Self Healing Materials

ENMA490CapstoneDesignCourse Fall2004 MelissaConsidine ErinDreyer PaulFreese PaulLedwith JoannaMeador

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

Onceaselfhealingcompositehasbeenrealized,itisanticipatedthatthe electricalinsulationfabricatedwiththisselfhealingcapabilitywillincreasethelifetime andreliabilityofcriticalcomponentswherecatastrophicfailureisunacceptable.Similar advantagescouldbeutilizedtoimprovesuchsystemsasthoseusedinspaceflight, undersearemoteprobes,nuclearpowerplants,biomedicalimplants,andremote militarysurveillance.Bydemonstratingthattheselfhealingmechanismcanbe extendedtootherpolymerclasses,futureworkmayincludeextensionofthisconceptto moregeneralpolymericapplications.

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

accommodatetheneedforanoptimumviscositythatwillbeabletobalancethe polymerizationratewiththerateofcrackfillingviacapillaryaction,theviscositycanbe easilyalteredwithfillers. WhenreactedwithGrubbscatalystasolutionofDCPDcanrapidlyundergoa ringopeningmetathesispolymerization(ROMP).Aschematicofthisreactionisshown inFigure1.Thelivingreactionthatoccursrequiresamonomertocatalystratioof 1:1000.Oncethereactionisunderwayitconsumesnoadditionalcatalyst,whichisan importantconsiderationinaselfhealingschemewherefewGrubbscatalystmolecules maybecontactedbyapropagatingcrack.

Figure2.SchematicofthereactionofDCPDmonomerwithGrubbscatalystinalivingringopening metathesispolymerization[1]

Dicyclopentadieneisalsopracticalintermsoffinancialconsiderations.The monomersolutionisavailableforapproximately50cents/lb.Fromanenvironmental pointofviewutilizingDCPDcanalsobeseenasasolution.LargequantitiesofDCPD aregeneratedannuallyaswastebythepetroleumindustry.

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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publisheddoesntmeanthatitiscorrect.However,despitethefailure,theattempted encapsulationwasgoodpracticeandwentmoresmoothlythanthefirstencapsulation. Matrix Mold Fabrication Thematrixmoldwasfabricatedusingtwo8.5x11x3/8acrylicsheetsheld

togetherpostcastingwithlargebinderclips.Thebottomacrylicsheethada6x8 roundedrectanglewitha0.125divotcutfromitinordertocreatetheholeinwhichthe mixturewouldbepouredinto.Thesedimensionswerechoseninorderto accommodatelatertensiletesting.Inordertodotensiletesting,adogbonecuttermust firstbeusedtocutoutdogboneshapesfromthesamplefortheactualtesting.This dictatedthethicknessoftheresultingsample.The6by8sizewaschosensothat manysamplescouldbecutfromthesubsequentmatrix.

Figure3.(a)Moldusedtocreatedogbonetensilespecimens,(b)MoldusedtocreateIzodspecimens

MatrixFabrication Weboughttwotypesofpolyurethanetouseaspotentialmatrixmaterials.One typewassuppliedbyPolytekandtheotherbyTAPPlastics(QuikCast).Bothtypes camewithtwoparts:partAandpartBthatpolymerizewhenmixedtogetherand allowedtocure.Webeganbymixingthefirsttypeofpolyurethane,Polytek153.This

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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

release.Oncepolymerizationhadbegun,itonlytookamatterorminutesfortheentire sampletopolymerizeandbecomehard.Thereactionwasexothermicasthesample becomemuchwarmertothetouchafterthetwopartsweremixed. Additionally,anothermatrixmoldwasfabricatedtocastsamplesforuseinan Izodtest.Tenholesmeasuring3by0.5werecutfroma0.5sheetofacrylic.Two sheetsofacrylicwereusedtosandwichthecutacrylic.Thesandwichingsheetshad threehelicalholescuttoallowscrewstobeputinsothatthesheetscouldbeseparated fromthemiddlelayeraftercastingasPUtendstospilloutofthesidesoftheholesand causethesheetstosticktogether.

Figure4.Polymerizationofpolyurethane

MatrixFabricationResults Thefabricatedmatrixwasanoverallsuccessafterseveralfabricationattempts. Thefirstbatchofpolyurethane(PU)matrixwasfabricatedfromPolytekpolyurethane parts.TheresultingPUwasalightbrowncolorthatwasveryporousyetveryhard.

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ThefirstPUfabricatedfromtheQuikCastsystemwasacreamywhitecolorthat showedsignificantlylessporesthatthanthePolytekPU.TheQuikCastPU polymerizedmuchfasterthanthePolytek,aswewereabletowitnesstheactual polymerizationwithinaboutafiveminutestimeafterpartsAandBhadbeenmixed. ThedemoldtimefortheQuikCastPUwasalsomuchfasterthanthePolytek,andthe totalcasttimewasabout36hours. Oneofthefirstdrawbackswefoundinfabricatingthematrixwastheonsetof

bubblesonthematrixsurfaceafterpouringthemixedPUintothemold.Thisproblem wassolvedbyslidingthetopmoldpieceacrossthelowerpiecetoeliminatetheamount ofairthatreachedthesurfaceandgotcaughtunderthemold.

Figure5.Moldedpolyurethanewithobviousexcessbubbles

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AnotherproblemoccurredwhenexcessPUleakedoutintothesidesofthemold

andpolymerizedbetweenthetwosheets.Thismadedemoldingdifficultastheexcess PUmadeitdifficulttopulltheacrylicsheetsapart.Wesolvedthisproblembycreating anothermoldwithscrewholesinit.Thisallowedforscrewstobeinsertedtopush aparttheacrylicsheetstoremovethemoldedPU.

Testing and Characterization

Microscopy OpticalcharacterizationwasperformedusingtheOlympusBLXmicroscope connectedtoaCCDcameraandvideosystemwithwhichpicturescouldbetaken. Magnificationsof100,200,and500Xwereused.Microscopywasdoneonsamplesof themicrocapsulessubjectedtovariousamountsoffiltrationandonthepolyurethane thatwasembeddedwithsilanewashedmicrocapsules.Characteristicparticlesofeach filtrationlevelareshowninfigure6aswellasacharacteristicviewofthepolyurethane. Noticethatinpartaoffigure6,thefirstleveloffiltrationshowsaparticlethatis approximately200mindiameter,andtheparticlesshowninpartboffigure6are fromthesecondleveloffiltrationandhaveadiameterofapproximately100m.Partc offigure6showsaparticlefromthemaximallyfiltratedparticles;noticeadiameterfor thisparticleisapproximately50m.Consequently,itcanbeseenthatwhensubjected tomorefiltrations,thecharacteristicparticlesizeoftherepresentativesamples decreases.Moreworkmustbedonetodetermineifthedecreasingparticlesizehasa directcorrelationtotheamountoffiltrationorifthesefindingsarepurelycoincidental. Partdoffigure6showssilanewashedmicrocapsulesinthepolyurethanematrix.The matrixdidnotpolymerizeinthepresenceofthesilane,andthereforelightcanbeseen

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transmittingthroughthematrix.Thereareairbubblespresentindicatedbyblack rimmedspheres.Itisdifficulttotelliftherearemicrocapsulespresentinthisview. Therewasextremelylittlecrystallinitypresentinthesample.Italsoappearsthatthe shelldoesnotprovidecompletecoverageoftheDCPDasseeninfigure6a.

Figure6.Characteristicmicrocapsulesfrom(a)onefiltration,(b)twofiltrations,(c)multiplefiltrations and(d)microcapsules(washedinsilane)embeddedinpolyurethane

Characterizationofthemicrocapsulesandpolyurethaneembeddedwithsilane

washedmicrocapsuleswasdoneusingtheenvironmentalscanningelectronmicroscope (ESEM).TheESEMisusedforsamplesthatarenotelectricallyconducting.First,the microcapsulesfromasinglefiltrationwerecharacterized.Partofthesamplewas crushedusingthetipofapentoseeiftheDCPDwouldbereleasedandifitcouldbe seen.TheresultsareshowninFigure7.Notetheappearanceofasphericalparticlewith arelativelyroughsurfaceinparta.Inpartb,agglomerationsofsmall,smooth,spherical

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particlesareseen.Itissuspectedthattheseparticlesaremonomerreleasedfromthe crushedparticles.However,itisalsopossiblethattheyaretinyparticlesofUFsinceit seemsthatthesespheresformtheroughoutsidelayeroftheUFshell.

Figure7.(a)Characteristicparticlefromsamplesubjectedtoasinglefiltration,(b)suspectedmonomer particles

Next,thesampleofmicrocapsulesthatwasfiltratedthemaximumamountwas

characterizedwiththeESEM.Theresultsareshowninfigure8.Inparta,a characteristicagglomerationofparticlesisshown.Thesectionofthemicrograph coveredinapurpleboxinpartaisshownatahighermagnificationinpartb.Notice thattheparticleismuchsmallerthanthatshowninfigure7.Alsonoticethatthesurface isrougher,andthereappeartobesmallparticlessimilartothoseshowninfigure7(b) intheroughoutersurfaceoftheparticle.

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Figure8.(a)Characteristicagglomerationofparticlesfoundinmaximallyfiltratedsampleof microcapsules,particleinboxissameasthatshowninpart(b)

Finally,theESEMwasusedtocomparethemicrocapsulesoftheresearchteamto

thoseprovidedbythegroupatUniversityofIllinois.Infigure9,thesurfaceofaparticle thathadbeenfiltratedmultipletimesisshowninparta;aparticlefromtheresearchers atUIUCisshowninpartb.Noticethesimilaritiesintheroughoutersurfaceofurea formaldehydeandasmoothinnersurface.TheparticleshownbytheUIUCgrouphas openedandonecanseethethicknessoftheshellwall.Thiswasnotpossibletodofor theparticleshowninparta.

Figure9.(a)SurfaceofmicrocapsulefromresearchgroupatUniversityofMaryland,and(b)Surfaceof amicrocapsulefromresearchgroupatUniversityofIllinoisatUrbanaChampaign[1]

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Tensile Testing TensiletestingwascarriedoutaccordingtoASTMstandardD638usinga Sintech20universaltestingmachineasshowninFigure10(a).Dogboneshapedtensile specimenswerecutoutofascastplaquesusingadogbonecuttershowninFigure 10(b).Thetestspecimens,oneofwhichisshowninFigure10(c),wereASTMTypeV havinganoveralllengthof2.5in.,awidthinthenarrowsectionof0.125in.anda thicknessof0.16in.Thecrossheaddisplacementratewassetat0.05in/min.

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Figure10.(a)Sintech20universaltestingmachineusedfortensiletesting,(b)Dogbonecutterusedto maketensiletestspecimens,(c)ASTMTypeVspecimencutfrommold

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Five(5)testspecimensoftheascastvirginpolyurethaneweretestedunder tensileloaduntilfailureoccurred.Duetothelimitationsofthecomputerizeddata acquisitionsystem,outputfilesofthetestdatasetscouldnotbegeneratedand thereforedigitalimagesoftheonscreendisplaywerecapturedasanalternative. Figure11(a)showsthetypicaldisplayedoutputdataforoneofthetensiletests.Figure 11(b)isthecorrespondingloadversuselongationcurvethatwasgeneratedbythedata acquisitionsoftwareduringthesametensiletest.Thegenerationofstressstraincurves foreachofthetensiletestscouldnotbeaccomplishedwithouttheoutputnumerical datafiles.

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Figure11.(a)Typicaltensiletestdatanumericaloutput,(b)Typicaltensiletestgraphofloadversus elongation

AsummaryofthecomputergeneratedtensiletestdataisprovidedinTableI. Thedatashowtheascastvirginpolyurethanehadanaveragetensilestrengthof3154 psi(22MPa).ThemanufacturerspropertydatasheetfortheQuikCastpolyurethane

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fromwhichthesesamplesweremolded,reportedatensilestrengthof5000psi(34 MPa).Thedifferencebetweenthemanufacturersreportedtensilestrengthandthe averagetestvaluecanmostprobablybeattributedtothepresenceofstress concentrationsintheformofmoldingdefectsintheasfabricatedtestspecimens leadingtoreducedtensileloadcapacity.Theaverageelasticmoduluswasfoundtobe approximately98,000psi(676MPa).Astraingageextensometerwasnotavailableto measuretheelongation(deformation)ofthespecimensduringtesting.

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

Units in. in. lb psi % lb psi % in-lb lb psi % in-lb psi

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

Std Dev 0 0 4 181 11 4 181 11 0.1 3.6 181 11 0.1 38169

Table1.Tensiletestingresultsofthevirginpolyurethanesamples

Impact Testing IzodimpacttestingwascarriedoutaccordingtoASTMstandardD256ona TestingMachines,Inc.IzodimpacttesterlocatedatAdellPlastics,Inc.(Baltimore,MD) andisshowninFigure12(a).AscastspecimensareshowninFigure12(b).Thetest specimenshadanoveralllengthof3in.andasquarecrosssectionofapproximately0.5 in.Priortoimpacttesting,eachoftheascastspecimenswasnotchedatAdellPlastics usingamillingmachineasshowninFigure12(c).

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Figure12.(a)IzodimpacttesteratAdellPlastics,Inc,(b)AscastIzodTestSpecimens(before notching),(c)MillingmachineatAdellPlasticsusedtonotchIzodtestspecimens

Five(5)notchedIzodspecimensoftheascastvirginpolyurethaneandone(1) polyurethanesampleembeddedwith5wt.%microcapsulesweretested.Asummary

27

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

Std 0.00 0.0 0.0

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

Fourier Transform Infrared Spectroscopy ThechemicalidentityofvariousreagentscanbeanalyzedwithFourier

transforminfraredspectroscopy(FTIR).Ourstartingmaterialsandsynthesisproducts wereexaminedusingthismethod.AreferencespectrumforDCPDisshowninfigure 15(a)[2].Theresultsoftheanaylsisoftheproductofourmicrocapsulesynthesisare showninfigure15(b).Duetotimeconstraints,analysisoftheFTIRresultswas incomplete.

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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

31

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

withmanypotentialapplicationstofieldsrangingfromelectronicstobiomedical interest.Theinherentlycomplexinteractionofdesignparametersinacompositesystem makesitdifficulttoapplytheoreticalmodelstoexplainmacroscopicproperties. Nevertheless,theENMA490designteamdevelopedamethodologysothatqualitative andquantitativedatacouldbeobtainedandusedtoestablishcriteriaforsuccessfulself healingmaterials. Avarietyofexperimentaltechniqueswereusedtounderstandvariousaspectsof

materialsscienceandengineeringchallengesnecessarytofabricateacomposite material.Whilethemechanicaltestspecimensdidnotshowanoverallincreasein tensilestrength,itwaslearnedthatothertestingcriteriaarenecessarytoargue 32

persuasivelyfortheuseofselfhealing.Theobservationsofmicrostructuresuggestthat ageneralmicroencapsulationprocesscanbeadaptedtodiversepolymermatriceswith carefulattentiontosurfacecharacterization. Thedesignprojectwasofgreatutilityinpreparingthestudentsforencountering

realworldengineeringproblems.Thecriticalthinkingnecessarytopreparea presentationforaspecificaudienceandtojustifyabudgetservedtoenhancetheoverall educationalexperience.

Acknowledgements
Wewouldliketothankthefollowingpeoplefortheirhelpwithourproject.

Forfacultyconsultations:Dr.AlSheikhly,Dr.Briber,andDr.Kofinas;fortheuseof labsandlaboratorymaterials:Dr.AlSheikhly,Dr.Kofinas,Dr.MartinezMiranda,Bani CaprianoandDr.Raghavan,andDr.Lloyd;forassistanceinlabs:JungChulAn,Von WaldCresce,AliaWeaver;forassistancewithESEM:TimZhang,fortheuseofvideo equipment:Exponent,Inc.

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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

Appendix A: Microcapsule Synthesis Procedure; Urea Formaldehyde Encapsulating DCPD

Chemicals Equipment/Supplies Preparation Steps: 1. 2. 3. 4. MakeEMAsolution.Solutionis2.5wt%ofEMAinwater. Make10%NaOHsolution Determinemixingspeedofmixer. SkillsVacuumFiltration,needanotherprocedureforthis Balancetomeasuremassofsolids 1000mLbeaker Graduatedcylindertomeasurevolumeofliquids pHstrips Mechanicalmixer(3bladedpropeller) Hotplate(programmableifpossible) Temperaturecontrolledwaterbath Coarsefrittedfilter Vacuumfiltrationsupplies 5.0gurea 0.5gresorcinol 0.5gammoniumchloride 50mL2.5wt%solutionofEMA 10wt%NaOHsolutiontoraisepH 60mLDCPD(dicyclopentadiene),purifiedbyfiltrationandvacuumdistillation 1octanol(12drops) 37%formaldehyde(12.67g)solution 11.7mL DIWater

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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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Appendix B: Material Safety Data Sheets

ChemicalstructuresfromCambridgeSoftware,ChemFind.
H2N NH2

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

Hazards Use/Purpose Amount Used Amount Purchased Supplier Purity/Grade

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.

Hazards Use/Purpose Amount Used Amount Purchased Cost Purity/Grade Storage

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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

Use/Purpose Amount Used Amount Purchased Purity/Grade

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

Hazards Use/Purpose Amount Used Amount Purchased Cost Purity/Grade

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EMA Copolymer (Ethylene Maleic Anhydride)

Physical descript. insolutble Density: 0.92 White powder, characteristic waxy odor Maybe mild skin irritant. Dust may be irritating Additive, emulsifier 1.25 g 16 oz Free sample Zeeland Chemicals

Hazards Use/Purpose Amount Used Amount Purchased Cost Supplier

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

Hazards Use/Purpose Amount Used Amount Purchased Purity/Grade

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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

Hazards Use/Purpose Amount Used Amount Purchased Purity/Grade

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

Use/Purpose Amount Used Amount Purchased Purity/Grade

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Appendix C: Committee Organization

6Committeeseachwithachairandvicechair Organization:Cochairs;ErinandMelissa Research:ChairPaul;VicechairJo Fabrication:ChairErin;VicechairS.Paul TestingandCharacterization:ChairMelissa;VicechairPaul Simulation/Calculation/Visual:ChairJo;VicechairErin PaperandPresentation:ChairS.Paul;VicechairMelissa

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43

Week by Week Project Schedule

Presentation/Paper Calculations Testing/Characterization Preliminary Characterization Preliminary Testing Fabrication- In Lab Fabrication - Research Research - Optimization Research- Crack Propagation Research - Materials Used

Appendix D: Timeline

W eek N um ber

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3 5 7 9

Research - Choose Topic 11 13 15

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

approx approx approx

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

ship? ship? ship? ship?

834.87

Total accounted for

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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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