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Module 15

Diffusion in solids I

Lecture 15
Diffusion in solids I

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Keywords:Lawsofdiffusion,natureofconcentrationprofileininfiniteandsemiinfinitediffusion
couples,diffusivity,diffusionpaths,effectoftemperatureandcrystalstructureondiffusivity,
homogenization,hotforging,uphilldiffusion,chemicalpotential,activity

Introduction
Threemodulesofthiscoursehavebeendevotedtointroducetheconceptofdiffusioninsolids.Atoms&
moleculesinsolid,liquidandgasareneverstationary.Theykeepmoving.Inaliquidoragasonecould
seeorfeelthatthishappens.Ifyouleavealightedcandleinthecornerofaroomyoudoseethesmoke
comingoutandspreadallovertheroom.Similarlyifyouleavesomearomaticsubstance(naphthalene
ball) in a dish you could feel the aroma even from a distance. This happens because the molecules /
particles responsible for the smoke or the aroma are able to move around. Such a movement in the
absenceofanyexternalforceiscalleddiffusion.Thistakesplaceinsolidsaswell.Weshalllookatthe
phenomenologicalaspectandlearnaboutthelawsgoverningdiffusioninthesemodules.Weshallalso
learnaboutexperimentaltechniquesbasedondiffusioncouplesthathelpsunderstandthemechanisms
ofdiffusion.

Whatisdiffusion?
Diffusion is the movement of any species in a medium along a given direction. It takes place in solid
liquidorgas.Itisassociatedwiththemovementofatoms/moleculesofthemediumandthespecies
presentinit.Itoccursevenintheabsenceofanyexternalforce.Inliquidorgassuchmovementscanbe
seen or felt easily. Slide 1 suggests a simple experiment to demonstrate the process of diffusion in a
liquid.
Slide 1: Take a glass of water with some soluble ink or
pigment at the bottom as shown in the sketch on the
extremeleft.Thegraphbesideitshowstheconcentrationof
inkalongthexaxis&theheightalongtheyaxis.Noteinthe
beginning only the extreme bottom appears red. With time
the color keeps changing. The glass in the middle shows its
appearance after a short time. The graph beside it shows
how the concentration changes with height. The top is still
colorless.Thecolorbecomesuniformafteralongtime.
This illustrates a case of mixing in absence of any external force. If we stir the liquid (or heat it) the
mixingwilltakeplacemuchfaster.Mixingintheabsenceofanyexternalforcedoesoccureveninsolid.

Lawsofdiffusion:
2

Diffusionistheprocessbywhichaspeciesmovesinagivendirection.Therateatwhichitmovescanbe
measuredintermsofthenumberofspecies/unitarea/unittime.Thisistermedasflux(J).Higherthe
differenceintheconcentrationofthespeciesinneighboringregionhigheristheflux.Theconcentration
(c) is defined as the number of species in a unit volume of the medium (or matrix). The diffusion of
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species (or material) is governed by Ficks first law. This states that the rate of flow of material is
proportional to its concentration gradient and it occurs down the gradient. In the case of a
unidirectionalflowthisisexpressedas:
(1)
Disknownasdiffusivity.OftenJisexpressedasnumber/(cm2sec)andconcentrationismeasuredas
number/cm3,thereforethedimensionofDiscm2/sec.ThecorrespondingSIunitism2/sec.

Figure 1 illustrates how concentration varies with distance.


Notethattheconcentrationofthespeciesatanypointdoes
notchangewithtime.Thisiswhytheconcentrationprofileof
a species in a medium is linear. This means that the
concentrationgradientandthefluxJremainconstant.

DerivationofFicksfirstlaw:
Atoms or molecules in a medium are not stationary. They keep moving randomly in all possible
directions. Using this it is possible to derive the first law of diffusion. Let the concentration of a
particularspeciesinamediumbec(x)atadistancexalongxaxis.Itsconcentrationatx+xisc(x+x)
anditsconcentrationatxxisc(xx).Letusconsidera2dimensionalcasewhereatomscanmovein
allthefourdirections.Thereforethechancethatthespeciesmovesalongthedirectionxis.

c(xx)
xx

c(x)
x

c(x+x)
x+x

Numberofspeciesmovingxalongxintimet:
Fromlefttoright

Fromrighttoleft

Fig.2Concentrationsofspeciesatthreelocationsnormaltothexaxisinamediumaregivenin
thesketch.Theexpressionsontherightgivestherateatwhichspecieskeepsmovingfromleft

toright&viceversa

Fromtheexpressiongiveninfig1theexpressionforthenetflux(J)canbeobtained.Notethatinthe
derivationtheconcentrationtermhasbeenwrittenintheformaTaylorseries.Thehigherorderterms
havebeenneglected.

3

(2)

Thisshowsthatthefluxisdirectlyproportionaltotheconcentrationgradientandthediffusivityisgiven
by

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(3)

Thisdefinesthemobilityofthespeciesinthemedium.Itisdeterminedbytheshortestdistance(jump
step)itcanmoveandthetimeittakesforthistohappen.

Fickssecondlaw:
What would happen if the concentration profile at a given time t is not linear as in fig 1. Here is a
situationwheretheconcentrationgradientkeepschangingwithdistance.Accordingtothefirstlawthe
flux is directly proportional to the local concentration gradient. Therefore the flux J at a given time t
wouldbedifferentatdifferentlocations.Thisisillustratedinfig3.

Fig 3: The sketch shows the concentration of an element in a


solid as a function of distance x at given time t. Flux at any
point is directly proportional to concentration gradient. The
fluxatxxisJ1andthatatx+xisJ2.J1>J2.Thisshowsthat
morenumberofatomsmoveintothespacebetweenthetwo
dotted lines than that leaving this space. Therefore the
concentrationofatominthiszonewouldincrease.

J1

J2

xx x x+x

Let J denote the flux at a point x. The flux at the two points at xx and x+x are given by the
and

respectively. The difference between the two gives the amount of

thespeciesthataccumulateinthisspaceoverasmalltimet.Sincethevolumeofthespacebetween
theplanesshowninfig3is2xtherateofchangeoftheconcentrationduringthetime,t,isgivenby

(4)

On substitution of equation 1 and making the time interval extremely small the expression for the
changeinconcentrationcouldbewrittenas
(5)
Thisshowsthattherateofchangeofconcentrationatagivenpointwithtimeisproportionaltotherate
ofchangeofconcentrationgradientandthediffusivitywiththedistance.ItisknownastheFickssecond
lawofdiffusion.Ifthediffusivityisindependentofconcentrationthelawcanbedescribedasfollows:
(6)
4

Theequation6describestherateofchangeofconcentrationduetodiffusionalongxaxisonly.However
inasolidsuchaprocesscantakeplacealonganydirection.Thereforeweneedamoregeneralformof
thelawtodescribediffusionofspeciesin3D.Letusfirstlookatthenatureofdiffusivity.Isthisascalar,
vector or something else? If you again go back to Ficks first law you find that it provides a relation
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betweentwovectors.BothfluxJandconcentrationgradientarevectors.Youmayrecallthatstresstoo
relatestwovectors;forceandarea.Weknowthatstress()isatensorofrank2.Therelationbetween
wheretheuseofrepeatedsuffix
theforce(Fi)andthearea(Aj)intensornotionisgivenby
denotessummation.Thereforediffusivitytooisatensorofrank2.Followingtheaboveanalogyfluxdue
todiffusionalongagivendirectionmaybewrittenas

.Notethatconcentrationisascalar.

Its nature is something similar to that of temperature or potential. You need two suffixes to denote
diffusivity.Dependingonthematerialitmayhavedifferentvaluesalongdifferentdirections.

SolutionofFickssecondlawina1Dcase:
Letuslookatasimplecaseofmixinginsolidduetothemovementofaparticularspeciesthroughthe
lattice.Takethecaseofdiffusionofcarboniniron.Carboncandissolveiniron.Itsconcentrationcanbe
increasedthroughsolidstatediffusion.Keepalongpieceofironinafurnaceatagiventemperature.In
fig4thisisrepresentedbyredcolorbarindicatingthatitisuniformlyheatedtoatemperatureT.For
simplicitywewouldconsidera1Dcaseonly.Thereforeallthesidesexceptthefrontfacelocatedatx=0
arecovered.Thisensuresthatcarboncanonlydiffusealongthexaxis.Theconcentrationofcarbonat
x=0 is maintained at cs for t > 0. This can be achieved by maintaining a suitable gaseous atmosphere
havingtheappropriatecarbonpotentialtomaintaintheconcentrationofcarbonatadesiredlevel.The
boundaryconditionandthestatementoftheproblemareillustratedinfig4.


c
cs

0,

0,

Fig4:TherectangledenotesapieceofironatatemperatureT
0 inafurnace.Thegraphshowsthatthecarboncontentatx=0
iscswhereasatx>0itis0.Thisdefinestheinitialcondition.
0
The carbon content at the exposed face is maintained at this
levelatalltimes.Theequation6istobesolvedtogetc(x,t).

There are standard methods to solve equation 6 for specified boundary conditions. If diffusivity is a
function of composition such equations are solved numerically. For the case described in fig 4 if D is
assumedtobeindependentofconcentrationthesolutionisgivenbythefollowingequation.
1

(7)

Whereerf()denoteserrorfunction.Itisgivenby:

(8)

Therearestandardtablestoevaluatesuchfunctions.Mostelectronicspreadsheetshavethisasabuilt
in function. Figure 5 gives a typical error function plot obtained using Excel. Note that the initial
concentrationofcarboninequation7hasbeenenteredasc0.Inthisspecificcaseitiszero.Thereforeon
directsubstitutionoftheinitialconditioninequation7itispossibletoshowthatatt=0c=csatx=0as
tapproachesinfinitycwouldapproachcsatallvaluesofx.
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Itisthereforepossibletogenerateconcentrationprofilesatanytimetasafunctionofdistancefora
givenvalueofD.Figure7presentsasetofsuchprofilesfordifferentvaluesoftime.InthiscaseDhas
beentakenas104cm2/sforanarbitraryspeciesandtimesinthefig7areinhours.Notethatatshorter
timestheprofileisstiffatlowervaluesof x anditbecomes asymptotic at highervaluesof x. Astime
approachesinfinitytheconcentrationtendstobecomeuniformallthroughthesection.Thereisaclose
similarity between the error function and standard normal distribution. This is why it is possible to
simulatediffusionasarandomwalkprocess.
1

erf(z)

0.8
0.6
0.4
0.2
0
0

0.5

1.5

2.5

Fig5:Atypicalerrorfunctionplotobtainedfromexcelspreadsheet.

1.20
1.00

0.80
1

0.60

0.40

0.20

1000

0.00
0.00

0.50

1.00

1.50

2.00

2.50

Fig6:Usingequation7theconcentrationofthespecieshasbeenplottedasafunctionofdistancefor
differentvaluesoftime.

Diffusioncoupleconsistingoftwosemiinfinitebarsofmetalsjoinedataninterface:
6
Diffusionisaprocessofmixing.Itisassociatedwithmovementofatomsinthelattice.Thedifferencein
concentrationofagivenspeciesinthematrixisthedrivingforce.Letusconsidertwoalloysmadeoftwo
metals (say Cu & Ni) having different compositions joined at an interface as shown in fig 7 where c
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denotesconcentrationofNioneithersidesoftheinterfaceasfunctionofdistance.Thealloyontheleft
has lower concentration of Ni than that on the right (c1 < c2). The alloy on the left has higher
concentration of Cu than that on the right. The mobility (diffusivity) of atoms is a strong function of
temperature.Ifthecoupleiskeptatroomtemperaturethemovementofatomswouldbetooslowto
detectanychange incomposition.Ifyouheatittoahightemperature youwouldfindthatCuatoms
woulddiffusefromthelefttotherightwhereastheNiatomswoulddiffusefromtherighttotheleft.
Thesolutionofequation6underthisconditionisgiventhefollowingexpression:
1

(9)

c2

c2

c1

x<0

x>0

c1

atany
timet

x>0

att=0

(c1+c2)/2
x<0

att=
0

x>0

x<0

Fig 7: Sketches showing how the concentration of a


given species in a diffusion couple consisting of two
different alloys changes with time. The sketch at the
top left defines initial condition; the one at the top
rightgivestheconcentrationprofileatanygiventime
t and the one at the bottom left gives concentration
profileattimeequaltoinfinity.

If follows from equation 9 that as t approaches infinity erf() becomes zero. Therefore c becomes
(c1+c2)/2atallvaluesofx.Inotherwordsitbecomesahomogeneousalloy.

Selfdiffusion:
Doesdiffusiontakeplaceinpuremetal?Inthiscasethereisnoconcentrationgradient.Inotherwords
thereisnodrivingforcefordiffusiontotakeplace.Howeveratomsinsolidarenotstationaryandthere
arevacantsitesinthelattice.Atomsinsolidskeepmovinginthelatticebyexchangingpositionswith
vacancies.Thisisillustratedinslide2.

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Self diffusion
Does atoms in pure metal move about?
Is there a way to find out?
No. atoms moving towards right
= No. atoms moving towards left
Net flux = 0
Use radioactive tracer

D*=Dt

Isotope has same electronic


structure but different mass.
Distinguishable.

Slide 2: The sketch on the left illustrates how


atoms are arranged in the lattice along with
vacantsites.Thelinedenotesanimaginaryplane.
Thearrowsrepresentthedirectionofmovement
of atoms. At any instant the number moving to
the right is samethe number movingtothe left.
Therefore the net flux is zero. Is there a way to
establish that diffusion takes place even in pure
metals? Is it possible to find its diffusivity? The
sketchontherightsuggeststhatbyaddingtracer
atomsitmaybepossibletodoso.

Slide2suggeststhatthattheselfdiffusioncoefficientcanbeestimatedbyaddingradioisotopesatone
end of the solid and monitoring how these atoms move into the solid. Isotopes are atoms having
identicalelectronicstructurebutdifferentmass.Oftenthemassdiffersbyoneatomicmassunit.Such
atomsareunstabletheytrytogetbacktothemorestablestructurebyemissionofradiations.Thiscan
be detected by suitable measuring devices like counters. If the concentration of tracer atoms can be
obtainedasafunctionoftime&distance;thediffusivityofthetracercanbeestimated.Sincethesize
and themassofthetracer atomandthebaseatom are nearlythe sameit maybeassumedthatthe
diffusivityofthetwospecieswouldbethesame.

Temperaturedependenceofselfdiffusioncoefficient:
We have just seen how the self diffusion coefficient can be estimated using radioactive tracer.
Diffusivity (D) of a given species in a specific medium can also be obtained from the concentration
profile along a diffusion couple. Diffusion of species is associated with the mobility of atoms. This
increases with increasing temperature (T). Therefore it is expected to be a strong function of
temperature.Thetemperaturedependenceofdiffusivityisoftenrepresentedasfollows:
(10)

WhereRistheuniversalgasconstant,QistheactivationenergyfordiffusionandD0isaconstant.IfDis
knownatseveraltemperaturesQ&D0canbeobtainedfromtheslopeandinterceptsoftheplotgiven
infig8.
D 0

Slope=Q/R
ln(D)

Fig8:Illustratestemperaturedependenceofdiffusivity.

Iffollowsfromequation10that
ln
.
Thereforeintercept=ln(D0)andslope=Q/R.

1/T

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Diffusionpathsinsolids:
Diffusionofspeciesinsolidsalsodependsonthepaththatitfollows.Inasolidwecanthinkofthree
distinctpaths.Metalsaremadeofseveralcrystalsthatmeetalonggrainboundaries.Ifaspecieshasto
movethroughthisitcouldeithermovethroughthegrain,thegrainboundaryorthetopsurface.Thisis
illustrated in slide 3. The diffusivity through the grain is denoted by Dg. This is often known as bulk
diffusioncoefficient.ThediffusivitythroughthegrainboundaryisdenotedbyDgb.Thespacebetween
atomsbecauseofirregulararrangementismoreatthegrainboundarythanthatwithinthegrains.This
iswhythemobilityofatomsthroughthegrainboundaryisexpectedtobehigherthanthatthroughthe
grain. The same logic can be extended to the exposed top surface. There is enough space to
accommodateextraatomsatthefreesurfaceifrequired.Thereforethemobilityoftheatomsalongthe
freesurface(Ds)ismuchhigher.TherelationbetweenthethreecouldbedescribedasDs>Dgb>Dg.
Slide3:Showsthreedistinctpathsinasolidthrough
whichanatomofagivenspeciescoulddiffuse.The
diffusivity of the species through these paths is
denoted as Ds (surface diffusion), Dgb (grain
boundary diffusion) and Dg (diffusion through the
grain). These are strong functions of temperature.
The temperature dependence is very much similar
totheexpressiongiveninequation10.Howeverthe
magnitudesofQ&D0arelikelytobedifferent.

Diffusion paths in solids


surface
grain

Grain
boundary

Ds
D

Dgb

Ds > Dgb > Dg

Dg
1/T

Theslide3alsoillustratesthetemperaturedependenceofthediffusivitythroughthreedifferentpaths.
Theactivationenergyofsurfacediffusionislikelytobethelowestandthatforthegrainisthehighest.
MathematicallythisisdenotedasQg>Qgb>Qs.

Diffusionasarandomwalkprocess:
The process of diffusion is governed by the movement of atoms. In solids where atoms are closely
packedsuchmovementswillbedifficultintheabsenceofvacantsites.Atagiventemperatureseveral
latticesitesarevacant.Ifthereareseveralsitesaroundanatomhowwouldanatomdecidewhereto
move? An obvious option could be a random selection. Slide 4 illustrates the difference between a
normalandarandomwalk.

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Slide4:Ifaspeciesmovesthroughthelatticeat
a velocity v, thedistancebetween its initial and
finalpositionaftertimetisequaltovt,provided
itcontinuestomoveinthesamedirection.Note
thatthelongredlinewithanarrowheaddenote
thedistancecoveredinthiscase.Howeverifthe
direction keeps changing randomly the distance
between the initial and final position is much
less.Thisisshownwiththehelpofashorterred
linewithanarrowhead.

Diffusion as random walk


Distance cover in time t during
normal walk along a specific
direction= velocity x time = v t

Distance covered in time t


during random walk along a
specific direction << v t
n

Rn r1 r2 rn ri
i 1

Thedistancebetweentheinitialandthefinalpositionisbestrepresentedasavectorsumofeachstep
( ).Thefinallocation
afternstepsofmovementisgivenby:

(11)

Thedotproductofavectorwithitselfgivesthesquareofitsmagnitude.Thisisgivenby

(12)

Eachtermofthesecondseriesinequation12denotesdotproductoftwovectors.Iftheanglebetween
thetwoisij,andeachstepsizeisequaltotheequation12onsimplificationbecomes:

(13)

Since the direction of motion is random the magnitude of cos could be both and negative. The sum
totalvalueisthereforelikelytobezero.Thustheaveragedistancebetweentheinitialandfinallocation
inthiscaseis asagainst ninthecaseofnormalwalk. representsaveragerootmeansquare
distance. In equation 3, x/t denotes the average velocity (v) of the diffusing species and x is the
averagestepsizewhichequivalentto.Thetotaldistancecoveredbythespeciesisn.Thereforethe
timeittakestocoverthisdistanceisn/v.Thusbyalittlealgebraicsimplificationyougetthefollowing
relations:

(14)

Thisshowsthataveragerandomwalkdistanceisequalto 2

Effectofcrystalstructureondiffusivity:
10

As we go through the course we would see how the composition of solid can be altered by allowing
certainatomstomoveintoitbydiffusion.Oftenitbecomesnecessarytoincreasethecarboncontentat
thesurfaceofsteelwhichismostlymadeofiron.Ironexistsintwodifferentcrystallineforms.Atroom
temperature it is BCC whereas above 910C it becomes FCC. The solubility of carbon in FCC state is
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higherthanthatofBCC.Ifwewantthesteeltodissolvesubstantialamountofcarbonwemusttakeitto
beyond 910C. However carbon can also diffuse in its BCC state. The rate of carbon pick up would
dependonitsdiffusivity.TheBCCformofironisknownasferriteandoftenrepresentedas.TheFCC
formofironisknownasaustenite.Itisrepresentedas.Thediffusivitiesofcarboninthesetwoforms
ofironareasfollows:
2

10

/ (15)

10

/ (16)

Ifyouestimatetheseoverarangeoftemperatures(6001000C)andplotthedataagainstreciprocalof
temperatureinKyougetaplotasshownin9.
1.00E09

Dm2/s

1.00E10
Ferrite
1.00E11

Austenite

1.00E12
6.00

7.00

8.00

9.00 10.00 11.00 12.00

10000/T,K1

Fig9:Diffusivityofcarbonintwoformsofironferriteandausteniteasfunctionoftemperature
Austenite is a close packed structure in comparison to ferrite. Therefore diffusivity of carbon in
austeniteislowerthanthatinferrite.Thesolubilityofcarboninausteniteismuchmorethanthatof
ferrite. Therefore in order to have uniform distribution of carbon in steel it has to be heated to
austeniticstate.Thediffusivityofcarboninaustenitebeingverylowthetimeneededhomogenization
ofcaststeelcanbeverylong.

Howtoreducetimeneededforhomogenization:

11

Solidificationofmetalsandalloysalwaysresultsinsegregation.Thisisbecausetheonlywayaspeciesin
asolidcanmoveisbydiffusionwhichisaslowprocess.Itmeanscaststructureisrarelyhomogeneous.
In order to make the solid homogeneous it is often held at a high temperature for long hours. The
effective diffusion distance is approximately equal to . A simple calculation would show that the
timeneededforhomogenizationevenifthedistanceoverwhichheterogeneityexistsisoftheorderofa
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fewmmcouldbeverylong.Hotforgingisaprocessthatcombinesdiffusionwithmechanicalworking.
Thecombinedeffectsofdiffusionandappliedstresshavingachurningeffectonthesolidcanhelpcut
downthetimeneededforhomogenizationsignificantly.Solidificationofmetalsandalloysalwaysresults
insegregation.Thisisbecausetheonlywayaspeciesinasolidcanmoveisbydiffusionwhichisaslow
process.Itmeanscaststructureisrarelyhomogeneous.Inordertomakethesolidhomogeneousitis
oftenheldatahightemperatureforlonghours.Theeffectivediffusiondistanceisapproximatelyequal
to .Asimplecalculationwouldshowthatthetimeneededforhomogenizationevenifthedistance
overwhichheterogeneityexistsisoftheorderofafewmmcouldbeverylong.Hotforgingisaprocess
thatcombinesdiffusionwithmechanicalworking.Thecombinedeffectsofdiffusionandappliedstress
having a churning effect on the solid can help cut down the time needed for homogenization
significantly.Applicationsthatdemandhomogeneousalloysprefertousecomponentsthathavebeen
producedbyhotupsetforging.

Uphilldiffusion:

12

Diffusion in solid as described above has been visualized as a process of mixing. The concentration
gradienthasbeenassumedtobeitsdrivingforce.Themassflowtakesplacedowntheconcentration
gradient.Thismaytrueforsolidsolutionshavingasingleminimuminitsfreeenergycompositionplotas
shown in fig 11. However there are several alloy systems where diffusion may take place against the
concentration gradient. Such a system has free energy composition plots having multiple minima as
showninfig12.Thisisknownasuphilldiffusion.Thisisbecausethetruedrivingforcefordiffusionisthe
chemicalpotentialorthepartialmolarfreeenergyandnottheconcentration.Themolarfreeenergy(G)
ofabinarysolidsolutionconsistingoftwometalsA&Bisgivenby:

NA&NBdenoteatomfractionA&B, & denotethefreeenergiesofpureA&B,Ristheuniversal


gasconstant,TisthetemperatureinKelvin, A& BdenotethechemicalpotentialsofA&BandaA&
aBdenotetheactivities(effectiveconcentrations)ofA&B.Thetwoactivitiesaregivenby

:Activitycoefficient
1 inanidealsolidsolution
:Activitycoefficient
1 inanidealsolidsolution

Figure10showsatypicalfreeenergycompositiondiagramofabinaryalloyatagiventemperature.The
interceptofthetangentatapointG1withtheverticalaxisatAdenotes denotesthepartialmolar
freeenergyofAinalloy1.Itisalsoknownasitschemicalpotential.Theinterceptofthesametangent
withtheaxisBdenotesthechemicalpotentialofBinalloy1denotedas .Notethemagnitudesofthe
and Bin 2 ( ).Figure 10includesthe sketchofadiffusioncouple
chemicalpotentialsofA in2
madeoftwoalloys1&2havingdifferentcompositions.Alloy1isrichinAwhereasalloy2isrichinB.In
this case
therefore A diffuses from 1 to 2. Here
as well. It represents a case where
diffusiontakesplacedowntheconcentrationgradient.

Figure11showsatypicalfreeenergycompositiondiagramofabinaryalloyatagiventemperature.It
hastwominima.TheinterceptofthetangentatapointG1withtheverticalaxisatAdenotes denotes
thepartialmolarfreeenergyofAinalloy1.TheinterceptofthesametangentwiththeaxisBdenotes
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thechemicalpotentialofBinalloy1denotedas .Notethemagnitudesofthechemicalpotentialsof
andBin2( ).Figure11includesthesketchofadiffusioncouplemadeoftwoalloys1&2
Ain2

having different compositions. Alloy 1 is rich in A whereas alloy 2 is rich in B. In this case
therefore A diffuses from alloy 2 to 1 although
. It represents a case where diffusion takes
placeagainsttheconcentrationgradient.

1 A

Fig 10: The sketch at the top represents a


diffusion couple consisting of two alloys 1 & 2.
Alloy 1 is rich in A and alloy 2 is rich in B. G
representsthefreeenergycompositionplot.G1
isthefreeenergyof1andG2isthefreeenergy
of 2. Gm is the free energy of the most stable
composition.Theverticalarrowheadendingat
this point is a measure of the driving force for
diffusion.Notethepointsofintersectionofthe
tangent at G1 & G2 with the vertical axis at A.
Since
Adiffusesfrom1to2.Diffusion
direction is shown with the help of an arrow.
:HenceBdiffusesasshownfromalloy
2to1.Thisisacaseofdownhilldiffusion

G2

G1
Gm

1 Arich

Brich 2
A

G
G1

Ga

G2

Gm

13
A

Fig 11: The sketch at the top represents a


diffusioncoupleconsistingoftwoalloys1&2.
Alloy1isrichinAandalloy2isrichinB.The
sketch at the bottom gives free energy
compositionplotG.G1isthefreeenergyof1
andG2isthefreeenergyof2.Gadenotesthe
combinedfreeenergyof1&2.Gmisthefree
energy of the most stable composition. The
vertical arrow head ending at this point is a
measure of the driving force for diffusion.
Notethepointsofintersectionofthetangent
at G1 & G2 with the vertical axis at A. Since
A diffuses from 2 to 1. Diffusion
directionisshownwiththehelpofanarrow.

: Hence B diffuses as shown from


alloy1to2.Thisisacaseofuphilldiffusion.

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Thissuggeststhatitisthechemicalpotentialgradientthatdeterminesthedirectionofflowofspecies.
Thereforethe moregeneralexpressionfor Fickslawshouldbeexpressed intermsof either chemical
potentialoractivitygradient.

The best known example of uphill diffusion was first reported by L S Darken in Trans AIME Vol. 180
(1949)p430438.Adiffusioncouplewasmadebyweldingtwopiecesofsteelonehaving3.5wt%Si&
0.49wt%Candtheotherhaving0.05wt%Si&0.45wt%C.Thiswaskeptto1050Cfor13days.Atsuch
a high temperature the most stable form of iron is austenite having FCC structure. The solubility of
carboninausteniteismuchhigherthantheamountofcarbonpresentinthetwosteel.Figure12shows
withthehelpofaschematicdiagramcarbonconcentrationprofilebeforeandafterhighertemperature
thermalexposure.Nodoubtcarbonisexpectedtodiffusefromthesteelonthelefthaving0.49%Cto
thaton the righthaving 0.45%C. However % carbon near the interface onthe left was foundto have
gonedownto0.33%whereasthatontherightoftheinterfacehadgoneupto0.59%.Clearlythisisa
casethatillustratesdiffusionofaspeciesinadirectionagainsttheconcentrationgradient.Thisunusual
phenomenonwasattributedtothepresenceofSithatalterstheactivity(orthechemicalpotential)ofC
iniron.
3.8Si0.49C

0.05Si0.45C

0.55%C
Time=0

Time=13days

0.49%C

0.45%C
Time=13days
0.33%C

Time=0

Fig12:Thesketchatthetopshowsaschematicrepresentationofadiffusioncouplemadeoftwo
steelhavingdifferentamountsofCandSi.Thesketchatthebottomshowstheinitial(t=0)and
thefinal(t=13daysat1050C)concentrationofCinthetwosteel.

Summary

14

In this module we have learnt about a solid state mixing process called diffusion. This is governed by
Fickslawsofdiffusion.Thefirstlawdescribessteadyastateprocesswhentheconcentrationofagiven
speciesatapointdoesnotchangewithtime.Inthiscasetheconcentrationgradientremainsconstant
at all points. If the concentration gradient is a function of distance then the concentration at a point
would keep changing with time. This is given by Ficks second law. This is expressed in the form of a
differentialequation.Thenatureofsolutionofsuchanequationin1Dhasbeendiscussedwithoutgoing
intoitsderivation.Attemptshavebeenmadetogiveaninsightintoitsmechanism.Itcanbesimulated
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as a random walk process. The average random walk distance has a direct correlation with diffusion
distance. We also looked at the effect of temperature on diffusivity. Using an illustration it has been
shownthatdiffusiondependsontemperatureaswellascrystalstructure.AlthoughFickslawisoften
writtenintermsofconcentrationgradienttherearecaseswherediffusionmaytakesplaceagainstthe
concentration gradient. This is known as uphill diffusion. This suggests that it is more appropriate to
definethisintermsofchemicalpotential.

Exercise:
1. If iron is kept at 1200K in a carburizing atmosphere for 8hrs to obtain a carbon
concentration of 0.75 at a depth of 0.5mm. Find the time it would take to reach same
carbon concentration at depth of 7.5mm at 1250K. (Given D0 = 0.2x104 m2/s & Q =
143kJ/mole/K)

2. Asteelcontaining0.2%carbonwasheatedto950Kfor15hours.Findthedepthoflayerin
whichthereisnocarbide.Assumethatsteelconsistsofferriteandcarbide.Thesolubilityof
carboninferriteatthistemperatureis0.015%and%Catthesurfaceisnegligible.(GivenD0
=2x106m2/s&Q=84.4kJ/mole/K)

3. The concentration of carbon on the surface of iron is maintained at 1.00% at 1175K for
2hours.Estimatethedepthatwhich%Cwouldbe0.5%.Usethediffusivityvaluesgivenin
question1.Assumeinitialcarboncontentofirontobenegligible.

Answer:
1. If iron is kept at high temperature in an environment having high carbon potential it diffuses
into iron. The depth of carburization (x) is proportional to

Therefore

11200=10.14hours

. Therefore

Since

.
.

2. IfinitialcarboninsteelisCi&solublecarboninferriteisCamountcarbontoremoved/unit
cross section through a distance dx = (CiC)dx = flux of carbon atom in time dt = Jdt =
Assuming carbon concentration at surface as 0
Thus

or;

0.2&Ca=0.015Therefore
15

10

.
.

4.55

10

m2/sNowCi =

0.00063m=0.63mm

3. Carbon content at surface Cs = 1.00, Initial carbon C0 = 0.0 & carbon content at a distance x
C=0.5

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Or,

Or,

0.477

. .

0.2

10

Or,
.

0.477
2

3600=0.000425m=0.445mm

16

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