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Queens University
KINGSTON, ONTARIO, CANADA.
Diffusion
Diffusion - Mass transport by atomic motion
Mechanisms Gases & Liquids random (Brownian) motion Solids vacancy diffusion or interstitial diffusion
Diffusion
Interdiffusion: In an alloy, atoms tend to migrate
from regions of high conc. to regions of low conc.
Initially After some time
RH11
vacancy
solute atoms
RH12
X ve = exp
S v H v exp k kT
exp
S v 3 k
H v = about 1 eV
Slide 6 RH12 You will use these equations in the assigments. First we consider defects arising in the crystal just due to thermal energy. Equilibrium concentration of vacancies (and interstitials) depends on temperature, since we require free energy to move atoms out of their position.
Richard Holt, 5/5/2007
RH13
exp
S i 3 k
about 4 eV
H i =
Diffusion Mechanisms
Interstitial diffusion smaller atoms can diffuse between atoms.
Slide 7 RH13 Same form of equation as for vacancies, but now energy term changes. Entropy term is the same.
Richard Holt, 5/5/2007
RH14
Interstitial diffusion
RH15
interstitial diffusion
r Number of atoms J i = 1 i n1 6 s concentration gradient J i = 1 i n2 6 r s Ci J i = J i J i = 1 i 2 x 6 C J i = Di i x
jump frequency
flux to left/right
net flux
Slide 9 RH14 If there is a concentration gradient random jumps lead to a net migraition migration. Here we have two adjacent planes of interstitial sites 1 and 2 separated by a distance alpha with different numbers of atoms. We'll consider the frequency with which atoms jump from plane 1 to plane 2 and vice versa.
Richard Holt, 5/5/2007
Slide 10 RH15 Since the number of jumps in one direction exceeds that in the other because of the concentration gradient, a random walk process leads to diffusion. Alpha is jump distance. This is how we define the diffusion coefficient.
Richard Holt, 5/5/2007
RH16
RH17
interstitial diffusion
entropy/enthalpy of migration vibration frequency
i = zi i exp
number of available sites
S mi H mi exp k kT
H mi Di = 1 i i2 = D0i exp 6 kT
jump distance
Slide 11 RH16 The jump frequency is controlled by the free energy barrier associated with interstitial jump.
Richard Holt, 5/5/2007
Slide 12 RH17 Formula gives probability for passing through this energy barrier, where subscript 'm' denotes migration. kT is a measure of the thermal energy available to each atom .
Richard Holt, 5/5/2007
Diffusion
Self-diffusion: In an elemental solid, atoms
also migrate.
Label some atoms After some time
C A D B
C A B D
RH18
Slide 14 RH18 To diffuse with the lattice an atom needs a vacancy next to it. Note a 'vacancy' can't move - its just the absence of an atom, so its movement is equivalent to atom movement.
Richard Holt, 5/5/2007
RH19
vacancy diffusion
v = zv h exp S mv H mv exp k kT
H mv Dv = 1 v 2 = D0 v exp 6 kT
RH20
Self diffusion
DA = 1 2 A 6 A = zX v exp
vacancy concentration*
Slide 15 RH19 Similar to interstitial diffusion, but now the values of entropy and enthalpy are for a vacancy.
Richard Holt, 5/5/2007
Slide 16 RH20 For self diffusion, the atom needs to move. But it needs a vacancy next to it in order to do so. The probability that a particular site is occupied by a vacancy is the vacancy concentartion. Hence an extra term is present here compared to the interstitial equation. So now there is a 'v' term for formation of a vacancy, and an 'm' term for migration of the atom.
Richard Holt, 5/5/2007
RH21
substitutional diffusion
in dilute binary alloys (solute concentrations < 1%) the rate of diffusion of the solute is also proportional to the vacancy concentration but
the equilibrium vacancy concentration can be increased if the solutes are attracted to the vacancies attraction of the solute and vacancy increases propobility that the solute has a vacancy in an adjacent site the energy barrier for the jump of the solute atom to the vacant site may be different for a solute than for the host atom
RH22
Slide 17 RH21 Zr alloys are always dilute. We dont want too much of anything else present, since it tends to then capture neutrons and reduce efficiency of the reactor.
Richard Holt, 5/5/2007
Slide 18 RH22 Migration of substitutional solute atom is very similar to self diffusion - we still need a vacancy to be present for the atom to hop into in order to move.
Richard Holt, 5/5/2007
RH23
Diffusion distance
- diffusion of a single atom or vacancy occurs by random walk - the direction of each jump is uncorrelated with the previous one - statistically, after n jumps, it moves a distance n1/2 jumps from its initial position, i.e., after a time t the distance from the initial position is:
r = t r = 2 .4 Dt
T(C)
C in
in Fe Fe Fe
e Fe in -F
-Fe
Al in
10-20
0.5 1.0 1.5
1000 K/T
Adapted from Fig. 5.7, Callister 7e. (Date for Fig. 5.7 taken from E.A. Brandes and G.B. Brook (Ed.) Smithells Metals Reference Book, 7th ed., ButterworthHeinemann, Oxford, 1992.)
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Diffusion
How do we measure the amount or rate of diffusion?
J Flux moles (or mass) diffusing mol kg or = (surface area )(time ) cm 2 s m 2s
Measured empirically
Make thin film (membrane) of known surface area Impose concentration gradient Measure how fast atoms or molecules diffuse through the membrane M= mass diffused
M l dM J = = At A dt
J slope time
Steady-State Diffusion
Rate of diffusion independent of time Flux proportional to concentration gradient =
C1 C1
dC dx
C2 x1 x2
C2
J = D
dC dx
dC C C 2 C1 if linear = dx x x 2 x1
D diffusion coefficient
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Cs
Adapted from Fig. 5.5, Callister 7e.
B.C.
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Solution:
C (x , t ) C o x = 1 erf Cs Co 2 Dt
CS
z 0
e y dy
2
C(x,t) Co
Summary
In solids diffusion occurs by the random motion of point defects For interstitial atoms (self or solute) this depends on the energy for migration from one interstitial site to another between lattice atoms For host atoms and substitutional solute atoms it depends on the energy for migration of vacancies and the vacancy concentration (i,.e., the vacancy formation energy). By random walk, the mean distance that an atom diffused is proportional to the square root of the product of the diffusion coefficient and time The energies can be determoned from plots of the logarythm of diffusion rate vs 1/T (called an Arrhenius plot). Steady state diffusion obeys Ficks first law. Transient diffusion obeys Ficks second law.
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