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1、CRYSTALLIZATIONINHIGHPOLYMERS397onsurface1isessentiallycomplete.16Underinhomogeneityhypothesisthetemperaturede•theseconditionstheratiooftheVmvaluesfoundpendenceofVBwouldprobablyalsobeconnectedwillbesimply61,i.e.VmI!(Vml+Vm2).withthepropertiesofsurface2,but
2、acompleteExperimentalresultsofthistypehavebeentestofsuchanexplanationmustawaitmeasure•frequentlyfound,notablybyArmbruster6whomentswhichextendthroughouttherangeofobtainedvaluesofv.,theLangmuirl7saturationabout0.05to1.5monolayers(basedontheadsorption(equival
3、entto61vmorVml,ifthelargestVmvalueobtained).presenttheoryapplies),correspondingto61ThisextensionoftheBETequationappearsvaluesintherange0.2-1forargon,nitrogen,tooffernoexplanationoftheobservedlowcarbonmonoxide,etc.onsilverfoilat78androughnessfactorsrecently
4、reportedbyEmmett,1890oK,basedontheassumptionthatsincetheseoccuratrelativepressuresof0.1orVmequalstheapparentgeometricarea.Whilesuchfiguresabove.Inconclusion,theauthorwishestothankDrs.arenotunreasonable,thisleavesunexplainedP.H.EmmettandS.W.Wellerforseveral
5、the"coefficientofthermalexpansion,"dlnv./dT,helpfuldiscussionsofthiswork.Gratefulac•observedinthatwork.OnthebasisoftheknowledgmentismadetotheJohnSimon16Herewehadbestmakeagaintherestrictioncz»I,GuggenheimMemorialFoundation,whichsup•forotherwiseCowillbelow,a
6、nd,correspondingly,thevalueportedthisinvestigation.ofXm=1/[1+(c)lJsolargethattheusualdeviationsatlargexmayappeardespitetheapproximateconstancyof18ReportedattheChicagomeetingoftheAmericancasgivenbyEq.(6).ChemicalSociety,September1946;SeeAbstractsof17Referen
7、ce2,pp.60,ff.Papers,110thMeeting,No.44,p.25E.TIlEJOURNALOFCHEMICALPHYSICSVOLUME15.NUMBER6JUNE,1947ThermodynamicsofCrystallizationinHighPolymers.I.CrystallizationInducedbyStretching*PAUL].FLORYResearchLaboratory,GoodyearTireandRubberCompany,Akron,Ohio(Recei
8、vedFebruary12,1947)Atheoryoforientedcrystallizationinelongatedpoly•Apparentdiscrepanciesbetweensomeofthesepredic•mershavingnetworkstructures(e.g.,invulcanizedrubber)tionsandvariousobservationsareattributedtos
