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CHAPTER6: DIFFUSIONINSOLIDS

Diffusion Masstransportbyatomicmotion.
Movementofaatomfromanareaofhigh concentrationofthatanareaoflowerconcentration

Gases&Liquids randommotion Solids vacancydiffusionorinterstitialdiffusion

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

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

C A D B
Conditions for Diffusion

C A B D

1) Energy to break the bond 2) Place at adjacent site

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DiffusionMechanisms
Vacancy Diffusion:

atoms exchange with vacancies applies to substitutional impurities atoms rate depends on: --number of vacancies --activation energy to exchange.

increasing elapsed time

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DiffusionSimulation
Simulation of interdiffusion across an interface:

Rate of substitutional diffusion depends on:

--vacancy concentration --frequency of jumping.

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Interstitialdiffusion smalleratomscan diffusebetweenatoms.

More rapid than vacancy diffusion

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ProcessingUsingDiffusion
Case Hardening:

--Diffuse carbon atoms into the host iron atoms at the surface. --Example of interstitial diffusion is a case hardened gear.

Result:

The presence of C atoms makes iron (steel) harder.

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ProcessingUsingDiffusion
Doping silicon with phosphorus for n-type semiconductors: Process: 0.5 mm

1. Deposit P rich layers on surface.

magnified image of a computer chip silicon

2. Heat it. 3. Result: Doped semiconductor regions.

light regions: Si atoms

silicon
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Diffusion
Howdowequantifytheamountorrateofdiffusion?

J Flux

M At

moles (or mass) diffusing mol kg or = 2 (surface area )(time ) cm s m2s

Measuredempirically Makethinfilm(membrane)ofknownsurfacearea Imposeconcentrationgradient Measurehowfastatomsormoleculesdiffusethroughthe membrane M= mass diffused time

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J slope

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MODELINGDIFFUSION:FLUX

Flux:

x-direction Unit area A through which atoms move.

J=

atoms 1 dM kg or 2 A dt m2s m s

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

Jx(left)

Jx(right)

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

Steady State: Jx(left) = Jx(right)

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SteadyStateDiffusion
Rate of diffusion independent of time Flux proportional to concentration gradient =

dC dx

C1 C1

Ficks first law of diffusion

C2 x1 x2

C2

J = D

dC dx

D diffusion coefficient

if linear

dC C C2 C1 = dx x x2 x1
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Fick's First Law:

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

Jx = D

dC dx

concentration gradient [kg/m4]

Factors influence Diffusion

1) Species 2) Temperature

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DiffusionandTemperature
Diffusion coefficient increases with increasing T. Qd D = Do exp RT D = diffusion coefficient [m2/s] Do = pre-exponential [m2/s] Qd = activation energy [J/mol or eV/atom] R = gas constant [8.314 J/mol-K] T = absolute temperature [K]

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DiffusionandTemperature
D has exponential dependence on T
1500 1000 600 300

T(C)

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

Dinterstitial >> Dsubstitutional C in -Fe C in -Fe Al in Al Fe in -Fe Fe in -Fe

10-20
0.5 1.0 1.5

1000 K/T

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OtherDiffusionpaths
Diffusion may also occur through Grain Boundaries, External Surface. This called Short Circuit diffusion

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6.7 A sheet of steel 2.5 mm thick has nitrogen atmospheres on both sides at 900 C and is permitted to achieve a steady-state diffusion condition. The diffusion coefficient for nitrogen in steel at this temperature is 1.2 x 10-10 m2/s, and the diffusion flux is found to be 1.0 10-7 kg/m2-s. Also, it is known that the concentration of nitrogen in the steel at the high-pressure surface is 2 kg/m3. How far into the sheet from this high-pressure side will the concentration be 0.5 kg/m3? Assume a linear concentration profile.

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