Diffusion

Atomic Motion in Solids

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Week6

Diffusion in Materials
Q. How do changes in microstructure and chemical
composition actually occur?
A. Atoms must be able to move around (diffusion)
Diffusion occurs in solids, liquids and gases:
Redistribution of non-uniform chemical species
(impurity diffusion or interdiffusion)
Random atomic movement can also occur in
chemically uniform materials (self diffusion)
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Diffusion is driven by Nonuniformity

B

Temperature

Concentration of A

Concentration of A

Time

Distance (x)

Distance (x)
Concentration Profile
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Interdiffusion forming a solid solution

Initial

Intermediate time

Much longer time

What is this time scale?

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Diffusion?
Diffusion is necessary for:
Redistribution of chemical species
Physical changes in microstructure
Densification of powder compacts
Deformation at high temperature (creep)
Formation of solid state reaction products
One kind of conductivity in ceramics (ionic)

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Diffusion:
Perfect crystal:

Atoms would not move around because

there would be no places for them to move to

(all sites would be occupied)-- locked in place

Point defects must be present in a crystal to permit atomic

movement (diffusion)

In a way, atomic diffusion is actually the movement of

defects.

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Diffusion Mechanisms
I. Vacancy diffusion
o Only adjacent atoms can move into a vacancy
o Vacancy moves in opposite direction of atomic
motion
o Rate depends on concentration of vacancies

Vacancy
flux

Atomic
flux
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Diffusion Mechanisms
II. Interstitial Diffusion
o Atom can move into any adjacent empty
interstitial position (usually smaller atoms)
o Rate depends on concentration of interstitial
atoms
(Usually faster than vacancy diffusion)

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Diffusion Mechanisms
o Would you expect vacancy or interstitial
diffusion to be faster?
o Why?

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Diffusion occurs by random jumps

After many random jumps by an atom, its displacment
can be calculated by the theory of random walks

Net migration
after n jump

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Quantitative Description of Diffusion

- The rate of diffusion is characterized by describing atomic
fluxes at particular locations in the material
- Critical quantities

area

J = atomic flux (atoms/m2-s, kg/ m2-s)

(dc/dx) = concentration gradient

(atoms/m4)
D = diffusion coefficient (m2/s)

dc/dx

Ficks first law: J = - D (dc/dx)

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Interrelating the quantities

Ficks first law: J = - D (dc/dx)
(negative sign indicates that the direction of diffusion flux
is down the concentration gradient from high to low
concentration)

For steady state diffusion (local flux doesnt change

with time), Ficks First Law can be solved directly

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Example
Hydrogen (H) gas can be purified by passing atomic
hydrogen through a thin sheet of palladium (Pa) at 700oC in
a paladium diffusion cell. If the impure hydrogen gas is
maintained at 1 atm on one side of a 1 mm thick Pd sheet
(A=1 m2), and the pressure on the purified side is
maintained at 0.1 atm by pumping, what is the mass of the
hydrogen purified in 1 hr? Assume steady state conditions.
The concentration of H2 at 1 atm is 9.0x10-3 gm/cm3 and
D(H) in Pa is 1.2x10-6 cm2/sec.

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Non-steady state diffusion

The diffusion flux at a particular point
varies with time
(There is a net accumulation or depletion
of the diffusing species at a given location)
i.e., local concentration of diffusing
species changes with time as diffusion
proceeds
This is the most common situation
What is this time scale?

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Non-steady state diffusion

Ficks Second Law governs

C(x, t)=Cx

C(0,t)=Cs

C = D 2C
t
x2

C(,t)=Co
x
C(x,0)=Co

Many solutions exist for particular geometries

(initial and boundary conditions)
Diffusion from a constant source into an semi-infinite solid
BC-1:

For t = 0, C = C0 at 0 x

BC-2:

t > 0, C = Cs at x = 0

BC-3:

C = C0 at x =

(Cx - C0) = 1 - erf x

(Cs-C0)
2Dt
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Week 6

Non-steady state diffusion

(Cx - C0) = 1 - erf x

(Cs-C0)
2Dt
?

C(x, t)=Cx

C(,t)=Co

C(0,t)=Cs
C(x,0)=Co

to< t1 < t2 < t3

Cs

C
to

C0

x=0
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t1

t2

t3
Cx

x
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Example
Surface Treatment of Steel:
For some applications (e.g. gears), it is necessary to harden
the surface of a steel (Fe-C alloy) above that of its interior.
One way of accomplishing this is by increasing the surface
concentration of carbon in the steel (as we will see later)
using a process termed carburizing. In carburizing the steel
piece is exposed, at elevated temperature, to an atmosphere
rich in a hydrocarbon gas, such as methane (CH4).

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Example: Surface Treatment of Steel:

Consider on such alloy that initially has a uniform carbon
concentration of 0.25 wt% and is to be treated at 950 C.
If the concentration of carbon at the surface is suddenly
brought to and maintained at 1.20 wt%, how long will it
take to achieve a carbon content of 0.80 wt% at a position
0.5 mm below the surface? The diffusion coefficient for C
in Fe at this temperature is 1.6 x 10-11 m2/sec. Assume
piece is semi-infinite.

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Factors that Influence Diffusion

I. Diffusing Species
magnitude of diffusion coefficient, D - indicates
the rate at which atoms diffuse
both diffusing species and host material
influence the coefficient
Relative sizes of atoms
Openess of lattice
Ionic charges

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Factors that Influence Diffusion

Atomic Size/Mechanism
For example:
For the host species of iron:
- Self diffusion at 500C (Fe moving in Fe)
D = 1.1 x 10-20 m2/s (vacancy diffusion)
- Carbon interdiffusion at 500C (C moving in Fe
D = 2.3 x 10-12 m2/s (interstitial diffusion)

This shows the contrast between rates of

vacancy and interstitial diffusion
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10

Factors that Influence Diffusion

II. Temperature
very strong effect on the diffusion coefficient:
Q d
D = Do exp
RT
Do = T independent preexponential
Qd = the activation energy for diffusion (J/mol, or eV/atom)
R = the gas constant, 8.31 J/mol - K or 8.662 x 10 -5 eV/ atom K
T = absolute temperature, (K)

A large activation energy results in a small D

ln D = ln D o
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Q d 1
R T
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Plot ln D vs 1/T - get straight line

(to measure activation energy and Do)
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Example:
o Using data from Table 5.2, compute the
diffusion coefficient of C in Fe and Fe
at 900C.

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11

Solution:
Q d
D = Do exp
RT
Do = T independent preexponential
Q = the activation energy for diffusion (J/mol, or eV/atom)

d
o C in Fe
(BCC) at 900C

R = the gas constant, 8.31 J/mol - K or 8.662 x 10 -5 eV/ atom K

D = 6.2x10-7 m2/sec exp (-0.83 eV/atom / (1173K)(8.62x10-5 eV/atom-K)

T = absolute temperature, (K)
D = 1.7x10-10 m2/sec

o C in Fe (FCC) at 900C
D = 2.3x10-5 m2/sec exp (-1.53 eV/atom / (1173K)(8.62x10-5 eV/atom-K)
D = 5.9x10-12 m2/sec

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What does this tell you about interstitial sites

in BCC and FCC?.
BCC more open than FCC for interstitial
diffusioni.e. it is easier to move from one
interstitial site to another in BCC
But it does not say anything about the size
or number of interstitial sites in
each.actually, as you will see, FCC has
bigger (and more) interstitial sites

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12

Other Diffusion Paths

(Besides through volume of the crystal)
Atomic migration often occurs more rapidly along socalled short circuiting paths
Dislocations
Grain boundaries
External surfaces
However, there is usually small total area
for this to occur - so not always important
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Week 6

Volume, grain boundary and surface diffusion

surface
Grain boundary

Ag in Ag

volume

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13

Diffusion and Materials Processing

o Properties of materials are altered through
diffusion
steelmaking
sintering
semiconductor doping

o Heat treatment is used to allow these to

occur over a reasonable time frame.

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Summary
Recognize various imperfections in crystals
Point imperfections
Impurities
Line imperfections (dislocations)
Bulk imperfections
Define various diffusion mechanisms
Identify factors controlling diffusion processes
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Reading Assignment
Shackelford 2001(5th Ed)
Read Chapter 5, pp 158-181

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