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Chapter 5 Diffusion

Materials Science And Engineering


An Introduction, William D. Callister, Jr.
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Objectives of Chapter 5
Examine the principles and applications of diffusion in materials.
Diffusion how do atoms move through solids?
Diffusion mechanisms
Vacancy diffusion
Interstitial diffusion
Impurities
The mechanism of diffusion
Steady-state diffusion (Ficks first law)
Factors that influence diffusion
Diffusion species
Host solid
Temperature
Microstructure

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What is diffusion?
Diffusion is material transport by atomic motion.

Inhomogeneous materials can become homogeneous by diffusion. For


an active diffusion to occur, the temperature should be high enough to
overcome energy barriers to atomic motion.
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Mechanisms for Diffusion


Self-diffusion
The random movement of atoms within an
essentially pure material. (Self-diffusion is a
diffusion in one-component material, when all atoms that
exchange positions are of the same type.)

Vacancy diffusion
Diffusion of atoms when an atom leaves a
regular lattice position to fill a vacancy in the
crystal.

Interstitial diffusion
Diffusion of small atoms from one interstitial
position to another in the crystal structure.
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Self Diffusion
Self-diffusion: In an elemental solid, atoms also migrate.

Label some atoms

After some time

C
A
D
B

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Vacancy Diffusion
Vacancy diffusion

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 ~ kT)

Material flow (the atom) is opposite the vacancy flow direction.


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Interstitial Diffusion
Interstitial diffusion

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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Substitutional Diffusion
Substitutional Diffusion:
applies to substitutional impurities
atoms exchange with vacancies
rate depends on:
--number of vacancies
--activation energy to exchange.

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Ionic Diffusion

2003 Brooks/Cole, a division of Thomson Learning, Inc. Thomson Learning is a trademark used herein under license.

Figure: Diffusion in ionic compounds. Anions can only enter


other anion sites. Smaller cations tend to diffuse faster
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Interdiffusion
In an alloy, atoms tend to migrate from regions of
large concentration to regions of low concentration.
Initially

After some time

100%

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0
Concentration Profiles
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2003 Brooks/Cole, a division of Thomson Learning, Inc. Thomson Learning is a trademark used herein under license.

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Figure: Diffusion of
copper atoms into
nickel. Eventually,
the copper atoms are
randomly distributed
throughout the nickel

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Rate of Diffusion (Ficks First Law)


Diffusion coefficient (D) m2/sec
A temperature-dependent coefficient related to
the rate at which atoms, ions, or other species
diffuse.

Concentration gradient (dC/dX) kg/m3.m


The change of composition with distance in a
non-uniform material, typically expressed as
atoms/cm3.cm or at%/cm or kg/cm3.cm.

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Diffusion Flux
The flux of diffusing atoms, J, is used to quantify how fast diffusion
occurs. The flux is defined as either the number of atoms diffusing
through a 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).
J = M / At (1/A) (dM/dt) (Kg m-2 s-1)
where M is the mass of atoms diffusing through the unit area A per unit time t.

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2003 Brooks/Cole, a division of Thomson Learning, Inc. Thomson Learning is a trademark used herein under license.

Figure : The flux


during diffusion
is defined as the
number of atoms
passing through a
plane of unit area
per unit time

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Steady-State Diffusion
Steady state diffusion: the diffusion flux does not change with time.
Concentration profile: concentration of atoms/molecules of interest as function of
position in the sample.
Concentration gradient: dC/dx (Kg.m-4): the slope at a particular point on
concentration profile.

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Concentration Profiles and Flux


Concentration Profile, C(x): [kg/m3]
Cu flux Ni flux
Concentration
of Cu [kg/m3]

Concentration
of Ni [kg/m3]

Adapted
from Fig.
5.2(c),

Callister 6e.

Fick's First Law:

Position, x

Diffusion flux along direction x is proportional to the concentration gradient

Steeper the concentration profile, greater the flux!


The concentration gradient is often called the driving force in diffusion

Factors that Influence Diffusion

Temperature diffusion rate increases very rapidly with increasing


temperature

Diffusion mechanism interstitial is usually faster than vacancy

Diffusion and host species: D= f (T, D0, Qd) is different for every
solute, solvent pair

Microstructure- diffusion is faster in polycrystalline vs. single crystal


materials because of the accelerated diffusion along grain
boundaries and dislocation cores.

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Diffusion Thermally Activated Process

In order for atom to jump into


a vacancy site, it needs to
possess enough energy
(thermal energy) to break the
bond and squeeze through its
neighbor. The energy
necessary for motion, Em, is
called the activation energy for
vacancy motion.

At activation energy Em has to


be supplied to the atom so that
it can break inter-atomic bonds
to move into the new position.

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Activation Energy for Diffusion


Diffusion couple - A combination of elements
involved in diffusion studies
2003 Brooks/Cole, a division of Thomson Learning, Inc. Thomson Learning is a trademark used
herein under license.

Figure:
- A high energy is
required to
squeeze atoms
past one another
during diffusion.
This energy is the
activation energy
Q.

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- Generally more
energy is required
for a substitutional
atom than for an
interstitial atom
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Diffusion Temperature Dependence (I)


Diffusion coefficient is the measure of
mobility of diffusing species.

D0 temperature-independent pre-exponential (m2/s)


Qd the activation energy for diffusion (J/mol or eV/atom)
R the gas constant (8.31 J/mol-K or 8.6210-5 eV/atom-K)
T absolute temperature (K)
The above equation can be rewritten as

The activation energy Qd and pre-exponential D0, therefore, can be


estimated by plotting ln D versus 1/T. Such plots are Arrhenius plots.
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Diffusion Temperature Dependence (II)

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Diffusion Temperature Dependence (III)

Arrhenius plot of
diffusivity data for some
metallic systems

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Diffusion of Different Species

Smaller atoms diffuse more readily than big ones, and diffusion is faster in open
lattices or in open directions
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Diffusion: Role of the Microstructure (I)

Self-diffusion coefficients for Ag depend on the diffusion path. In


general the diffusivity is greater through less restrictive structural
regions grain boundaries, dislocation cores, external surfaces.
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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 "Case" is


--hard to deform: C atoms
"lock" planes from shearing.
--hard to crack: C atoms put
the surface in compression.
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Fig. 5.0,

Callister 6e.
(Fig. 5.0 is
courtesy of
Surface
Division,
MidlandRoss.)

Summary: Structure and Diffusion


Diffusion FASTER for...

Diffusion SLOWER for...

open crystal structures

close-packed structures

lower melting T materials

higher melting T materials

materials w/secondary
bonding

materials w/covalent
bonding

smaller diffusing atoms

larger diffusing atoms

cations

anions

lower density materials

higher density materials

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Summary
Make sure you understand language and concepts:

Activation energy
Concentration gradient
Diffusion
Diffusion coefficient
Diffusion flux
Driving force
Ficks first law
Interdiffusion
Interstitial diffusion
Self-diffusion
Steady-state diffusion
Vacancy diffusion

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