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TableofContents Introduction .................................................................................................................................. 4 Motivation................................................................................................................................. 4 Objectives .................................................................................................................................. 5 IntellectualMerit ...................................................................................................................... 5 BroaderImpact ......................................................................................................................... 5 MaterialSelection......................................................................................................................... 6 MatrixMaterialPolyurethane.............................................................................................. 6 MicrocapsuleShellUreaFormaldehyde ........................................................................... 7 EncapsulatedMonomerDicyclopentadiene ..................................................................... 8 Fabricationsection ....................................................................................................................... 9 Microcapsulefabrication......................................................................................................... 9 Background......................................................................................................................... 10 MicrocapsuleFabricationProcess ................................................................................... 10 Results.................................................................................................................................. 12 BackupPlans....................................................................................................................... 13 MatrixMoldFabrication ....................................................................................................... 14 TestingandCharacterization ................................................................................................... 18 Microscopy.............................................................................................................................. 18 TensileTesting........................................................................................................................ 22 ImpactTesting ........................................................................................................................ 26 ContactAngle ......................................................................................................................... 29 FourierTransformInfraredSpectroscopy.......................................................................... 30 FutureWork................................................................................................................................ 31 Conclusions................................................................................................................................. 32 Acknowledgements ................................................................................................................... 33 References ................................................................................................................................... 34 AppendixA:MicrocapsuleSynthesisProcedure;................................................................. 36 UreaFormaldehydeEncapsulatingDCPD ............................................................................ 36 Chemicals ............................................................................................................................ 36 Equipment/Supplies .......................................................................................................... 36 PreparationSteps: .............................................................................................................. 36 Procedure ............................................................................................................................ 37 AppendixB:MaterialSafetyDataSheets............................................................................... 38 AppendixC:CommitteeOrganization................................................................................... 42 AppendixD:Timeline ............................................................................................................... 44 AppendixE:Budget .................................................................................................................. 45 AppendixF:Recommendations .............................................................................................. 46
TableofFigures Figure1.Castcastingresinforpolyurethanefabrication[4] ................................................ 7 Figure2.SchematicofthereactionofDCPDmonomerwithGrubbscatalystinaliving ringopeningpolymerization[1]........................................................................................ 9 Figure3.(a)Moldusedtocreatedogbonespecimen,(b)MoldusedtocreateIzod specimens ............................................................................................................................ 14 Figure4.Polymerizationofpolyurethane.............................................................................. 16 Figure5.Moldedpolyurethanewithobviousexcessbubbles ............................................ 17 Figure6.Characteristicmicrocapsulesfrom(a)onefiltration,(b)twofiltrations,(c) multiplefiltrationsand(d)microcapsules(washedinsilane)embeddedin polyurethane....................................................................................................................... 19 Figure7.(a)Characteristicparticlefromsamplesubjectedtoasinglefiltration,(b) suspectedmonomerparticles........................................................................................... 20 Figure8.(a)Characteristicagglomerationofparticlesfoundinmaximallyfiltrated sampleofmicrocapsules,particleinboxissameasthatshowninpart(b).............. 21 Figure9.(a)SurfaceofmicrocapsulefromresearchgroupatUniversityofMaryland, and(b)SurfaceofamicrocapsulefromresearchgroupatUniversityofIllinoisat UrbanaChampaign[1] ..................................................................................................... 21 Figure10.(a)Sintech20universaltestingmachineusedfortensiletesting,(b)Dogbone cutterusedtomaketensiletestspecimens,(c)ASTMTypeVspecimencutfrom mold ..................................................................................................................................... 23 Figure11.(a)Typicaltensiletestdatanumericaloutput,(b)Typicaltensiletestgraphof loadversuselongation ...................................................................................................... 25 Figure12.(a)IzodimpacttesteratAdellPlastics,Inc,(b)AscastIzodTestSpecimens (beforenotching),(c)MillingmachineatAdellPlasticsusedtonotchIzodtest specimens ............................................................................................................................ 27 Figure13.Izodtestspecimenembeddedwithmicrocapsulesshowingporosity............ 28 Figure14.ContactanglemeasurementofDCPDonpolyurethane.Theanglewas measuredas1923degrees ............................................................................................... 30 Figure15.a)ReferenceFTIRforDicyclopentadiene[2],(b)FTIRspectrumfor microcapsulepowder(red),background(green) ......................................................... 31
Introduction
Motivation Microcrackformationduetofatigueinevitablydegradespropertiesand eventuallycausescatastrophicfailureinstructuralmaterials.Detectionofmicrocracksis difficult,andoftenrepairisnotanoption,especiallyforinaccessiblecomponents. Previousresearchhasdemonstratedthatmonomerfilledmicrocapsulesand solidcatalystcantheoreticallybeembeddedinathermosettingpolymericmatrix.Asa microcrackpropagates,itisattractedtothemicrocapsule,andthetipofthecrack rupturestheshell,releasingmonomerintothecrack.Asthelowviscositymonomer flowsintothecrackviacapillaryaction,itinteractswiththedispersedcatalystand quicklypolymerizes.Thepolymerizedmonomerbondsthecrackfaces,thusblunting thecracktipandpreventingpropagation.Whilethehealedmaterialisnotfully restoredtoitsoriginalstate,ithasbeenshownthathealingrecoversalargeportionof theoriginalproperties.Bypreventingmicrocrackpropagation,selfhealingmechanisms lengthenlifetimeandimprovereliability. TheENMA490capstonedesignprojectconsistedofthedesignandfabricationof apolymercompositedesignedtohealmicrocracksautonomously.Initialmotivation wasprovidedbyaNASAsolicitationtodevelopaselfhealingwire.Thesolicitation andexistingliteratureonselfhealingcompositesformedabasisfordesigninganovel system.
Objectives Newselfhealingpolymersystemswillextendlifetimeofcomponentsthatare inaccessibleforroutinemaintenance.Thisprojectwillcenteronthedevelopmentofa thermosettingpolymerwithselfhealingproperties.Specificmonomers,catalysts, supplies,andprocessingequipmentwillbeneededtocarryoutthesynthesisofthe proposedsystem.Initialresearchhasisolatedthecomponentsthatwillbenecessaryfor ahighprobabilityofsuccess. Intellectual Merit Selfhealingisanintriguingmechanisminspiredbybiologicalsystemsthat includesmanycomplexinterdependentvariables.Bycomparingtheresultsobtainedto previousresearch,wecandetermineifselfhealingisageneralphenomenonormatrix materialspecific. Broader Impact
Materials Selection
Allmaterialsselectedwerechosenbasedprimarilyontheirmaterialproperties,
thepreviousresearch,andfacultyrecommendations.Someotherfactorsinfluencing materialselectionincludedfabricationfeasibility,safetyandethicalissues,cost, commercialavailability,anddeliverytime. Matrix Material - Polyurethane Thematrixmaterialselectedforthisprojectwaspolyurethane.Thismaterialwas selectedforavarietyofdifferentreasons.Inpreviousresearch,anepoxymatrix materialwasused[1].Polyurethane(PU)isagoodchoiceforamatrixmaterialbecause ithassuperiortoughnessandhighabrasionresistance.Additionally,thetwopartresin systemishighlyreactive,hasalowviscosity,andalowglasstransitiontemperature. Thesepropertiescombinedmakeitsuitableforprocessing.Dr.Briberhas recommendedthismaterialbecause,inadditiontotheaforementionedproperties,PU shapesareveryeasytofabricatebysandwichingthepolyurethanemixturebetween twoglasssheetsthatareheldtogetherbybinderclips.Therearetwopartstothe polyurethane:partAisadiorpolyisocyanate,andpartBisapolyol.WhenpartA andpartBaremixedtogether,thetwopartspolymerizetoformthepolyurethane compound.ThestructuresofthesetwopartscanbeseeninappendixB.Polyurethane isalsorelativelyinexpensiveandcommerciallyavailable.Polyurethaneisalsoa relativelyharmlesspolymerandwaseasytofabricateinalabprovidedbyDr.Al Sheikhly.
Figure1.QuikCastcastingresinforpolyurethanefabrication[4]
Microcapsule Shell Urea Formaldehyde Microencapsulationisawidelyusedprocesstocontainliquidsinshells.There areseveralbasicmethods,mostofwhichinvolvetheformationofanemulsion.Inthe caseofpoly(ureaformaldehyde)(UF)shells,microencapsulationisexecutedusinga variationofinterfacialencapsulationcalledinsitupolymerization[5]. Thereareseveralspecificationsthatthecapsulemustmeetinordertobe successfulintheselfhealingsystem.Fortheshell,theelasticmodulusmustbelessthan thatofthematrix.Iftheelasticmodulusoftheshellislarger,thecrackwillbediverted awayfromthecapsule.Thiswillsucceedinstrengtheningthecompositeduetothe lengtheningofcrackpropagationdistance.However,selfhealingwillbeavoided becausethecracktipwillgoaroundthecapsuleratherthanpierceitsshell.Thus,the selfhealingmechanismbecomesuseless. Ureaformaldehyde(UF)capsulesareverywidelyusedinindustryandthe processiswellstudiedandunderstood.ThismadeUFanespeciallyattractive encapsulationmediumbecausescientistsandengineersoftenspendyearstodecades researchingtheeffectofprocessingparametersonthepropertiesofthemicrocapsules
likesize,permeability,wallthickness,percentyield,shape,anddegreeof agglomeration.Inthiscase,UFhadbeenstudiedbyagroupattheUniversityofIllinois atUrbanaChampaign(UIUC)andspecificrecipeshadbeendevelopedandmade availablewithchemicalnamesandquantitiesaswellasafull,relativelydetailed procedure.UIUChadalreadyfoundsuccesswithUFsoitwaschosenbecausewhilewe wouldhavelikedtohavebeeninventive,wedidnothavethetimeorexpertiseto developourownprocess. TheUFselectionwasfoundtohaveanotherbenefit.Whilewritingtheproposal forfunds,werealizedourintentiontoshowthattheselfhealingmechanismisnot exclusivetoepoxycomposites.TheAutonomicHealingresearchgroupatUIUChas demonstratedsuccessfulselfhealinginepoxycompositesandhassuggestedthatthe samemechanismappliestootherpolymermatrixmaterials.However,theydidnottest anyothermaterials.Bykeepingallelseconstant,itispossibletoseetheeffectofthe matrixontheselfhealingefficiencyofthesystem.Iftoomanyvariablesareintroduced, oneisnotabletodeterminewhathascausedthedifferences.Polyureacapsuleswere chosenforplanB.However,recipeslikethosefoundinWhitesU.S.PatentNo. 6,518,330forUFwerenotavailableforpolyureasothateventhoughmaterialswere orderedjustincase,muchworkwouldhavetobedonetoconcoctarecipe.Thusthe selectionofUFwasagooddecision. Encapsulated Monomer Dicyclopentadiene Dicyclopentadiene(DCPD)wasthemonomerselectedtobeencapsulated becauseithasmanysuitablepropertiesforthisapplication.Dicyclopentadieneisa strainedcyclicmoleculecontainingtwobonds.Previousresearchhasshownthata solutioncontainingDCPDcansuccessfullybeencapsulatedinureaformaldehyde microcapsules.ThelowviscosityoftheDCPDsolutionallowsittoeasilyfillcracks.To 8
Figure2.SchematicofthereactionofDCPDmonomerwithGrubbscatalystinalivingringopening metathesispolymerization[1]
Fabrication
Microcapsule fabrication
Background Microcapsuledesignisveryimportanttotheselfhealingeffectivenessofthe material.Thesizeofthecapsuleandthethicknessoftheshellareimportantdesign parameters.Thesmallerthecapsules,thebettertheprobabilityisthatthecapsuleswill berupturedbyacracksincetheyaremorespreadthroughoutthematrix.Also,smaller capsuleswereshowntohavealargervirginfracturetoughnessthanthatofspecimens withlargermicrocapsules[3].However,smallercapsulesinteractmoreduetoincreased surfaceareaandthustendtoagglomerate.Separationbecomesmoredifficultand surfacemodificationisneededtopreventagglomerationthatpreventsuniform, randomdispersion.Inaddition,thecapsulesmustcontainenoughmonomertoblunt thecracktipwhenpolymerizedandinteractwithcatalyst. Microcapsulediameterisdeterminedbythestirringrate.AccordingtoBrown [1],thereisalinearrelationshipbetweenthelogofthemeandiameterandthelogofthe agitationrate.Ingeneral,thefasterthestirringis,thesmallerthecapsulesare. However,iftherateistoohigh,ahighshearsituationdevelops.Thiscausesabuildup ofcapsulesonthereactionbeaker[1].Thebuildupisunrecoverable.Alsoin[1],itwas reportedthatspeedsaround550rpmareneededfor100mcapsules. Adhesionofthecapsulestothematrixalsoaffectstheselfhealingsuccess.To increasethebondstrengthbetweentheshellandthematrix,asilanewashwas performedbeforemixingintothematrixasreportedintherelevantpatent[5]. Microcapsule Fabrication Process ThemicrocapsulesweremadebyadaptingarecipefoundinthepaperInsitu poly(ureaformaldehyde)microencapsulationofdicyclopentadienebyBrownetal. TheprocedureislistedintheappendixA.Severaladjustmentstotherecipewere necessaryinordertocarryouttheprocessinatimelyfashionandwithoutspendinga lotofmoneyonequipment.Firstathreebladedmechanicalstirrerasdescribedin[1] 10
wasnotavailable.Instead,alowshear,footballshapedmagneticstirringrodwasused assuggestedbyVonCresce,agraduatestudentworkingforDr.Kofinas.TheDCPD wasprobablythelargestobstaclemetintheencapsulationprocess.SincetheDCPD providedbyDr.Kofinasslabwasalowmeltingsolidatroomtemperatureratherthan aliquidasexpected,ithadtobeheatedabove33Cbeforeusingitforencapsulation. However,despiteheatingitbyrunningitunderhotwater,itwouldquicklycooldown, cloggingthepipettes.UponaddingtheDCPD,itquicklysolidifiedinthesolution. Thus,ratherthankeepthesolutionat2024Cassuggestedforstabilization,ithadtobe heatedtoaround35C.Thisbecameaproblembecausethehotplatewouldnotheatup andsosolidDCPDspheresformedratherthandroplets.Beforetheformaldehydewas addedtostartthepolymerizationreaction,theDCPDhadtomelt,formdroplets,and thenstabilizeasanemulsion.Anoftenrefreshedhotwaterbathwasusedto temporarilyraisethetemperatureandusedtohelpmaintainthetemperatureforlater steps.However,evenoncethehotplatewasworking,itcouldnotsupplyenough energytoheatthewaterbathandsolutionbeforetheDCPDsolidifiedagain.Thusit tookmuchlongerthanexpected(aboutanhour)toclimbtoatemperatureof35C. Afterstabilizingtheemulsionandaddingtheformaldehyde,thesolutionwasheatedto thetargettemperature(55C).However,theactualheatingratewasmuchslowerthan thatsuggestedinthepaperof1C/min[1]. Aftermaintainingthetemperatureandstirringforfourhours,thecapsuleswere cooledtoroomtemperature.Visually,theyappearedtohavealargesizedistribution. TherewerelargespheresofDCPDthathadsolidifiedwithoutbeingencapsulatedon thesurface,microcapsules,andalotofwhatseemedtobeUFparticlesthathadfailed toattachtoaDCPDdroplet.Theyieldwasnotverygoodandthecapsules agglomeratedalotlikelyduetothelargeamountofsmallUFparticles.Also, agglomerationonthebeakerwallscouldbeduetohighspeedscausingahighshear environment. 11
Afterdilutingthemixturewithlargevolumesofdeionizedwater,theexcess solventwasremovedbyvacuumfiltration.Thevacuumfiltrationwasverytedious becauseofthelargeamountofsolidsformed.Afterpouringsomefiltrantonthecenter ofthepaper,itwaswashedmanytimeswithwatertohelprinseoffthesolvent.The particleswerethendriedforabout10minutesandwererecoveredintoabeakereven thoughtheystillreekedofDCPD.Thisprocesswasrepeatedforhoursuntilallthe capsuleswerecleanedanddried.Thentheywerespreadoutequallyintothreepetri dishestodryinthehoodovertheweekend. Results TodetermineiftheprocesswassuccessfulencapsulatingDCPD,snifftestswere originallyplannedaswellastobreakopencapsulesandtoobservethemusingoptical microscopy.ThesnifftestturnedouttonotbepracticalbecausetheDCPDodorwas presentwithoutevendisturbingthemicrocapsules.Evenafterwashingmultipletimes andfiltering,theDCPDodorwasstillpresent.EitherDCPDresidueswerestillpresent onthesurfacesorthecapsuleshellsweretoothinorpermeable.Itislikelythatthe delaysduetothehotplate,thedifferenttypeofDCPD,andtypeofstirringaffectedthe capsulesnegatively. Previousworksuggeststhatwhilesmallcapsulesaredesired,thestirringrate usedwastoohigh,oratleastcontainedtoolargeashearcomponent.Thishighrate likelyproducedlargeshearstresses,whichisevidencedbythelargebuildupof capsulesonthebeakerwalls.Sincethosecapsuleswererecoveredandwerenot separatedfromtherest,thislikelyruinedtheresults.Thegoodcapsulesshouldhave beenseparatedfromtheagglomeratedones. Uponmorecarefulresearch,silanewashistobedoneina1:20ratioofsilaneto hexane.WhensilanewashedcapsulesweremixedintothePU,itdidnotpolymerize
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andinsteadformedagoop.Therewerenopolymerizationproblemshoweverwhen silanewasomitted.Also,Whiteused1wt%silaneinthepolymer,SilaneX6032 (StyrylamineCationicreactivegroup)[5].Furtherinvestigationisneededtodetermine theroleofthesilane. Backup Plans Sincethefirstroundofmicrocapsulesdidnotgosmoothlyduetothehotplate problemsandthehigherthanexpectedDCPDmeltingpoint,thebackupplanwas executedusingtheplanBmaterial,butonlyforthemonomer.Duetopreviouspractice andtheUFrecipe,UFcapsuleshellsweremaintainedsincetheinterfacial polymerizationprocesswouldworkforanywaterinsolublemonomer.Becauseofthe versatilityofthistypeofencapsulation,onlythemonomerwouldhavetobechanged, whichwasthebiggestprobleminthefirstplaceanyway.Brownin[5]suggestedusing caprolactonemonomerasthecoresothatwaschosenasabackupmonomermaterial. Theprocedurewentverysmoothlywitheveryonecontributingandthereactiongoing asplanned.However,anemulsiondidnotformwhenthecaprolactonewasadded.At firstitwasthoughtthatmaybeitwasbecausethemonomerhadsimilardensity, viscosity,andrefractiveindextowatersothatwecouldnotseeanemulsion.However, whentheformaldehydewasadded,thesolutionwasstillclear.Atthetarget temperaturetherewasstillnosignofmicrocapsuleformation.Suspectingfailure,the solutionwaslefttoreactwhilethecaprolactonesolubilityinwaterwaslookedup.The solubilitywastobecheckedbeforesynthesis,buttimewasveryshortandthegroup wasinarush.Itwasdiscoveredthatcaprolactoneisoneofthefewmonomersthatis solubleinwater.ApparentlythisissomethingthattheUIUCgroupneglectedto mentionorrealizewhenwritingthepatentandtheirotherpapers.Thismistakeshows howimportantitistoreadwithcarefulconsideration.Justbecausesomethingis
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Figure3.(a)Moldusedtocreatedogbonetensilespecimens,(b)MoldusedtocreateIzodspecimens
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materialwasdifficulttostirforhomogeneousmixing,hadapotlifeof15minutesand hadacuretimeof24hours.PartAwasatancoloredviscousliquidthatturned greenishwhenstirredcompletely.PartBwascamelcoloredandmoreviscousthanpart A;itbecamemilkywhitewhenstirredcompletely.Thepartsweremixedtogetherwith aratioof1:1.Combined,themixturewasamediumbrowngreencolor.Bubblesformed whichcouldhavebeenduetomoistureintheairormaterials.Weusedthissampleto testtheadhesionofthematrixtoLexanwithoutsprayreleaseandtheacrylicmold materialwiththesprayrelease.Acrylic(3/8thick)wasusedinsteadofglass,andLexan wasproposedasanalternativetoTeflonduetoavailability.After2days,thesamples wereremoved. Next,wetestedthepolyurethaneobtainedfromTAPPlastics,theQuikCast.This materialwaseasytoshaketoensureahomogeneoussample,hadapotlifeof5minutes beforepolymerization,ademoldtimeofabout15minutes,andatotalcuretimeof36 hours.PartAwasveryviscousandwasayellowishcornsyrupcolor.Wechosetouse 120mL,andbecausethesamplecouldbepipettedwewereabletofairlyaccurately measurethisexactamount.PartBwasathinnerliquidthanPartA,andadarker yellow,moreofabuttercupcolor.Becausethepartsneededtobemixedequally,120 mLofPartBwasalsoused.PartB,likePartA,couldalsobepipetted,allowingfora moreaccuratemeasurement. Uponmixingthetwoparts,thesolutionimmediatelythickened,andthe viscositycontinuedtoincreaseasitwasstirred.Thesampleturnedacloudywhite,and stirringcontinuedforaboutaminute.Inordertotesttheeffectivenessofthemold release,halfofthemixturewaspouredintoapetridishwithoutmoldrelease,andthe otherhalfpouredintoapetridishwithmoldrelease.Bothsamplespolymerizedwithin about5minutes,atwhichtimeamilkywhitecloudseemedtoexpandandconsumethe sample,turningitallintoacloudywhitecolor.Itcanalsobenotedthatthesample withoutmoldreleasedturnedwhiteorpolymerizedfasterthanthesamplewithmold 15
Figure4.Polymerizationofpolyurethane
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Figure5.Moldedpolyurethanewithobviousexcessbubbles
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AnotherproblemoccurredwhenexcessPUleakedoutintothesidesofthemold
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Figure6.Characteristicmicrocapsulesfrom(a)onefiltration,(b)twofiltrations,(c)multiplefiltrations and(d)microcapsules(washedinsilane)embeddedinpolyurethane
Characterizationofthemicrocapsulesandpolyurethaneembeddedwithsilane
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Figure7.(a)Characteristicparticlefromsamplesubjectedtoasinglefiltration,(b)suspectedmonomer particles
Next,thesampleofmicrocapsulesthatwasfiltratedthemaximumamountwas
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Figure8.(a)Characteristicagglomerationofparticlesfoundinmaximallyfiltratedsampleof microcapsules,particleinboxissameasthatshowninpart(b)
Finally,theESEMwasusedtocomparethemicrocapsulesoftheresearchteamto
Figure9.(a)SurfaceofmicrocapsulefromresearchgroupatUniversityofMaryland,and(b)Surfaceof amicrocapsulefromresearchgroupatUniversityofIllinoisatUrbanaChampaign[1]
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Figure10.(a)Sintech20universaltestingmachineusedfortensiletesting,(b)Dogbonecutterusedto maketensiletestspecimens,(c)ASTMTypeVspecimencutfrommold
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Figure11.(a)Typicaltensiletestdatanumericaloutput,(b)Typicaltensiletestgraphofloadversus elongation
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Results Width Thickness Peak Load Peak Stress %Strn @ Pk Ld Break Load Break Stress %Strn @ Break Energy @ Break Yield Load Yield Stress %Strain @ Yield Energy @ Yield Modulus
Average Values 0.125 0.16 63.1 3154 4.0 63 3154 4.0 3.0 63.1 3154 4.0 3.0 97727
Table1.Tensiletestingresultsofthevirginpolyurethanesamples
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Figure12.(a)IzodimpacttesteratAdellPlastics,Inc,(b)AscastIzodTestSpecimens(before notching),(c)MillingmachineatAdellPlasticsusedtonotchIzodtestspecimens
Five(5)notchedIzodspecimensoftheascastvirginpolyurethaneandone(1) polyurethanesampleembeddedwith5wt.%microcapsulesweretested.Asummary
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oftheresultsofthistestingisprovidedinTableII.Thedatashowstheascastvirgin polyurethanehadanIzodimpactresistanceof0.56ftlbs/in.EachoftheIzodtest specimenscleanlybrokeinabrittlefracturemodeemanatingfromthenotch.The resultsoftheIzodimpacttestsaresummarizedinTableII.Boththeascastvirgin polyurethaneandthepolyurethaneembeddedwithmicrocapsulesspecimensexhibited areasofporosity.TheIzodpolyurethaneembeddedwithmicrocapsuleshadalarge visibleareaofporositycoincidentwiththemillednotchandalsoexhibitgeneral porositythroughoutasshowninFigure13.Thismayexplainthelowertestedimpact resistancevalueofthemicrocapsuleembeddedspecimenascomparedtothevirgin polyurethanespecimens.
Figure13.Izodtestspecimenembeddedwithmicrocapsulesshowingporosity
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Virgin PU Thickness Izod Value 1 Resultant Izod Average PU w/ microcapsules Sample 1 Sample 2 Sample 3 Sample 4 Sample 5 Average Values 0.45660 0.44385 0.45680 0.44790 0.44330 0.44969 0.280 0.299 0.335 0.258 0.276 0.290 ft-lbs/in. 0.53 0.59 0.66 0.49 0.54 0.56 Units in. Sample 6
Thickness in. 0.46275 Izod Value 1 0.149 Resultant Izod Average ft-lbs/in. 0.24 Table2.Izodimpacttestresultsforsamplesofpolyurethanewithandwithoutembedded microcapsules
Contact Angle Contactanglemeasurementswereperformedinordertodeterminethe wettabilityofthepolyurethanesubstratewiththeDCPD.Thesmallertheangleis,the morewettingtheliquidis.Asmallangleisdesiredinthiscasesothatthemonomer willflowintothecrack.Ifthemonomerdoesnotspread,thenitwillcontractintoitself andinhibitflow.Thisnonwettingsituationwillhinderandmostlikelypreventthe selfhealingmechanismfromoccurring. Todothemeasurements,DCPDwaswarmedunderhotwatertomelt.Usinga plasticpipette,severaldropswereplacedonthesurfaceofcleanpolyurethane.Witha digitalcamera(Figure14),pictures of thedrop weretakeninorderto measure theangle and estimationsweremadewithonlythenakedeye.Theanglewasfoundtobe1923 degreesusingthepicturebelowandaprotractor.HeatingtheDCPDtohigher temperatureswilllikelydecreasetheangleandincreasewetting.Toincreasewetting further,asurfactantcouldbeaddedtotheDCPDtoincreasecompatibilitybetweenthe surfacesandthusincreasewetting.
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Figure14.ContactanglemeasurementofDCPDonpolyurethane.Theanglewasmeasuredas1923 degrees
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Figure15.a)ReferenceFTIRforDicyclopentadiene[2],(b)FTIRspectrumformicrocapsulepowder (red),background(green)
Future Work
Theprojectresearchhasonlybegun.Thefirststepistofabricatemoremicrocapsules usingtheDCPDthatisalowviscosityliquidatroomtemperature.Oncemicrocapsules ofpropersizearecreated,thenextstepistointegratetheentiresystemof microcapsulesandcatalystintothematrix.Oncetheprocessiscemented,therelative amountsofcatalystandmicrocapsulesshouldbealteredtofindthebestratio.In addition,theweightpercentofmicrocapsulesinthematrixshouldbevariedalongwith
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thecapsulediametersandshellthickness.Allthesevariablesneedtobeexploredto determinewhatprovidesthebestselfhealingeffectiveness.Experimentaltestsmustbe usedsincetheoryisnotdevelopedenoughtoexplainthephenomenon. Alsotoincreaseeffectiveness,thesilanewashshouldbefurtherinvestigatedto determinewhyitpreventspolyurethanepolymerization.Itislikelythesilanechosen wasnotappropriateforthissystemeventhoughitwasfortheepoxysystem.Adhesion studiesbetweenUFandPUshouldbedoneusingdifferentsurfacetreatments.To increasethespeedofrecoveryandcrackfilling,surfactantsorotheradditivescouldbe incorporatedintotheDCPDtoincreasewettingandspreading. Toanalyzetheselfhealingeffectiveness,furtherfailureanalysismustbecompleted. Izodtestingofthecompletesystemshouldbedonetodeterminethefracturetoughness ofthevirgin,andthenprestressedandhealedcomposite.Failureduetofatigueis beingpreventedsofatiguetestingshouldalsobeexecutedtodeterminethedegreeof selfhealingsuccess.
Conclusions
Theconceptofaselfhealingisarelativelynewareaoftechnologicalinterest
Acknowledgements
Wewouldliketothankthefollowingpeoplefortheirhelpwithourproject.
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References
1. Brown,etal.Insitupoly(ureaformaldehyde)microencapsulationof dicyclopentadiene.JournalofMicroencapsulation.20.6:719730(2003). 2. Pouchert,C.,TheAldrichLibraryofFTIRSpectra,Edition1,Volume1,The AldrichChemicalCompany,Inc.1985 3. Brown,E.N.,Sottos,N.R.andS.R.White.FractureTestingofaSelfHealing PolymerComposite.ExperimentalMechanics.42:4,372379,2002. 4. TAPQuickCastPolyurethaneCastingResinSystem.TapPlastics,Inc.(2004). Dec.9,2004<http://www.tapplastics.com/shop/product.php?pid=74&>. 5. Whiteetal.UnitedStatesPatentNo.6,518,330.Feb.11,2003.
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APPENDICES
35
36
Procedure 1.Add50mlof2.5wt%aqueoussolutionofEMAcopolymerto200mlofdeionized waterina1000mlbeaker@roomtemperature(2024_C). 2.Suspendedbeakerinatemperaturecontrolledwaterbathonaprogrammable hotplatewithexternaltemperature 3.Agitatesolutionwithadigitalmixerdrivingathreebladed,63.5mmdiameterlow shearmixingpropellerplacedjustabovethebottomofthebeaker. 4.Underagitation,dissolve5.00gurea,0.50gammoniumchlorideand0.50gresorcinol inthesolution. 5.RaisepHfrom2.60to3.50bydropwiseadditionofsodiumhydroxide(NaOH) solution. 6.Add12dropsof1octanoltoeliminatesurfacebubbles. 7.Addslowstreamof60mlDCPDtoformanemulsion. 8.Stabilizefor10min. 9.Add12.67g(11.7mL)of37wt%aqueoussolutionofformaldehyde(1:1.9molarratio offormaldehydetourea) 10.Coverandheatemulsionatarateof1C/mintothetargettemperatureof55C. 11.Agitate4handmaintaintemperature.Thenswitchoffmixerandhotplate.Coolto ambienttemperature. 12.Separateundervacuumwithacoarsefrittedfilterthesuspensionofmicrocapsules. 13.Rinsewithdeionizedwater.Airdryfor2448h.Asievewasusedtoaidin separationofthemicrocapsules(USAstandardtestingsieves,W.S.Tyler).
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Urea
Physical description CH4N2O White crystals or powder, mild aromatic odor MW: 60.0554 Density: 1.335 MP: 135 C 100% Water soluble May cause irritation, particular on damp skin Aqueous wall former 5g 500 g JT Baker ACS Reagent
Resorcinol / 1,3-benzenediol
Physical descript. C6H4(OH)2 MW: 110.11 Density: 1.272 MP: 110-113 C 100% water soluble White to off-white needle crystals, slight characteristic odor. Becomes pink on contact with air, light or iron. HYGROSCOPIC. Strong irritant to skin; Inhalation of dust causes irritation to respiratory tract Make formaldehyde resin 0.5 g 100 g $26 ACS 99+% Crystal (Alfa Aesar) Keep in a tightly closed container. Store in a cool, dry, ventilated area away from sources of heat or ignition.
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Formaldehyde
Physical descript. CH2O MW: 30.0262 BP: 96 C FP: 60 C Density: 1.083 pH 2.8 Very soluble, colorless liquid, pungent odor detectable at 1 ppm Corrosive--Causes burns. Very toxic by inhalation, ingestion and through skin absorption. Readily absorbed through skin. Probable human carcinogen. Lachrymator at levels from less than 20 ppm upwards. Very destructive of mucous membranes and upper respiratory tract, eyes and skin. Organic wall former, for resin 11.7 mL 500 mL Fisher 37% ACS
Hazards
DCPD (Dicyclopentadiene)
Physical descript. C10H12 MW:132.2048 Density: 0.986 MP: 33 C BP: 170 C Insoluble organic, colorless to pale yellow, mild camphor like odor May cause skin, respiratory irritation. Core/monomer 60 mL Use Dr. Kofinass free BHT Stabilized, from Aldrich
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Sodium Hydroxide
Physical descript. HNaO MW: 39.99707 White, deliquescent solid water soluble, exothermic dissolution Density = 2.13 Corrosive, hygroscopic Raise pH (base) Made 10 wt% solution 500 g Pellets, ACS reagent from JT Baker
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Ammonium Chloride
Physical descript. NH4Cl MW: 53.49 Density: 1.53 MP: 338 C White, odorless powder, pH ~5, HYGROSCOPIC. Skin and respiratory irritation. hardener for formaldehydebased adhesives 0.5 g 500 g Fisher USP/FCC
1-octanol
Formula Physical descript. C8H18O Clear, colorless liquid. Penetrating aromatic odor. MW: 130.23 Density: 0.826 BP: 195 C Slightly soluble. Mild skin irritant, respiratory tract irritation. Flash point: 81C (178F)--Combustible Liquid and Vapor! To eliminate surface bubbles 1-2 drops 1 mL 99+%, Acros Organics
Hazards
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Appendix D: Timeline
W eek N um ber
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3 5 7 9
Activity
Appendix E: Budget
Materials Category MATRIX Supplier TAP Plastics Item PU and supplies Cost 114.5 65 25.76 30.6 50 80 4.99 11.83 114.5 65 25.76 30.6 50 80 4.99 11.83 123.02 26 2.61 7.46 7.43 29.31 32.66 83.33 48.6 13.14 8.55 18 0 0 0 0 11.08 37.06 13.22 8.22 approx; ship? Shipping Total Cost ship? ship?
Polytek PU Physics store1 acrylic sheets Physics store2 acrylic sheets Machine shop 1 Sheet Mold for dogbones Machine shop 2 Izod mold Physics store3 Screws (still need receipt) Physics store 4 zip disk and CD-R MICROCAPSULES Chem store Fisher Sigma Sigma Sigma Fisher Fisher Fisher Fisher Chem store Chem store Chem store Composite Characterization Equip Chem store ESEM FTIR Izod Tensile chemicals and supplies Resorcinol, 100g EDA TDI Silane Scandium Triflate Caprolactone 1-ocatanol PVA petri dishes and beakers books, towels slides bottles, weighing paper
0 0 0 0 0 0
123.02 0 26 26.7 25.2 75.9 48.6 13.14 8.55 18 11.08 37.06 13.22 8.22
834.87
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Appendix F: Recommendations
TheseareourcommentsontheclassandsuggestionsforthefutureofENMA490: Havetimeinclasswithouttheprofessorpresent,especiallyatthebeginningof theclass.Wehavenoothertimetomeetasagroupandneedtoupdateeach otherwithoutpressureandcommentsthatinterruptourmindsets. BeforespendingalotoftimeatthelibraryorontheInternet,talktoprofessors onceyouhaveanideaandsomeconstraints.Theyareafantasticresourceand saveyoualotoftimeandpain/stress. Pickatopicassoonaspossibleandhaveseveralbackupideas.Onceyouhave lookeddeeperintothetopic,aslongasitseemsfeasible,getstartedimmediately. Keepontask.Theendofthesemestercomesfasterthanyouthink.Setgoalsfor eachweek,eachclass,andeachquarter,andalwayskeeptheendinmind. Moreemphasisonlearningteamwork,projectdesign,theprocessofresearch andlessonbeinginnovative.Therewasalargeamountofpressuretodo somethingnewandhightech,whichmakesitveryeasytogetoveryourheads. Thereistoomuchfocus,atleastinourclasstherewas,onsuccessoftheproject, oninvention,andnotenoughonlearningtheprocess. Anintermediatereviewwithfacultywillintroducethemtowhatyouaredoing andexposeanyshowstoppers.Facultyhaveawidevarietyofexpertiseand theycanoffersuggestionsintheirfield.Also,theywillbeabletoseewhereyou areinthebeginningandhowyouendup,seetheamountofprogress. Compareandcontrastthedesignprocessinindustryandinacademia.Discuss howthiscontextplacesconstraintsonthedesignprocess. Dontschedulemacro,kineticsandseniordesignallinthesamesemester. Breakingitupwouldbehelpful. Forgeneralcurriculum:Itishardandforlargeclasses,notfeasibletodo fabrication.However,thatiswhatwelearn.Wehavenobackgroundtodo simulations;wehavealmostnoexperiencewithsoftwareotherthanPowerPoint andExcel.Thisputsusinaverydifficultsituation.
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