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5.3(a)Compareinterstitialandvacancyatomicmechanismsfordiffusion.
(b)Citetworeasonswhyinterstitialdiffusionisnormallymorerapidthanvacancydiffusion.
(a)Withvacancydiffusion,atomicmotionisfromonelatticesitetoanadjacentvacancy.Selfdiffusion
andthediffusionofsubstitutionalimpuritiesproceedviathismechanism.Ontheotherhand,atomicmotionis
frominterstitialsitetoadjacentinterstitialsitefortheinterstitialdiffusionmechanism.
(b) Interstitial diffusion is normally more rapid than vacancy diffusion because: (1) interstitial atoms,
beingsmaller,aremoremobile;and(2)theprobabilityofanemptyadjacentinterstitialsiteisgreaterthanfora
vacancyadjacenttoahost(orsubstitutionalimpurity)atom.
5.5(a)Brieflyexplaintheconceptofadrivingforce.
(b)Whatisthedrivingforceforsteadystatediffusion?
(a)Thedrivingforceisthatwhichcompelsareactiontooccur.
(b)Thedrivingforceforsteadystatediffusionistheconcentrationgradient.
5.6ThepurificationofhydrogengasbydiffusionthroughapalladiumsheetwasdiscussedinSection5.3.Compute
thenumberofkilogramsofhydrogenthatpassperhourthrougha5mmthicksheetofpalladiumhavinganarea
of0.20m2at500C.Assumeadiffusioncoefficientof1.0108m2/s,thattheconcentrationsatthehighandlow
pressure sides of the plate are 2.4 and 0.6 kg of hydrogen per cubic meter of palladium, and that steadystate
conditionshavebeenattained.
Thisproblemcallsforthemassofhydrogen,perhour,thatdiffusesthroughaPdsheet.Itfirstbecomes
necessarytoemploybothEquations5.1aand5.3.Combiningtheseexpressionsandsolvingforthemassyields
M = JAt = DAt
x
0.6 2.4 kg / m3
= (1.0 10 -8 m2 /s)(0.20 m2 ) (3600 s/h)
5 103 m
=2.6103kg/h
5.8AsheetofBCCiron1mmthickwasexposedtoacarburizinggasatmosphereononesideandadecarburizing
atmosphereon theother side at 725C. After having reached steadystate, the iron wasquickly cooled to room
temperature.Thecarbonconcentrationsatthetwosurfacesofthesheetweredeterminedtobe0.012and0.0075
wt%.Computethediffusioncoefficientifthediffusionfluxis1.4 108kg/m2s.Hint:UseEquation4.9toconvert
theconcentrationsfromweightpercenttokilogramsofcarbonpercubicmeterofiron.
Letusfirstconvertthecarbonconcentrationsfromweightpercenttokilogramscarbonpermetercubed
usingEquation4.9a.For0.012wt%C
CC" =
CC
CC
C
C Fe
10 3
Fe
0.012
10 3
99.988
0.012
+
7.87 g/cm3
2.25 g/cm3
0.944kgC/m3
Similarly,for0.0075wt%C
CC" =
0.0075
10 3
99.9925
0.0075
+
7.87 g/cm3
2.25 g/cm3
=0.590kgC/m3
Now,usingarearrangedformofEquation5.3
x x
B
D = J A
CA C B
103 m
= (1.40 10 -8 kg/m 2 - s)
=3.951011m2/s
5.11Determinethecarburizingtimenecessarytoachieveacarbonconcentrationof0.45wt%ataposition2mm
intoanironcarbonalloythatinitiallycontains0.20wt%C.Thesurfaceconcentrationistobemaintainedat1.30
wt%C,andthetreatmentistobeconductedat1000C.Usethediffusiondatafor FeinTable5.2.
InordertosolvethisproblemitisfirstnecessarytouseEquation5.5:
C x C0
x
= 1 erf
2 Dt
Cs C0
wherein,Cx=0.45,C0=0.20,Cs=1.30,andx=2mm=2103m.Thus,
x
Cx C0
0.45 0.20
=
= 0.2273 = 1 erf
2 Dt
1.30 0.20
Cs C0
or
x
erf
= 1 0.2273 = 0.7727
2 Dt
BylinearinterpolationusingdatafromTable5.1
erf(z)
0.85
0.7707
0.7727
0.90
0.7970
0.7727 0.7707
z 0.850
=
Fromwhich
z = 0.854 =
Now,fromTable5.2,at1000 C(1273K)
2 Dt
=1.931011m2/s
Thus,
0.854 =
2 103 m
(2) (1.93 1011 m2 /s) (t)
Solvingfortyields
t=7.1104s=19.7h
5.13Nitrogenfromagaseousphaseistobediffusedintopureironat700C.Ifthesurfaceconcentration
is maintained at 0.1 wt% N, what will be the concentration 1 mm from the surface after 10 h? The diffusion
coefficientfornitrogeninironat700Cis2.51011m2/s.
This problem asks us to compute the nitrogen concentration (Cx) at the 1 mm position after a 10 h
diffusiontime,whendiffusionisnonsteadystate.FromEquation5.5
x
C x C0
Cx 0
=
= 1 erf
2 Dt
Cs C0
0.1 0
= 1 erf
(2)
103 m
(2.5 1011
=1erf(0.527)
UsingdatainTable5.1andlinearinterpolation
erf(z)
0.500
0.5205
0.527
0.550
0.5633
y 0.5205
0.527 0.500
=
0.550 0.500
0.5633 0.5205
fromwhich
y=erf(0.527)=0.5436
Thus,
Cx 0
= 1.0 0.5436
0.1 0
Thisexpressiongives
Cx=0.046wt%N
Note:thisproblemmayalsobesolvedusingtheDiffusionmoduleintheVMSEsoftware.OpentheDiffusion
module,clickontheDiffusionDesignsubmodule,andthendothefollowing:
1.Enterthegivendatainlefthandwindowthatappears.InthewindowbelowthelabelDValueenter
thevalueofthediffusioncoefficientviz.2.5e11.
2.InthewindowjustbelowthelabelInitial,C0entertheinitialconcentrationviz.0.
3.InthewindowtheliesbelowSurface,Csenterthesurfaceconcentrationviz.0.1.
4. Then in the Diffusion Time t window enter the time in seconds; in 10 h there are (60 s/min)(60
min/h)(10h)=36,000ssoenterthevalue3.6e4.
5.Next,atthebottomofthiswindowclickonthebuttonlabeledAddcurve.
6. On the right portion of the screen will appear a concentration profile for this particular diffusion
situation. A diamondshaped cursor will appear at the upper lefthand corner of the resulting curve. Click and
dragthiscursordownthecurvetothepointatwhichthenumberbelowDistance:reads1.00mm.Thenread
thevalueundertheConcentration:.Forthisproblem,thisvalue(thesolutiontotheproblem)is0.05wt%.
5.20 The activation energy for the diffusion of carbon in chromium is 111,000 J/mol. Calculate the
diffusioncoefficientat1100K(827C),giventhatDat1400K(1127C)is6.251011m2/s.
TosolvethisproblemitfirstbecomesnecessarytosolveforD0fromEquation5.8as
Q
D0 = D exp d
RT
111,000 J / mol
= (6.25 10 -11 m2 /s) exp
=8.7107m2/s
Now,solvingforDat1100K(againusingEquation5.8)gives
=4.61012m2/s
5.21Thediffusioncoefficientsforironinnickelaregivenattwotemperatures:
T(K)
D(m2/s)
1273
9.41016
1473
2.41014
(a)DeterminethevaluesofD0andtheactivationenergyQd.
(b)WhatisthemagnitudeofDat1100C(1373K)?
(a)UsingEquation5.9a,wesetuptwosimultaneousequationswithQdandD0asunknownsasfollows:
ln D1 = lnD0
ln D2 = lnD0
Qd 1
R T1
Qd 1
R T2
Qd = R
= (8.31 J/mol - K)
ln D1 ln D2
1
1
T1 T2
1
1
1273 K
1473 K
=252,400J/mol
Now,solvingforD0fromEquation5.8(andusingthe1273KvalueofD)
Q
D0 = D1 exp d
RT1
252,400 J/mol
= (9.4 10 -16 m2 /s) exp
=2.2105m2/s
(b)UsingthesevaluesofD0andQd,Dat1373 Kisjust
D = (2.2 10 -5
=5.41015m2/s
Note:thisproblemmayalsobesolvedusingtheDiffusionmoduleintheVMSEsoftware.OpentheDiffusion
module,clickontheD0andQdfromExperimentalDatasubmodule,andthendothefollowing:
1. In the lefthand window that appears, enter the two temperatures from the table in the book (viz.
1273 and 1473, in the first two boxes under the column labeled T (K). Next, enter the corresponding
diffusioncoefficientvalues(viz.9.4e16and2.4e14).
3.Next,atthebottomofthiswindow,clickthePlotdatabutton.
4. A logD versus 1/T plot then appears,with a line for the temperature dependence for this diffusion
system.AtthetopofthiswindowaregivevaluesforD0andQd;forthisspecificproblemthesevaluesare2.17
105m2/sand252kJ/mol,respectively
5.Tosolvethe(b)partoftheproblemweutilizethediamondshapedcursorthatislocatedatthetopof
the line on this plot. Clickanddrag this cursor down the line to the point at which the entry under the
Temperature(T):labelreads1373.Thevalueofthediffusioncoefficientatthistemperatureisgivenunderthe
labelDiffCoeff(D):.Forourproblem,thisvalueis5.41015m2/s.