Diffusion

Atomic Motion in Solids

Week6

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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 A

Concentration of A

Time Temperature Concentration of A

Distance (x) Concentration Profile

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Distance (x)

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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

Atomic flux
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Vacancy flux

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 J = atomic flux (atoms/m2-s, kg/ m2-s) (dc/dx) = concentration gradient (atoms/m4) D = diffusion coefficient (m2/s)
dc/dx

area

c J

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 = D 2C t x2

C(x, t)=Cx

C(0,t)=Cs

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: BC-2: For t = 0, C = C0 at 0 x 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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Non-steady state diffusion

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

(Cx - C0) = 1 - erf x (Cs-C0) 2Dt ?

C(,t)=Co

Cs

to< t1 < t2 < t3 t1 t2 t3

Cx

C
C0

to
x=0

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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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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Qd 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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Solution:
Q d D = Do exp RT Do = T independent preexponential
d o C in Fe (BCC) at 900C

Q = the activation energy for diffusion (J/mol, or eV/atom)

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

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

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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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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Volume, grain boundary and surface diffusion

surface Grain boundary

Ag in Ag

volume

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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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