids are in constant motion rapidly changing positions.
 Diffusion is just the stepwise migration of atoms from a lattice site
to other lattice site.
Two conditions for movement:
1. There must be an empty adjacent site
2. Atom must have sufficient energy to break bonds with neighbor
atoms.
Atomic vibration:
 Every atom is vibrating very rapidly about its lattice position within
the crystal.
 At any instant, not all vibrate with same frequency and amplitude.
 Not all atoms have same energy.
 Same atom may have different level of energy at different time.
 Energy increases with temperature.
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Vacancy Diffusion
• Involves interchange of an atom from a normal
lattice position to an adjacent vacant lattice site or
vacancy.
• Necessitates presence of vacancies.
• Substitutional diffusion generally proceeds by the
vacancy mechanism.
• Diffusing atoms and vacancies exchange
positions.
• They move in opposite directions.
• Both self- and inter-diffusion occurs by this
mechanism. 8
Cont’d
Vacancy Diffusion:
 Applies to substitutional impurities
 Atoms exchange with vacancies
Rate depends on:
1. Number of vacancies;
2. Activation energy to exchange.

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Cont’d

To jump from lattice site to lattice site, atoms need energy
to break bonds with neighbors, and to cause the necessary
lattice distortions during jump. This energy comes from the
thermal energy of atomic vibrations (Eav ~ kBT)
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Cont’d
Interstitial diffusion:
 Interstitial diffusion – smaller atoms can
diffuse between atoms.

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Cont’d
 Interstitial diffusion is generally faster than
vacancy diffusion because bonding of
interstitials to the surrounding atoms is
normally weaker and there are many more
interstitial sites than vacancy sites to jump to.
 Requires small impurity atoms (e.g. C, H, O) to
fit into interstices in host.

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Processing Using Diffusion
 Case Hardening:
Diffuse carbon atoms into the host iron atoms at the surface.
Example of interstitial diffusion is a case hardened gear.

 Result: The presence of C atoms makes iron (steel) harder.

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Diffusion Flux
 The quantity of an element that is transported within another is a
function of time. Diffusion is a time-dependent process.
 The flux of diffusing atoms, J, is used to quantify how fast
diffusion occurs. The flux is defined as either in number of atoms
diffusing through unit area and per unit time (e.g., atoms/m2-
second) or in terms of the mass flux - mass of atoms diffusing
through unit area per unit time, (e.g., kg/m2-second).
 Mathematically: J = M / (At)
 In differential form: J = (1/A)(dM /dt)
Where M is the mass of atoms diffusing
through the area A during time t.

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Cont’d
 How do we quantify the amount or rate of diffusion ?
moles (or mass) diffusing mol kg
J  Flux   or
surface areatime  2
cm s m2s
• Measured empirically
– Make thin film (membrane) of known surface area
– Impose concentration gradient
– Measure how fast atoms or molecules diffuse through the
membrane

M=
M l dM mass J  slope
J 
At A dt diffused
time

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Steady-State Diffusion
Rate of diffusion independent of time
Flux proportional to concentration gradient =

C1 C1 Fick’s first law of diffusion

dC
C2 C2 J  D
dx
x1 x2
x
D  diffusion coefficient
dC C C2  C1
if linear  
dx x x2  x1

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Cont’d

If the diffusion flux does not change with time steady-


state diffusion
Example:
 Diffusion of a gas through a plate of metal
 Concentration (or pressure) of diffusing species on both side
are held constant
 Concentration profile: Concentration versus position
 Assumed linear concentration profile as shown in figure (b)
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Cont’d
 Concentration gradient = dC / dx
 For linear concentration shown in the above:
 Conc. Gradient = ΔC/Δx = (CA – CB) / (xA – xB)
 Fick’s first law: For steady-state diffusion, the
flux is proportional to the concentration gradient
J = -D(dC/dx)
 D: diffusion coefficient (sq. m per second )
 -ve sign: direction of diffusion from a high to a
low concentration
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Cont’d
Example problem

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Cont’d
J = -D(dC/dx)
 Diffusion coefficient is the measure of
mobility of diffusing species.

DO : temperature-independent preexponential
(m2/s)
Qd– the activation energy for diffusion (J/mol )
R – the gas constant (8.31 J/mol-K)
T – absolute temperature (K)

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Cont’d
The above equation can be rewritten as

The activation energy Qd and preexponential D0 therefore,


can be estimated by plotting lnD versus 1/T or logD versus
1/T. Such plots are Arrhenius plots.

Graph of log D vs. 1/T has slop of –


Qd/2.3R, intercept of ln Do

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Diffusion coefficient (D)
• Diffusivity D depends on:
 Diffusion mechanism
 Temperature of diffusion
 Type of crystal structure (bcc > fcc)
 Crystal imperfections
 Concentration of diffusing species

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Cont’d
Example: At 3000c the diffusion coefficient and
activation energy for Cu in Si are:
D(3000c) = 7.8 x 10-11 m2/s
Qd = 41.5 kJ/mol
R=8.314J/ mol.ok
What is the diffusion coefficient at 3500c?
ANSWER: D2 = 15.7 x 10-11 m2/s

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Non-steady-State Diffusion: Fick’s second law
 The concentration of diffusing species is a
function of both time and position C = C(x,t)
 In this case Fick’s Second Law is used
d Cx d  d Cx 
= D 
dt d x d x 
In words, The rate of change of composition at position x with
time, t, is equal to the rate of change of the product of the
diffusivity, D, times the rate of change of the concentration
gradient, dCx/dx, with respect to distance, x.

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Non-steady-State Diffusion: Fick’s second law

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Cont’d

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Cont’d
 Solution of this equation is concentration
profile as function of time, C(x,t):
Cs

at t = 0, C = Co for 0  x  
at t > 0, C = CS for x = 0 (constant surface
conc.)
C = Co for x = 
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Cont’d

C x - Co  x  CS
= 1 - erf  
C s - Co  2 Dt 
C(x,t) = Conc. at point x at C(x,t)
time t
erf (z) = error function Co
erf(z) values are given in Table 5.1

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Cont’d
Tabulation of Error Function Values

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Cont’d
Sample Problem: An FCC iron-carbon alloy
initially containing 0.20 wt% C is carburized at
an elevated temperature and in an atmosphere
that gives a surface carbon concentration constant
at 1.0 wt%. If after 49.5 h the concentration of
carbon is 0.35 wt% at a position 4.0 mm below
the surface, determine the temperature at which
the treatment was carried out.

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Cont’d
Selected Values of Do and Ea for Diffusion Systems

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Diffusion Coefficient

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Cont’d
Factors that influence diffusion
 Temperature - diffusion rate increases very rapidly
with increasing temperature.
 Diffusion mechanism – diffusion by interstitial
mechanism is usually faster than by vacancy
mechanism.
 Diffusing and host species - Do, Qd are different for
every solute, solvent pair.
 Microstructure - diffusion is faster in polycrystalline
materials compared to single crystals because of the
accelerated diffusion along grain boundaries.
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Atomic mobility
 Atomic diffusion is a diffusion process whereby the
random thermally-activated movement of atoms in a
solid results in the net transport of atoms.
 The rate of transport is governed by the diffusivity
and the concentration gradient.
 Segregation to grain boundaries, interfaces &
dislocations is of great technological importance. For
example the diffusion of C,or N to dislocations in
mild steel is responsible for strain ageing and blue
brittleness.
 The segregation of impurities such as Sb, Sn, P and
As in low alloy steels produces temper
embrittlement.
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Cont’d
 Segregation to grain boundaries affects the mobility
of the boundary & has an effect on recrystallization
and grain growth.
 The problem of atom migration can be solved by
considering the thermodynamic condition for
equilibrium; namely the chemical potential of an
atom must be the same everywhere.
 An alternative way to describe a flux of atom is to
consider a net drift velocity(v) super imposed on the
random jumping motion of each diffusing atom. The
drift velocity is related to the flux by:
JB= VB CB ---------1
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Cont’d
 Since atoms always migrate so as to remove
differences in chemical potential is reasonable to
suppose that the drift velocity is proportional to
the chemical potential gradient,i.e
VB= -MB -----------2
 Where MB is a constant of proportionality known
as atomic mobility. From 1 & 2
JB=-MBCB ------------3
( ) is the chemical force for migration of atoms.

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High diffusivity paths
 In this section diffusion along dislocations,
interfaces, grain boundaries& free surfaces are
discussed. It will become apparent that under
certain circumstances diffusion along these
defects can be the dominant diffusion path.
Diffusion along the grain boundaries & free surfaces
 It is experimentally found that diffusion along
grain boundaries & free surfaces can be described
by:
Db=Dbo
Or
DS=DS0
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Cont’d
 Where Db & DS are the grain boundary and surface
diffusivities, Dbo & DS0 are the frequency factors.
 Qb & Qs are experimentally determined values of
activation energies for diffusion.
 In general, at any temperature the magnitude of Db &
DS relative to the diffusivity through defect free
lattice D1 are such that:
DS >Db>D1
 This mainly reflects the relative ease with which
atoms can migrate along free surfaces, interior
boundaries & though the lattice. 38
MULTIPHASE DIFFUSION IN BINARY
AND TERNARY SOLID-STATE SYSTEMS

 If two solid materials are in contact at a sufficiently


high temperature, interdiffusion will occur.
 Depending on the nature of the starting materials,
temperature & annealing time, a new concentration
distribution of the element is set up.
 If the materials are completely miscible at that
temperature, the concentration profiles are more or
less smooth without any discontinuity.
 If however they are only partially miscible or if they
react to form new phases, discontinuities in the
concentration profile occur which are closely related
to the phase diagram of the system.
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Cont’d

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Cont’d

THE END!!!

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