History and Current Status of the Plastics Industry.ppt

1 EngineeringThermoplastics Nylons PA Acetals POM Polyesters PBTandPET PC Acrylics PMMA PTFE PPO PPS PEEK ProfessorJoeGreeneCSU CHICO 2 PolyamideHistory PAisconsideredthefirstengineeringthermoplasticPAisoneofmanyheterochainthermoplastics whichhasatomsotherthanCinthechain PAinventedin1928byWallaceCarothers DuPont insearchofa superpolyester fiberwithmolecularweightsgreaterthan10 000 Firstcommercialnylonin1938 PAwascreatedwhenacondensationreactionoccurredbetweenaminoacids dibasicacids anddiamines NylonsaredescribedbyanumberingsystemwhichindicatesthenumberofcarbonatomsinthemonomerchainsAminoacidpolymersaredesignatedbyasinglenumber asnylon6Diaminesanddibasicacidsaredesignatedwith2numbers thefirstrepresentingthediamineandthesecondindicatingtheadipicacid asinnylon6 6ornylon6 10withsebacicacid 3 Chemistry ChemicalStructurelinearpolyamides Thermoplasticnylonshaveamide CONH repeatinglinkNylon6 6 poly hexamethylene diamine linear NH2 CH2 6NH2 COOH CH2 4COOHhexamethylenediamine AdipicAcidn NH2 CH2 6NH CO CH2 4COOH heat nylonsalt NH2 CH2 6NH CO CH2 4CO n nH2ONylon6 6polymerchainNylon6 polycaprolactam linear NH CH2 5CO n 4 Chemistry ChemicalStructurelinearpolyamides Nylon6 10 polyhexamethylenesebacamide linear NH2 CH2 6NH CO CH2 8CO nNylon11 Poly 11 amino undecanoic amide linear NH CH2 10CO nNylon12 Poly 11 amino undecanoic amide linear NH CH2 11CO nOtherNylonsNylon8 9 46 andcopolymersfromotherdiaminesandacids 5 Chemistry ChemicalStructureAromaticpolyamides aramids PMPI polym phenyleneisophthalamide LCPfiber NHCO NHCO nPPPT polyp phenyleneterephthalamide LCPfiber NHCO NHCO nNomaxPMPI firstcommercialaramidfiberforelectricalinsulation LCPfibersfeaturestraightchaincrystalsKevlar29PPPT textilefiberfortirecord ropes cablesetc Kevlar49PPPT reinforcingfiberforthermosettingresins 6 Chemistry ChemicalStructureTransparentpolyamides PA 6 3 T CH2C3H6C2H4 NHCO NHCO nPA 6 T CH2 6NHCO NHCO nTransparentpolyamidesarecommerciallyavailableReducedcrystallizationduetointroductionofsidegroups 7 ApplicationsforPolyamides Fiberapplications50 intotirecords nylon6andnylon6 6 rope thread cord belts andfiltercloths Monofilaments brushes sportsequipment andbristles nylon6 10 Plasticsapplicationsbearings gears camsrollers slides doorlatches threadguidesclothing lighttents showercurtains umbrellaselectricalwirejackets nylon11 Adhesiveapplicationshotmeltorsolutiontypethermosetreactingwithepoxyorphenolicresinsflexibleadhesivesforbreadwrappers driedsouppackets bookbindings 8 MechanicalPropertiesofPolyamides 9 PhysicalPropertiesofPolyamide 10 AdvantagesDisadvantagesofPolyamide AdvantagesTough strong impactresistantLowcoefficientoffrictionAbrasionresistanceHightemperatureresistanceProcessablebythermopalsticmethodsGoodsolventresistanceResistanttobasesDisadvantagesHighmoistureabsorptionwithdimensionalinstabilitylossofupto30 oftensilestrengthand50 oftensilemodulusSubjecttoattackbystrongacidsandoxidizingagentsRequiresUVstabilizationHighshrinkageinmoldedsectionsElectricalandmechanicalpropertiesinfluencedbymoisturecontentDissolvedbyphenols 11 AdditivesandReinforcementstoPA Additives antioxidants UVstabilizers colorants lubricantsFillersTalcCalciumcarbonateReinforcementsGlassfiber shortfiber 1 8 orlongfiber1 4 Mineralfiber wolastonite carbonfibersgraphitefibersmetallicflakessteelfibers 12 PropertiesofReinforcedNylon 13 OtherHeterochainPolymers PolyimideDevelopedbyDuPontin1962ObtainedfromacondensationpolymerizationofaromaticdiamineandanaromaticdianhydrideCharacterizedasLinearthermoplasticsthataredifficulttoprocessManypolyimidesdonotmeltbutarefabricatedbymachiningMoldingcanoccurifenoughtimeforflowisallowedforT TgAdvantagesHightemperatureservice upto700C Excellentbarrier electricalproperties solventandwearresistanceGoodadhesionandezpeciallysuitedforcompositefabrication 14 OtherHeterochainPolymers PolyimideDisadvantagesDifficultytofabricateandrequiresventingofvolatilesHydroscopicSubjecttoattacksbyalkalinesComparativelyhighcostApplicationsAerospace electronics andnuclearuses competeswithflurocarbons Officeandindustrialequipment Laminates dielectrics andcoatingsValveseats gaskets pistonrings thrustwashers andbushingsPolyamide imideAmorphousmemberofimidefamily marketedin1972 Torlon andusedinaerospaceapplicationssuchasjetenginecomponentsContainsaromaticringsandnitrogenlinkageAdvantagesinclude Hightemperatureproperties 500F lowcoefficientoffriction anddimensionalstability 15 OtherHeterochainPolymers PolyacetalorPolyoxymethylene POM PolymerizedfromformaldehydegasFirstcommercializedin1960byDuPontSimilarinpropertiestoNylonandusedforplumbingfixtures pumpimpellers conveyorbelts aerosolstemvalves VCRtapehousingsAdvantagesEasytofabricate hasglossymoldedsurfaces providesuperiorfatigueendurance creepresistance stiffness andwaterresistance Amongthestrongestandstiffestthermoplastics Resistanttomostchemicals stains andorganicsolventsDisadvantagesPoorresistancetoacidsandbasesanddifficulttobondSubjecttoUVdegradationandisflammableToxicfumesreleasedupondegredation H O CH2 O CH2 O NH R 16 MechanicalProperties 17 PolyesterHistory 1929W H Carotherssuggestedclassificationofpolymersintotwogroups condensationandadditionpolymers Carotherswasnotsuccessfulindevelopingpolyesterfibersfromlinearaliphaticpolyestersduetolowmeltingpointandhighsolubility Nocommercialpolymerisbasedonthese p phenylenegroupisaddedforstiffeningandleadstopolymerswithhighmeltingpointsandgoodfiber formingproperties e g PET PolymersusedforfilmsandforfibersPolyestersisoneofmanyheterochainthermoplastics whichhasatomsotherthanCinthechain Polyestersincludesunsaturated thermosets saturatedandaromaticthermoplasticpolyesters 18 Chemistry ChemicalStructurelinearpolyesters versusbranched Thermoplasticpolyestershaveester C O repeatinglinkPolyester linear PETandPBTC6H4 COOH 2 CH2 2 OH 2 CH2 2 O C C O terephthalicacid ethyleneglycolPolyethyleneterephthalate PET C6H4 COOH 2 CH2 4 OH 2 CH2 4 O C C O terephthalicacid butyleneglycolPolybutyleneterephthalate PBT 19 Chemistry ChemicalStructurelinearpolyesters versusbranched Whollyaromaticcopolyesters LCP Highmeltingsintered Oxybenzoyl doesnotmeltbelowitsdecompositiontemperature Mustbecompressionmolded Injectionmoldablegrades XydarandVectraXydar AmocoPerformanceProducts terephthalicacid p p dihydroxybiphenyl andp hydroxybenzoicacidGrade1 HDTof610FGrade2 HDTof480FVectra HoechstCelaneseCorp para hydroxybenzoicacidandhydroxynaphtholicacidContainsrigidchainsoflong flatmonomerunitswhicharethoughttoundergoparallelorderinginthemeltandformtightlypackedfibrouschainsinmoldedparts 20 PETChemicalStructureandApplications Theflexible butshort CH2 2groupstendtoleavethechainsrelativelystiffandPETisnotesforitsveryslowcrystallization IfcooledrapidlyfromthemelttoaTempbelowTg PETsolidifiesinamorphousform IfPETisreheatedaboveTg crystallizaitontakesplacetoupto30 InmanyapplicationsPETisfirstpre shapedinamorphousstateandthengivenauniaxial fibersortapes orbiaxial filmorcontainers crystallineorientation DuringInjectionMoldingPETcanyieldamorphoustransparentobjects Coldmold orcrystallineopaquesobjects hotmold 21 PBTChemicalStructureandApplications Thelonger moreflexible CH2 4groupsallowformorerapidcrystallizationthanPET PBTisnotasconvenientlyorientedasPETandisnormallyinjectionmolded PBThasasharpmeltingtransitionwitharatherlowmeltviscosity PBThasrapidcrystallizationandhighdegreeofcrystallizationcausingwarpageconcerns 22 ThermoplasticAromaticCopolyesters PolyarylestersRepeatunitsfeatureonlyaromatic typegroups phenylorarylgroups betweenesterlinkages CalledwhollyaromaticpolyestersBasedonacombinationofsuitablechemicalsp hydroxybenzoicacidterephthalicacidisophthalicacid bisphenol APropertiescorrespondtoaverystiffandregularchainwithhighcrystallinityandhightemperaturestabilityApplicationsincludebearings hightemperaturesensors aerospaceapplicationsProcessedininjectionmoldingandcompressionmoldingMostthermoplasticLCPappeartobearomaticcopolyesters 23 ApplicationsforPolyesters PET Blowmoldedbottles100 of2 literbeveragecontainersandliquidproductsFiberapplications25 ofmarketintirecords rope thread cord belts andfiltercloths Monofilaments brushes sportsequipment clothing carpet bristlesTapeform uniaxiallyorientedtapeformforstrappingFilmandsheetsphotographicandx rayfilms biaxialsheetforfoodpackagesMoldedapplications ReinforcedPET Rynite Valox Impet luggageracks grille openingpanels functionalhousingssuchaswindshieldwipermotors bladesupports andendbellssensors lampsockets relays switches ballasts terminalblocksAppliancesandfurnitureovenandappliancehandles coilformsformicrowaves andpanels pedestalbases seatpans chairarms andcasters 24 ApplicationsforPolyesters PBTandLCP PBT 30Mlbsin1988Moldedapplications PBT Valox Xenoy Vandar Pocan distributers doorpanels fenders bumperfasciasautomotivecables connectors terminalblocks fuseholdersandmotorparts distributorcaps doorandwindowhardwareExtrudedapplicationsextrusion coatwireextrudedformsandsheetproducedwithsomedifficultyElectronicDevices LCP 26Mlbs Terylene Dacron Kodel fuses oxygenandtransmissionsensorschemicalprocessequipmentandsensorscoil 25 MechanicalPropertiesofPolyesters 26 PhysicalPropertiesofPolyester 27 AdvantagesandDisadvantagesofPolyesters AdvantagesToughandrigidProcessedbythermoplasticoperationsRecycledintousefulproductsasbasisforresinsinsuchapplicationsassailboats showerunits andfloortilesPETflakesfromPETbottlesareingreatdemandforfiberfillforpillowsandsleepingbags carpetfiber geo textiles andregrindforinjectionandsheetmoldingPBThaslowmoistureabsorptionDisadvantagesSubjecttoattackbyacidsandbasesLowthermalresistancePoorsolventresistanceMustbeadequatelydriedindehumidifierpriortoprocessingtopreventhydrolyticdegradation 28 ThermoplasticCopolyesters Copolyesterisappliedtothosepolyesterswhosesynthesisusesmorethanoneglycoland ormorethanonedibasicacid CopolyesterchainislessregularthanmonopolyesterchainandasaresulthaslesscrystallinityPCTAcopolyester Polycyclo hexane dimethanol terephthalateacid amorphous ReactionincludescyclohexanedimethanolandterephthalicacidwithanotheracidsubstitutedforaportionoftheterephthalicacidExtrudedastransparentfilmorsheetsthataresuitableforpackagingapplications frozenmeatsshrinkbags blisterpackages etc Glycol modifiedPET PETG amorphous Blow moldedcontainers thermoformedblisterpackages 29 ABS PCBackground ABSwasinventedduringWWIIasareplacementforrubberABSisaterpolymer acrylonitrile chemicalresistance butadiene impactresistance andstyrene rigidityandprocessingease GraftpolymerizationtechniquesareusedtoproduceABSFamilyofmaterialsthatvaryfromhighglosstolowmattefinish andfromlowtohighimpactresistance AdditivesenableABSgradesthatareflameretardant transparent highheat resistance foamable orUV stabilized PCwasinventedin1898byF BayerinGermanyCommercialproductionbeganintheUSin1959 Amorphous engineeringthermoplasticthatisknownfortoughness clarity andhigh heatdeflectiontemperatures Polycarbonatesarelinear amorphouspolyestersbecausetheycontainestersofcarbonicacidandanaromaticbisphenol 30 AcrylicandCellulosicBackground Acrylics 1901 Includesacrylicandmethacrylicesters acids andderivatives Usedsingularlyorincombinationwithotherpolymerstoproduceproductsrangingfromsoft flexibleelastomerstohard stiffthermoplasticsandthermosets Cellulosics 1883 Cellulosenitratewasfirstdevelopedinthe1880s Firstuseswerebilliardballs combs andphotographicfilm Celluloseacetatewasdevelopedin1927reducedthelimitationsofflammability andsolventrequirement In1923 CAbecamethefirstmaterialtobeinjectionmolded Celluloseacetatebutyrate CAB in1938andCelluloseacetatepropionate CAP in1945foundapplicationsforhairbrushes toothbrushes combs cosmeticcases handtoolhandles steeringwheels knobs armrests speakers grilles etc 31 AcrylicsChemicalStructure Acrylics Basicformula PolymethylacrylatePolymethylmethacrylate AcrylateStyreneAcrylonitrile ASA 32 PS PC ABSChemicalStructure PS homopolymer addition PC condensationpolymerization atactic amorphousABSacrylonitrilebutadienestyrene Terpolymer addition 33 ApplicationsforPCandAcrylics PC highimpactstrength transparency excellentcreepandtemperature lenses films windshields lightfixtures containers appliancecomponentsandtoolhousingshotdishhandles coffeepots popcornpopperlids hairdryers Pumpimpellers safetyhelmets beveragedispensers trays signsaircraftparts films cameras packagingAcrylicsOpticalapplications outdooradvertisingsigns aircraftwindshields cockpitcovers bubblebodiesforhelicoptersPlexiglass windowframes glassfilled tubs counters vanities 34 MechanicalPropertiesofAcrylic PC PC ABS 35 PhysicalPropertiesofAcrylic PC PC ABS 36 Advantages PCHighimpactstrength excellentcreepresistance transparentVerygooddimensionalstabilityandcontinuoustempover120CAcrylicsOpticalclarity weatherability electricalproperties rigid highglossDisadvantagesPCHighprocessingtemp UVdegradationPoorresistancetoalkalinesandsubjecttosolventcrackingAcrylicsPoorsolventresistance stresscracking combustibility UseT93C 37 OtherCrystallineThermoplasticsReference AppendixE IndustrialPlastics PEEKHistoryChemistryandChemicalStructureApplicationsMechanicalPropertiesPhysicalPropertiesProcessingCharacteristicsAdvantages DisadvantagesPPOandPPSReviewQuestions 38 PEEKHistory Polyether ether ketone PEEK andPolyetherketone PEK PEEKinventedbyICIin1982 PEKintroducedin1987PEEKandPEKarearomaticpolyketonesVolumeforpolyketonesis500 000lbsperyearin1990 Estimatedtoreach3to4millionby2000 Costis 30perpound asofOctober1998 ProductNamesICI VivtrexBASF UltrapakHoechstCelanese HostatecDuPont PEKKAmoco Kadel 39 Chemistry ChemicalStructure PEEK Poly ether ether ketoneOOCPEK Poly ether ketoneOC 40 ChemicalSynthesis SynthesisofpolyketonesPEK Formationofthecarbonyllinkbypolyaroylationfromlowcoststartingmaterials RequiressolventssuchasliquidHF Excessivesolventsandcatalystcausethehighmaterialcost PEEK Formationofetherlinkusingphenoxideanionstodisplaceactivatedhalogen PEEK CO2 H20 KF 41 PEEKandPEKApplications Aerospace replacementofAlFuellinebrakestoreplacementofprimarystructureElectricalwirecoatingfornuclearapplications oilwells flammability criticalmasstransit Semi conductorwafercarrierswhichcanshowbetterrigidity minimumweight andchemicalresistancetofluoropolymers OtherapplicationsChemicalandhydrolysisresistantvalves replacedglass Internalcombustionengines replacedthermosets Cookercomponents replacedenamel Automotivecomponents replacedmetal HightemperatureandchemicalresistantfiltersfromfiberLowfrictionbearings 42 MechanicalPropertiesofPEEK 43 PhysicalPropertiesofPEEK 44 PropertiesofReinforcedPEEK 45 ProcessingPropertiesofPEEK 46 AdvantagesandDisadvantagesofPolyketones AdvantagesVeryhighcontinuoususetemperature 480F OutstandingchemicalresistanceOutstandingwearresistanceExcellenthydrolysisresistanceExcellentmechanicalpropertiesVerylowflammabilityandsmokegenerationResistanttohighlevelsofgammaradiationDisadvantagesHighmaterialcostHighprocessingtemperatures 47 PolyphenyleneMaterials SeveralplasticshavebeendevelopedwiththebenzeneringinthebackbonePolyphenylenePolyphenyleneoxide amorphous Poly phenylenesulfide crystalline Polymonochloroparaxylyene 48 PPOandPPSMaterials AdvantagesofPPS AdvantagesofPPO UsageTempat450F Goodfatigueandimpactstrength Goodradiationresistance Goodradiationresistance Excellentdimensionalstability Excellentdimensionalstability Lowmoistureabsorption Lowoxidation Goodsolventandchemicalresistance Excellentabrasionresistance DisadvantagesofPPS DisadvantagesofPPO HighCost Highcost Highprocesstemperatures Poorresistancetocertainchemicals Poorresistancetochlorinatedhydrocarbons 49 PPOandPPSApplications PPSApplications PPOApplications Computercomponents Videodisplayterminals Rangecomponents Pumpimpellers Hairdryers Smallappliancehousings Submersiblepumpenclosures Instrumentpanels Smallappliancehousings Automotiveparts 50 PPSandPPOMechanicalProperties 51 PPSandPPOPhysicalProperties 52 PPSandPPOProcessingProperties PPSfrequentlyhasglassfibersloadedupto40 byweightTensilestrength 28kpsi tensilemodulus 2Mpsi HDT 500FPPOisfrequentlyblendedwithPSoverawiderangeofpercentages NorylfromG E 53 SectionReview PEEKandPEKarearomaticpolyketones KetonegroupshaveR O Rfunctionality ChemicalstructureofPEEKandPEKdepictsbenzene oxygen benzeneinbackbone PEEKandPEKareusedprimarilyinapplicationsrequiringhightemperatureuseandchemicalresistance AP2CisaspecialversionofPEEKwith68 continuouscarbonfiber Polyphenylenematerialsareplasticswiththebenzeneringinthebackbone PPOandPPSarecharacterizedasheterochainthermoplastics whichhasatomsotherthanCinthechain PPOandPPSaremadeviaCondensationPolymerization PPSfrequentlyhasglassfibersloadedupto40 byweight PPOisfrequentlyblendedwithPSoverawiderangeofpercentages 54 HomeworkQuestions 1 DefinePEEK PPOandPPSchemicalstructures 2 HowarethepropertiesofPEEKandPPSalike 3 DensityofPEEKis PPSis andPPOis whichishigher lowerthanPBTandnylon 4 WhatisthetensilestrengthofPEEKwith0 30 glassfibers Whatisthetensilemodulus 5 PlottensilestrengthandtensilemodulusofPEEK PPO PPS PET PBT Nylon6 PP LDPEandHPDEtolooklikethefollowing TensileModulus Kpsi TensileStrength Kpsi 2 5 10 50 xLDPE xHDPE 55 HomeworkQuestions 6 FourtypicalPhysicalPropertiesofPEEKareOptical Resistancetomoisture UVresistance acidresistance 7 TheAdvantagesofPEEKare and 8 TheDisadvantagesofPEEKare and 9 HowarethepropertiesofPPOandPPSalike Howaretheydifferent 10 Whatare3advantagesthatNylonhasoverPPOandPPS 56 SectionReview Polyestersisoneofmanyheterochainthermoplastics whichhasatomsotherthanCinthechain Polyester