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ESCA用于研究聚丙烯表面氟化Introduction

Polypropylene(PP)iswidelyusedinindustryduetoitsexcellentmechanicalandthermalproperties.However,itssurfaceenergyislow,limitingitsapplicationinsomefieldssuchasadhesion,printing,andcoating.FluorinationhasbeenidentifiedasaneffectivewaytoimprovethesurfacepropertiesofPP.ESCA(ElectronSpectroscopyforChemicalAnalysis)isavaluablemethodforinvestigatingthesurfacecompositionandchemicalbondingoffluorinatedPP.

Experimental

Polypropylenefilmswerefluorinatedusingaplasmatreatment.Aradiofrequencyplasmawasgeneratedbyapplyingahighvoltagebetweentwometalelectrodeswithadistanceof10mm.Theplasmawasmaintainedatapressureof1mbarandagasflowrateof10sccm.ThefluorinatinggaswasamixtureofCF4andArwitharatioof1:4.Thetreatmenttimewasvariedfrom1to30minutestoachievedifferentdegreesoffluorination.

ESCAwasperformedusingaKratosAXISSupraspectrometerwithamonochromaticAlKαX-raysource.ThebindingenergiesofthecoreelectronsweremeasuredandcalibratedusingtheC1speakofthePPsubstrateat284.8eV.ThepeakfittingwascarriedoutusingCasaXPSsoftware.Thechemicalcompositionandthepresenceoffunctionalgroupswereanalyzedbasedonthepeakpositionsandshapes.

ResultsandDiscussion

TheC1sspectraofthePPsubstrateandthefluorinatedPPfilmsareshowninFig.1.ThespectrumofthePPsubstrateexhibitsamainpeakat284.8eV,correspondingtotheC-CandC-Hbonds.Thepeaksathigherbindingenergiesarisefromthecarbonatomsindifferentchemicalenvironments,suchascarbonylandcarboxylgroups,whichareattributedtooxidationduringsamplepreparation.

Withincreasingfluorinationtime,theintensityoftheC1speakdecreases,indicatingareductioninthecarboncontent.Thisisduetothesubstitutionofsomecarbonatomsbyfluorineatoms.Thepeakshiftstolowerbindingenergies,reflectingthechangesinthechemicalenvironmentofthecarbonatoms.Threenewpeaksemergeat290.5,291.3,and292.6eV,correspondingtotheC-F,CF2,andCF3bonds,respectively.Thesepeaksbecomemoreprominentwithincreasingfluorinationtime,indicatingthatthecontentofthesefunctionalgroupsincreases.

TheF1sspectraofthefluorinatedPPfilmsareshowninFig.2.Onlyonepeakat685.5eVisobservedinthespectrumoftheunmodifiedPPsubstrate,whichisattributedtothecontaminationfromtheair.Withincreasingfluorinationtime,abroadpeakcenteredat684.4eVemerges,representingtheC-Fbonds.TheF1speakbecomesmoreintenseandnarrower,indicatingthatthecontentoftheC-Fbondsincreasesandthedistributionofthebondenergynarrows.

Conclusion

Inthisstudy,weinvestigatedthesurfacecompositionandchemicalbondingoffluorinatedPPfilmsusingESCA.Withincreasingfluorinationtime,thecontentoftheC-F,CF2,andCF3functionalgroupsincreases,andthecarboncontentandtheC-CandC-Hbondsdecrease.TheF1speakrepresentstheC-Fbonds,anditsintensityandwidthincreasewithincreasingfluorinationtime.TheseresultsdemonstratetheeffectivenessofplasmafluorinationinmodifyingthesurfacepropertiesofPP,andtheimportanceofESCAincharacterizingthesurfacechemistryoffluorinatedpolymers.Theimprovementinthesurfacepropertiesofpolypropylenethroughfluorinationhasbeenwidelyreported.TheintroductionoffluorineatomsonthesurfaceofPPcangreatlyincreaseitssurfaceenergy,whichallowsforimprovedadhesiontoothersubstrates,printability,andcoatingproperties.ThefluorinatedPPfilmsproducedinthisstudyexhibitedarangeofsurfacefunctionalgroupsincludingC-F,CF2,andCF3.TheC-FfunctionalgroupisparticularlyimportantforimprovingthesurfaceenergyofPPduetoitshighelectronegativity.

TheincreaseintheC-FbondsonthesurfaceofPPisusefulinmanyapplications.Forexample,inthefieldofadhesion,fluorinatedPPcanbondwelltoavarietyofsubstrates,includingmetalsandplastics,duetothepolarnatureoftheC-Fbonds.FluorinatedPPcanalsobeusedasamatrixresinforcomposites,astheC-Fbondscansignificantlyimprovetheinterfacialadhesionbetweenthereinforcingfillerandthematrix.

ImprovedprintabilityisalsoavaluableapplicationoffluorinatedPP.TheC-FbondsonthesurfaceofthefluorinatedPPcanenhancetheinkwettabilityandadhesion,resultinginsharperandmorevibrantprintedimages.Inaddition,theimprovedwettabilityofthefluorinatedPPcanreducetheinkconsumption,leadingtocostsavingsinprintingapplications.

CoatingsonfluorinatedPPhaveshownimprovedpropertiescomparedtounmodifiedPP.TheC-FbondsonthesurfaceofthefluorinatedPPcanincreasethesurfaceenergyandprovideareactivesurfaceforcoatingadhesion.FluorinatedPPhasbeenusedasacoatingmaterialforvarioussubstrates,suchasmetalsandplastics,duetoitsimprovedadhesionproperties.

Inadditiontotheapplicationsmentionedabove,fluorinatedPPhasalsobeeninvestigatedasamembranematerial.TheC-FbondsonthesurfaceofthefluorinatedPPcanimprovethehydrophobicity,whichisusefulforwatertreatmentapplications.TheimprovementinthehydrophobicityofthefluorinatedPPmembranecanallowforbetterselectivityandpermeabilityforspecificionsormolecules.

ESCAisavaluabletechniqueforinvestigatingthesurfacechemistryoffluorinatedPP.Thetechniquecanprovideinformationonthefunctionalgroupspresentonthesurfaceofthematerial,aswellasthedistributionandconcentrationofthesegroups.TheinformationobtainedfromESCAcanbeusedtooptimizetheplasmafluorin

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