MECH 270 Material Science and Engineering 9.

Diffusion in Solids Chapter 5 Rick Holt

Queens University
KINGSTON, ONTARIO, CANADA.

Chapter 5: Diffusion in Solids

ISSUES TO ADDRESS...
How does diffusion occur? Why is it an important part of processing? How can the rate of diffusion be predicted for some simple cases? How does diffusion depend on structure and temperature?

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

Adapted from Figs. 5.1 and 5.2, Callister 7e.

RH11

point defects in crystals

substitutional interstitial

vacancy

self-interstitial atom (SIA)

solute atoms

RH12

equilibrium concentration of vacancies

entropy/enthalpy of formation

X ve = exp

S v H v exp k kT

exp

S v 3 k

H v = about 1 eV

Slide 5 RH11 Three basic classes of 0 dimensional defects

Richard Holt, 5/5/2007

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

equilibrium concentration of Self Interstitial Atoms (SIAs)

X ie = exp S i H i exp k kT

exp

S i 3 k
about 4 eV

H i =

Diffusion Mechanisms
Interstitial diffusion smaller atoms can diffuse between atoms.

Adapted from Fig. 5.3 (b), Callister 7e.

More rapid than vacancy diffusion

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

Ficks first law

jump distance diffusion coefficient units of m2s-1

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

interstitial jump frequency

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

vacancy and self-diffusion

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*

S m H m exp k kT S H v S H m = z exp v exp exp m exp k kT k kT (H v + H m ) DA = D0 exp kT H sd = H v + H m

* for an atom to diffuse, it must be adjacent to a vacancy

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

Note radiation damage will change vacancies present!

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

Substitutional Solute Diffusion

sol DA = 1 2A vacancy concentration 6 sol sol S m H m A = zX v exp exp kT k sol sol Sv H v S m H m = z exp exp exp exp k kT k kT sol (H v + H m ) DA = D0 exp kT sol H sd = H v + H m

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

Diffusion and Temperature

D has exponential dependence on T
1500 1000 600 300
Ci

T(C)

10-8 D (m2/s) 10-14

C in
in Fe Fe Fe
e Fe in -F

-Fe

D interstitial C in -Fe C in -Fe

Al

>> D substitutional Al in Al Fe in -Fe Fe in -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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Slide 19 RH23 2.4 is roughly sqrt(6) - see slide 19

Richard Holt, 5/5/2007

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

Ficks first law of diffusion

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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Non-steady State Diffusion

The concentration of diffucing species is a function of both time and position C = C(x,t) In this case Ficks Second Law is used
C 2C =D t x 2

Ficks Second Law

Non-steady State Diffusion

Copper diffuses into a bar of aluminum.
Surface conc., C s of Cu atoms bar pre-existing conc., Co of copper atoms

Cs
Adapted from Fig. 5.5, Callister 7e.

B.C.

at t = 0, C = Co for 0 x at t > 0, C = CS for x = 0 (const. surf. conc.) C = Co for x =

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Solution:
C (x , t ) C o x = 1 erf Cs Co 2 Dt

C(x,t) = Conc. at point x at time t erf (z) = error function

= 2

CS

z 0

e y dy
2

C(x,t) Co

erf(z) values are given in Table 5.1 of the text

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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