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Chapter5.Diffusion

Chapter5.Diffusion
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5.1Introduction
Manyimportantreactionsandprocessesinmaterialsoccurbythemotionofatomsinthesolid
(transport),whichhappensbydiffusion.
Inhomogeneousmaterialscanbecomehomogeneousbydiffusion,ifthetemperatureishighenough
(temperatureisneededtoovercomeenergybarrierstoatomicmotion.

5.2DiffusionMechanisms
Atomdiffusioncanoccurbythemotionofvacancies(vacancydiffusion)orimpurities(impurity
diffusion).Theenergybarrieristhatduetonearbyatomswhichneedtomovetolettheatomsgoby.
Thisismoreeasilyachievedwhentheatomsvibratestrongly,thatis,athightemperatures.
Thereisadifferencebetweendiffusionandnetdiffusion.Inahomogeneousmaterial,atomsalsodiffuse
butthismotionishardtodetect.Thisisbecauseatomsmoverandomlyandtherewillbeanequal
numberofatomsmovinginonedirectionthaninanother.Ininhomogeneousmaterials,theeffectof
diffusionisreadilyseenbyachangeinconcentrationwithtime.Inthiscasethereisanetdiffusion.Net
diffusionoccursbecause,althoughallatomsaremovingrandomly,therearemoreatomsmovingin
regionswheretheirconcentrationishigher.

5.3SteadyStateDiffusion
Thefluxofdiffusingatoms,J,isexpressedeitherinnumberofatomsperunitareaandperunittime
(e.g.,atoms/m2second)orintermsofmassflux(e.g.,kg/m2second).
SteadystatediffusionmeansthatJdoesnotdependontime.Inthiscase,Ficksfirstlawholdsthatthe
fluxalongdirectionxis:
J=DdC/dx
WheredC/dxisthegradientoftheconcentrationC,andDisthediffusionconstant.Theconcentration
gradientisoftencalledthedrivingforceindiffusion(butitisnotaforceinthemechanisticsense).The
minussignintheequationmeansthatdiffusionisdowntheconcentrationgradient.
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Chapter5.Diffusion

5.4NonsteadyStateDiffusion
Thisisthecasewhenthediffusionfluxdependsontime,whichmeansthatatypeofatomsaccumulates
inaregionorthatitisdepletedfromaregion(whichmaycausethemtoaccumulateinanotherregion).

5.5FactorsThatInfluenceDiffusion
Asstatedabove,thereisabarriertodiffusioncreatedbyneighboringatomsthatneedtomovetoletthe
diffusingatompass.Thus,atomicvibrationscreatedbytemperatureassistdiffusion.Also,smalleratoms
diffusemorereadilythanbigones,anddiffusionisfasterinopenlatticesorinopendirections.Similarto
thecaseofvacancyformation,theeffectoftemperatureindiffusionisgivenbyaBoltzmannfactor:D=
D0exp(Qd/kT).

5.6OtherDiffusionPaths
Diffusionoccursmoreeasilyalongsurfaces,andvoidsinthematerial(shortcircuitslikedislocationsand
grainboundaries)becauselessatomsneedtomovetoletthediffusingatompass.Shortcircuitsareoften
unimportantbecausetheyconstituteanegligiblepartofthetotalareaofthematerialnormaltothe
diffusionflux..

Terms:
Activationenergy
Concentrationgradient
Diffusion
Diffusioncoefficient
Diffusionflux
Drivingforce
Ficksfirstandsecondlaws
Interdiffusion
Interstitialdiffusion
Selfdiffusion
Steadystatediffusion
Vacancydiffusion

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Chapter5.Diffusion

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