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?
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DIFFUSION DEMO
Glass tube filled with water. At time t = 0, add some drops of ink to one end of the tube. Measure the diffusion distance, x, over some time. Compare the results with theory.

to t1 t2 t3 xo
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x (mm)

x1

x2 x3
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time (s)

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DIFFUSION: THE PHENOMENA (1)

Interdiffusion: In an alloy, atoms tend to migrate
from regions of high concentration to regions of low concentration.
Initially After some time

Adapted from Figs. 5.1 and 5.2, Callister 6e.

100% 0

Cu

Ni

100% 0 Concentration Profiles

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Concentration Profiles
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DIFFUSION: THE PHENOMENA (2)

Self-diffusion: In an elemental solid, atoms
also migrate.
Label some atoms After some time

C A D B

C A B D

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Diffusion: The Mechanism

All atoms are constantly vibrating around their lattice positions (as long as temperature is above absolute zero). The atoms vibrate with a distribution of frequencies and amplitudes, i.e. there is a distribution of vibrational energies For one atom, the vibrational energy will vary over time As temperature increases the average vibrational energy increases Diffusion is the movement of an atom from one lattice position to another. An atom can diffuse if (1) there is an adjacent space and (2) the atom has sufficient energy
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Substitutional Diffusion
applies to substitutional impurities atoms exchange with vacancies rate depends on: --number of vacancies --activation energy to exchange.

increasing elapsed time

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INTERSTITIAL DIFFUSION
Applies to interstitial impurities. More rapid than vacancy diffusion.

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PROCESSING USING DIFFUSION (1)

Case Hardening:
--Diffuse carbon atoms into the host iron atoms at the surface. --Example of interstitial diffusion is a case hardened gear.
Fig. 5.0,

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

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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MODELING DIFFUSION: FLUX

Flux:
atoms 1 dM kg J= or 2 2 A dt m s m s Flux is perpendicular to this plane Metal A

Directional Quantity y J y Jz Jx x

z Flux can be measured for:

--vacancies --host (A) atoms --impurity (B) atoms
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Metal B
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CONCENTRATION PROFILES & 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:

flux in x-dir. [kg/m2-s]

Position, x
Diffusion coefficient [m2/s] concentration gradient [kg/m4]

dC Jx = D dx

The steeper the concentration profile, the greater the flux!

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STEADY STATE DIFFUSION

Steady State: the concentration profile doesn't
change with time.
Steady State:

Jx(left)

Jx(right)

Jx(left) = Jx(right)

x
Concentration, C, in the box doesnt change w/time.

dC Apply Fick's First Law: J x = D dx dC dC = If Jx)left = Jx)right , then dx left dx right

Result: the slope, dC/dx, must be constant

(i.e., slope doesn't vary with position)!
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Diffusion Coefficient, D Also called diffusivity Units: m2/s Depends on diffusing species and host Depends on temperature Higher diffusivity means a higher flux for the same concentration gradient

dC Fick's First Law: J x = D dx

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EX: STEADY STATE DIFFUSION

Steel plate at 700C with Carbon geometry rich shown: gas

3 m g/ 2k 3 . =1 /m g C1 .8k =0 C2 Steady State = straight line! Adapted

Carbon deficient gas

from Fig. 5.4,

Callister 6e.

0 x1 x2
5m m

D=3x10-11m2/s

Q: What is the flux of carbon from the left to the right?

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m 10 m

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NON STEADY STATE DIFFUSION

Concentration profile, C(x), changes J(left) w/ time. To conserve matter: J(right) J(left) = dC dx dt dJ = dC dt dx Governing Eqn.:
equate

dx
J(right) Concentration, C, in the box

Fick's First Law: dC = D J or dx d2 C (if D does dJ = D not vary dx dx2 with x)

dC d2C =D dt dx 2

Ficks 2nd Law

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Non-steady state diffusion

dC d2C =D dt dx 2

Ficks 2nd Law

In order to analyze non-steady state diffusion behavior we must solve this partial differential equation. The solution depends on the initial conditions and the boundary conditions. We will consider one type of non-steady state diffusion only.
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Diffusion through a semi infinite solid with constant surface concentration

We can use this approximation if L > 10 Dt Before diffusion begins the diffusing atoms are uniformly distributed in the solid at a concentration C0. At t=0 the concentration at the surface of the solid is suddenly changed to CS.
t<0, C=C0 CS t=0, C=C0 CS t=t1, C=C(x,t)

x=0
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x=0
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x=0
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Diffusion through a semi infinite solid with constant surface concentration

CS Blue line is the concentration profile at t=0. C0

Solution to Ficks 2nd Law for this case:

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x C(x, t) Co = 1 erf 2 Dt Cs Co
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Error Function Table

x Note: z is the independent variable, i.e. Z = 2 Dt

and erf(z) is the dependent variable.

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Example 1
Consider the impurity diffusion of gallium into a silicon wafer at 1100C. Prior to commencement of diffusion the wafer was free of gallium. At time = 0 the surface concentration is changed to 1024 atoms/m3. Find the depth below the surface at which the concentration will be 1022 atoms/m3 after 3 hours. Given: D=7.0 x 10-17 m2/s

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Example 2
Consider the gas carburizing of steel at 927C. The diffusion coefficient of carbon in steel at this temperature is 1.28 x 10-11 m2/s. The carbon content at the surface is 0.90% and the initial carbon content is 0.20%. Calculate the carbon content 0.50 mm below the surface after 5 hours of carburizing time.

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Example 3
Consider the surface treatment of steel with C at 950C. The initial concentration of C in the steel is 0.25 wt% and the surface concentration during treatment is 1.2 wt%. How long will it take to reach 0.8 wt% C at a position of 0.5 mm below the surface? Given: D=1.6 x 10-11 m2/s

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DIFFUSION AND TEMPERATURE

Diffusivity increases with T.
diffusivity D = Do
1000

pre-exponential [m2/s] (see Table 5.2, Callister 6e) activation energy Q [J/mol],[eV/mol] exp d (see Table 5.2, Callister 6e )

RT
300

Experimental Data:
1500 600

gas constant [8.31J/mol-K]

10-8 D (m2/s)

T(C)

Ci

n -Fe

10-14

10-20

0.5

1.0

1.5

D has exp. dependence on T Recall: Vacancy does also! Dinterstitial >> Dsubstitutional Cu in Cu C in -Fe Al in Al C in -Fe Fe in -Fe Fe in -Fe Zn in Cu 2.0 1000K/T
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Adapted from Fig. 5.7, Callister 6e. (Date for Fig. 5.7 taken from E.A. Brandes and G.B. Brook (Ed.) Smithells Metals Reference Book, 7th ed., Butterworth-Heinemann, Oxford, 1992.)

C in Fe
in Fe
Al in Al Cu Cu in Fe in Cun i Zn Fe Fe -

Diffusion Coefficient

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PROCESSING QUESTION
Copper diffuses into a bar of aluminum. 10 hours at 600C gives desired C(x). How many hours would it take to get the same C(x) if we processed at 500C? Key point 1: C(x,t500C) = C(x,t600C). Key point 2: Both cases have the same Co and Cs.

Result: Dt should be held constant. x C(x,t) Co (Dt)500C =(Dt)600C = 1 erf 2Dt Cs C o 5.3x10-13m2/s 10hrs Answer:
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4.8x10-14m2/s

(Dt)600 = 110 hr t 500 = D500

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Note: values of D are provided here.

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SUMMARY: STRUCTURE & DIFFUSION

Diffusion FASTER for...
open crystal structures lower melting T materials materials w/secondary bonding smaller diffusing atoms cations lower density materials
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Diffusion SLOWER for...

close-packed structures higher melting T materials materials w/covalent bonding larger diffusing atoms anions higher density materials
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