Silicone Surface Science PDF
Preview Silicone Surface Science
Advances in Silicon Science ADVANCES IN SILICON SCIENCE VOLUME4 SeriesEditor: JANISMATISONS GelestInc.,11EastSteelRoad,Morrisville,PA19067,USA AdvancesinSiliconScienceisabookserieswhichpresentsreviewsofthepresentand futuretrendsinsiliconscienceandwillbenefitthoseinchemistry,physics,biomedical engineering, and materials science. It is aimed at all scientists at universities and in industrywhowishtokeepabreastofadvancesinthetopicscovered. SeriesEditor Prof.JanisMatisons SeniorR&DManager GelestInc 11EastSteelRoad Morrisville Pennsylvania19067 USA [email protected] Volume4 SiliconeSurfaceScience VolumeEditors MichaelJ.Owen PetarR.Dvornic MichiganMolecularInstitute Midland,MI USA Forfurthervolumes: www.springer.com/series/7926 Michael J. Owen (cid:2) Petar R. Dvornic Editors Silicone Surface Science Editors MichaelJ.Owen PetarR.Dvornic MichiganMolecularInstitute MichiganMolecularInstitute Midland,MI Midland,MI USA USA Chapter6wascreatedwithinthecapacityofanUSgovernmentalemploymentandthereforeisinthe publicdomain. ISSN1875-3108 ISSN1875-3086(electronic) AdvancesinSiliconScience ISBN978-94-007-3875-1 ISBN978-94-007-3876-8(eBook) DOI10.1007/978-94-007-3876-8 SpringerDordrechtHeidelbergNewYorkLondon LibraryofCongressControlNumber:2012939196 ©SpringerScience+BusinessMediaDordrecht2012 Thisworkissubjecttocopyright.AllrightsarereservedbythePublisher,whetherthewholeorpartof thematerialisconcerned,specificallytherightsoftranslation,reprinting,reuseofillustrations,recitation, broadcasting,reproductiononmicrofilmsorinanyotherphysicalway,andtransmissionorinformation storageandretrieval,electronicadaptation,computersoftware,orbysimilarordissimilarmethodology nowknownorhereafterdeveloped.Exemptedfromthislegalreservationarebriefexcerptsinconnection with reviews or scholarly analysis or material supplied specifically for the purpose of being entered and executed on a computer system, for exclusive use by the purchaser of the work. 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Printedonacid-freepaper SpringerispartofSpringerScience+BusinessMedia(www.springer.com) Preface Godmadethebulk;surfaceswereinventedbythedevil WolfgangPauli1 It is somewhatsurprising,in our opinion,that this book,to thebest of our knowl- edge, is the first to be devoted to the surface properties and behavior of silicone polymers.Thesituationisallthemoreperplexingwhenoneconsidersthatsurface- relatedapplicationshaveconsistentlyaccountedforthemajorpartofthecommer- cialsuccessofsiliconessincetheestablishmentofthisindustryintheearly1940s. The importance of surfaces and interfacial phenomena cannot be overempha- sized.Whenanytwomaterialsarebroughttogetheritistheirsurfacesthatinitially matterandtheirinterfacialinteractionsthatneedtobestudiedandunderstoodfirst. Therefore,inordertocontributetothis,inthisbookweattempttopresentabroad overviewofthestate-of-the-artofsiliconesurfacesciencebyagroupofwidelyrec- ognizedexpertsintheirfieldssummarizingboththehistoricaldevelopmentandthe currentprogressineachselectedarea.Withalmost70yearsofscientificandtech- nologicalinterestinsiliconeswecanhardlyclaimtoberigorouslycomprehensive, butwearesurethatthemostexcitingdevelopmentsinthisfieldtodayarecovered inthisvolume. Muchofthecontentofthisbookdealswithpolydimethylsiloxane(PDMS)since it has been the mainstay of the silicone industry from its very beginnings to the present day. Furthermore, looking into the future, while anticipatingcontinued in- terest in and development of other polymers derived from organosilicon entities, thereisnoreasonnottobelievethatthescienceandapplicationsofPDMSandre- latedorganosiloxanepolymerswillcontinuetogrowandplayasimportantaroleas theyhaveinthepast. Asiscommoninthefieldofsilicon-containingpolymers,weusethetermsili- conetodescribepolymerswhosebackboneissiloxane,i.e.alternatingarrangement ofsiliconandoxygenatoms,withpendentorganicgroupsattachedtothatbackbone. Consequently,polyhedraloligomericsilsesquioxanes(POSS),whichcertainlymeet 1Quotedin“Growth,DissolutionandPatternFormationinGeosystems”(1999)byBjornJamtveit andPaulMeakin,p.291. v vi Preface the“alternatingsiloxanebonds”requirement,arenotusuallyconsidered“silicones”, becauseoftheirinsufficientmolecularweightsandfundamentallydifferentmacro- scopicproperties.Nevertheless,weconsidertheseoligomerstobeapropersubject forinclusioninthisvolumebecauseoftheircriticalimportancetosiliconesurface scienceasexplainedindetailintwochaptersdealingwithPOSSderivatives. Whatmightappeartosometobeasomewhatcapriciouschapterorderisbased on our attemptto marry two seemingly “incompatible”concepts: (i) a progressive shiftfromfundamentalstomoreappliedtopics,and(ii)adevelopmentfrom“pure” PDMStootherimportant,surface-activesiliconessuchasfluorosiliconesandmod- ifiedmaterialssuchassurfactantsandcouplingagents.Thebookopenswithagen- eralintroductiontosiliconesurfaceswithanemphasisonthesurfacepropertiesof PDMS.Followingthis,inChap.2AhnandDhinojwaladescribethesumfrequency generationvibrationalspectroscopyofsiliconesurfacesandinterfaces,arelatively recentlyintroducedtechniquethat has providedconsiderablenew insightintosur- facestructureandmostnotablytoburiedinterfacesaswell.Genzerandco-workers havemadegreatstridesincreatingdifferentfunctionalitiesonsiliconesurfacesand their contributions are reviewed in Chap. 3. Superhydrophobic surfaces have fea- tured strongly in the last decade, and McCarthy et al. review their silane/siloxane studiesofthistopicinChap.4.Chapters5and6dealwithfluorine-containingsili- coneswhereGanachaudandAmeduriandtheircolleaguesreviewstructure/property relationshipsinfluorosiliconesandTutejaandMabrycontributeachapteronfluoro- POSSmaterialswhicharehighlyrelevanttotheearliertopicofsuperhydrophobic- ity,respectively.Ourstronginterestinfluorosiliconesderivesfromtheirpotentialto producesignificantlylowersurfaceenergiesthanconventionalPDMSsurfaces. Langmuir trough investigations of silicones have been of interest since surface studiesofsiliconesbegan.InChap.7EskerandYuprovideasummaryofthistopic withanupdateofrecentworksthatoffersanotherfacetofthegrowingimportance ofPOSScompoundstoorganosiliconsurfacesciencetoday.Atopicofhigh-interest tocurrentsiloxanesciencewithconsiderablesurface-relatedimplicationsisthein- teractionofproteinsandsilicon-basedmaterialswhichisthesubjectofChap.8by Clarsonandco-workers.Thisisfollowedbyareviewofsiliconesurfactantfunda- mentalsandapplicationsbySnowandPetroffinChap.9,whileMatisons’Chap.10 deals with the adsorption of polymeric siloxanes on glass surfaces and their cou- pling behavior as well as with more conventional silane coupling agents. Surface treatments such as plasma and corona have been widely exploited in silicone sur- face modification.These are summarized in Chap. 11 by Hillborg and Gedde (see alsoChap.3whichdealswithaspectsofthistopic). Analyticaltechniquesareself-evidentlycentraltounderstandingofsiliconesur- face behavior. A review of these studies with emphasis on X-ray photoelectron spectroscopy (XPS), secondary ion mass spectrometry (SIMS), scanning electron microscopy(SEM)andscanningprobemicroscopy(SPM)isprovidedbyLeadley, O’HareandMcMillaninChap.12.Finally,weclosewithanoutlineofsomeimpor- tantsurfaceapplicationsofsiliconesrelatingtoboththescienceandtechnologyof siliconesurfaces.Someoftheseapplicationsarealsoincludedinseveraloftheear- lierchapters,underliningadominantthemeofthisbook,therelationshipbetween Preface vii thestructureandsurfacepropertiesofsiliconesandtheirutilizationinvariousevery- dayaswellasmoresophisticatedapplications. A variety of authors contributed different perspectives to this work, including academicandindustrialspecialistsfromEuropeandNorthAmerica.Wesincerely thankallofthemfortheirimpressivecontributionsandtheirpatienceandpersever- ance throughout the process of bringing this book to fruition. We are particularly gratefultoourpublishingeditor,Dr.SoniaOjoandherSpringercolleaguesfortheir experthelpduringthepreparationofthemanuscriptandtoDonatasAkmanavicˇius ofVTeXUABintherealizationofthisfinishedwork. Midland,MI,USA MichaelJ.Owen PetarR.Dvornic Contents 1 GeneralIntroductiontoSiliconeSurfaces . . . . . . . . . . . . . . . 1 MichaelJ.OwenandPetarR.Dvornic 1.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1 1.2 LiquidSurfaceTension . . . . . . . . . . . . . . . . . . . . . . . 4 1.3 WaterContactAngleStudies . . . . . . . . . . . . . . . . . . . . 7 1.4 SolidSurfaceEnergyDetermination . . . . . . . . . . . . . . . . 10 1.5 ContactMechanicsApproach . . . . . . . . . . . . . . . . . . . . 12 1.6 LangmuirTroughStudies . . . . . . . . . . . . . . . . . . . . . . 15 1.7 OtherSilicones . . . . . . . . . . . . . . . . . . . . . . . . . . . . 17 1.8 ConcludingRemarks. . . . . . . . . . . . . . . . . . . . . . . . . 19 References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 19 2 SumFrequencyGenerationVibrationalSpectroscopyofSilicone Surfaces&Interfaces . . . . . . . . . . . . . . . . . . . . . . . . . . 23 DongchanAhnandAliDhinojwala 2.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 23 2.2 Fundamentals . . . . . . . . . . . . . . . . . . . . . . . . . . . . 24 2.2.1 TheoryofSurface-SensitiveSFG . . . . . . . . . . . . . . 24 2.2.2 ExperimentalSet-upandSampleConsiderations . . . . . . 28 2.2.3 Simulation . . . . . . . . . . . . . . . . . . . . . . . . . . 30 2.2.4 SiliconeCureSystems . . . . . . . . . . . . . . . . . . . . 31 2.3 ApplicationsofSFGtoSiliconeSurfacesandInterfaces . . . . . . 32 2.3.1 SiliconeSurfaceOrientationandRearrangement . . . . . . 32 2.3.2 FrictionandLubrication . . . . . . . . . . . . . . . . . . . 34 2.3.3 Adhesion . . . . . . . . . . . . . . . . . . . . . . . . . . . 42 2.3.4 Sensors . . . . . . . . . . . . . . . . . . . . . . . . . . . . 50 2.4 ConclusionsandFutureDirections . . . . . . . . . . . . . . . . . 51 2.4.1 Materials . . . . . . . . . . . . . . . . . . . . . . . . . . . 51 2.4.2 InstrumentationandTechniques . . . . . . . . . . . . . . . 53 References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 54 ix x Contents 3 Creating Functional Materials by Chemical and Physical FunctionalizationofSiliconeElastomerNetworks . . . . . . . . . . . 59 Jan Genzer, Ali E. O˝zçam, Julie A. Crowe-Willoughby, and KirillEfimenko 3.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 59 3.2 PhysicalModificationofSENSurfaces . . . . . . . . . . . . . . . 62 3.3 ControllingMolecularandMacromolecularPackingUsingSENs . 67 3.4 TurningFlatSENsintoTopographicallyCorrugatedSurfaces . . . 74 3.5 SENasaMaterialPlatformforCreatingResponsive/“Smart” Materials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 78 3.6 AQuestTowardsUniversalCoatingLayers . . . . . . . . . . . . . 85 3.7 Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 89 References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 90 4 UsingSurface-AttachedOrganosilanestoControlandUnderstand HydrophobicityandSuperhydrophobicity . . . . . . . . . . . . . . . 95 Joseph W. Krumpfer, Lichao Gao, Alexander Y. Fadeev, and ThomasJ.McCarthy 4.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 95 4.2 MonofunctionalSilanes:MolecularTopographyandFlexibility ContributetoContactAngleHysteresis . . . . . . . . . . . . . . . 96 4.3 MethylchlorosilanesReacttoFormSuperhydrophobicSurfaces . . 102 4.3.1 Methyltrichlorosilane and a Perfectly Hydrophobic Surface[32] . . . . . . . . . . . . . . . . . . . . . . . . . 104 4.3.2 The(CH ) SiCl/SiCl Azeotrope[34] . . . . . . . . . . . 105 3 3 4 4.4 “Unreactive”SiliconesReactwithInorganicSurfaces . . . . . . . 109 4.5 ClosingComments. . . . . . . . . . . . . . . . . . . . . . . . . . 113 References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 113 5 ComparisonofSurfaceandBulkPropertiesofPendantandHybrid Fluorosilicones . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 115 Cedric Pasquet, Claire Longuet, Siska Hamdani-Devarennes, BrunoAmeduri,andFrançoisGanachaud 5.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 115 5.2 SomeInsightsonFluorosiliconeSynthesis . . . . . . . . . . . . . 117 5.2.1 SynthesisofPendantFluorosilicones . . . . . . . . . . . . 118 5.2.2 SynthesisofHybridFluorosilicones. . . . . . . . . . . . . 121 5.3 SurfaceProperties . . . . . . . . . . . . . . . . . . . . . . . . . . 125 5.3.1 SurfaceTensionofPendantFluorosilicones. . . . . . . . . 125 5.3.2 SurfaceTensionofHybridFluorosilicones . . . . . . . . . 133 5.3.3 ConclusionstoSect.5.3 . . . . . . . . . . . . . . . . . . . 134 5.4 ThermalPropertiesofFluorosilicones . . . . . . . . . . . . . . . . 134 5.4.1 PendantFluorosilicones . . . . . . . . . . . . . . . . . . . 135 5.4.2 HybridFluorosilicones . . . . . . . . . . . . . . . . . . . 136 5.4.3 ConclusionstoSect.5.4 . . . . . . . . . . . . . . . . . . . 146 Contents xi 5.5 SwellingPropertiesofFluorosilicones . . . . . . . . . . . . . . . 146 5.5.1 PendantFluorosilicones . . . . . . . . . . . . . . . . . . . 146 5.5.2 HybridFluorosilicones . . . . . . . . . . . . . . . . . . . 148 5.5.3 ConclusionstoSect.5.5 . . . . . . . . . . . . . . . . . . . 152 5.6 MechanicalPropertiesofFluorosilicones . . . . . . . . . . . . . . 152 5.6.1 PendantFluorosilicones . . . . . . . . . . . . . . . . . . . 152 5.6.2 HybridFluorosilicones . . . . . . . . . . . . . . . . . . . 161 5.6.3 ConclusionstoSect.5.6 . . . . . . . . . . . . . . . . . . . 165 5.7 NewAvenuesinFluorosiliconeElastomerSynthesis . . . . . . . . 165 5.7.1 RandomCopolymers . . . . . . . . . . . . . . . . . . . . 165 5.7.2 BlockCopolymers . . . . . . . . . . . . . . . . . . . . . . 167 5.8 Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 171 AppendixA DefinitionandMeasurementsofSurfaceTensionforSoft Polymers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 171 A.1 DefinitionofSurfaceTension . . . . . . . . . . . . . . . . 171 A.2 MeasurementofLiquidSurfaceTensions . . . . . . . . . . 172 A.3 MeasurementofSolidSurfaceTensions . . . . . . . . . . 173 Appendix B Swelling Measurements, Solubility Parameters and PDMSCase . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 174 References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 175 6 TheDesignofNon-wettingSurfaceswithFluoroPOSS . . . . . . . . 179 AnishTutejaandJosephM.Mabry 6.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 179 6.1.1 Non-wettingSurfaces . . . . . . . . . . . . . . . . . . . . 179 6.1.2 FluoroPOSS . . . . . . . . . . . . . . . . . . . . . . . . . 180 6.1.3 DesignParameters . . . . . . . . . . . . . . . . . . . . . . 182 6.2 PreparationofMaterials . . . . . . . . . . . . . . . . . . . . . . . 184 6.2.1 FluorodecylPOSSSynthesis . . . . . . . . . . . . . . . . 184 6.2.2 FluoroPOSSCompositePreparation . . . . . . . . . . . . 185 6.3 CharacterizationTechniques . . . . . . . . . . . . . . . . . . . . . 185 6.3.1 ContactAngleAnalysis . . . . . . . . . . . . . . . . . . . 185 6.3.2 Microscopy . . . . . . . . . . . . . . . . . . . . . . . . . 186 6.4 FluoroPOSSMaterialProperties . . . . . . . . . . . . . . . . . . 186 6.4.1 FluoroPOSSCompounds . . . . . . . . . . . . . . . . . . 186 6.4.2 FluoroPOSSComposites . . . . . . . . . . . . . . . . . . 186 6.5 Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 190 References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 190 7 LangmuirMonolayersofSiloxanesandSilsesquioxanes . . . . . . . 195 AlanR.EskerandHyukYu 7.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 195 7.2 SiliconeLangmuirFilms . . . . . . . . . . . . . . . . . . . . . . 195 7.2.1 SurfacePressure-AreaperRepeatUnit(Π-A)Isotherms ofPDMSLangmuirFilms . . . . . . . . . . . . . . . . . . 196 7.2.2 ViscoelasticPropertiesofPDMSLangmuirFilms . . . . . 199
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