Chapter1PolymericFundamental1:BasicConceptsofPolymerScienceP7

Thescienceofmacromoleculeisdividedinto:biologicalandnonbiologicalmaterialsPolymers,thesyntheticmaterials,referto:

plastics,fibersandelastomers.

Butnature

rubber,woolandcellulose

arealsoincluded.

Polymerchaincanbe

linear,branchedandinterconnectedThemolecularweightofthepolymeristheproductof

themolecularweightoftherepeatunitandthedegreeofpolymerizationNormallythemolecularweightofthepolymersarebetween

10,000and1,000,000Theonlyforcebetweenpolymermoleculesare

secondarybondforcesofattraction.2:TypesofpolymersP14Thermoplastics:wouldsoftenuponheating,couldthenbemadetoflowwhenastresswasapplied,cooledagain,wouldreversiblyregainsolidorrubberynature.Thermosets:couldbeheatedtothepointwheretheywouldsoftenandbemadetoflowunderstressonce,wouldnotdosoreversiblybecauseofacuringreaction.Naturerubber:both,beforeandaftervulcanization.CharlesGoodyearin1839discoveredthecuringreactionwithsulfur3:StructureofsynthesisP19Theformationconditionoflinearpolymer:difunctionalmonomerBranchedpolymer:afewpointsoftrifunctionality(higher)areintroducedatrandompointsalonglinearchains.Poly(A-g-B)Crosslinkedorinterconnectedorcuredpolymer:chainsareconnectedinthreedimensionsbycovalentbonds.Appreciation:理解,欣賞,判斷

schematicdiagram示意圖，difunctionalmonomer雙官能團單體，ascalemodel成比例的模型，assume假設，呈現(xiàn)，承擔Graftcopolymer接枝共聚物nakedeyeBondinginpolymersP21Typesofbonds:primarybonds-covalentbonds;hydrogenbond;vanderWaals--dipoleinteraction;ionic—secondarybondsInlinearandbranchedpolymers,secondarybondsholdtheindividualchainstogether,canflowuponheating-thermoplastics.4:PolymerMorphology-形態(tài),聚集態(tài)結構,高分子鏈的幾何排列P24Anordered,regularchainsaremorelikelythanirregularonestopackintocrystallattice.Hydrogenbondinganddipoleinteractionpromotecrystallinity.Contrasttocrystalis

amorphous,likecookedspaghetti,orwrigglingsnakesSinglecrystal:

folded-chainmodel---regularreentrymodelandirregularreentrymodel/switchboardreentrymodel.Lamellaethichness:10nm/0.01umor50-60carbonatoms.AmorphouspolymermodelCookedSpaghettiAmorphouspolymer:ReptationmodelCrystallinepolymer:Reptationmodel5:TransitionsinpolymersP38TheglasstransitiontemperatureTg:GlassystateexistsbelowTg,rubberystate(橡膠態(tài)或高彈態(tài))aboveTg.TheapplicationTofPlasticsisbelowTgwhilethatofrubberisaboveitsTg.Tg,Tm---first-ordertransitionorαtransition,motionofsegments;Second-ordertransitionorβγtransition---blowTg,motionofchainlinks,sidegroups,branchedchainsTanδvs.TemperatureofPolymer

Chapter2PolymericMaterialsPolymerChemistry—polymersynthesisstep-growth（逐步聚合）chainsofanylengthsAandBcombinetoformlongerchains---condensationpolymerization?chain-growth（連鎖聚合）---freeradicaladdition(自由基加成)

Threestagesoffreeradicaladdionpolymrization:initiation,propagation,andtermination.PolymerizationmethodsEmulsionPolymerization:charge:monomer(waterinsoluble),water,fattyacidsoap,water-solubleinitiator,chain-transferagent//CMC:criticalmicelleconcentration（乳液聚合）Ionicpolymerization:cationic（懸浮聚合）BulkPolymerization（本體聚合）Solutionpolymerization(溶液聚合)Thecategoriesofpolymericmaterialsbiologicalsystemssuchasthehumanbody-proteins,andthelikearenotdiscussedFigure2SpectrumofpolymericmaterialsNaturalpolymersNaturalrubberfromHeveatreeswasbeingusedbytheAmericanIndianswhenColumbusarrivedin1492.Cellulose(纖維素)indifferentforms,starch(淀粉)andcollagen(膠原蛋白)inleatherareotherexamplesofnaturalpolymersused.Manydifferentplasticsmaybeobtainedbymanipulating__themoleculesandchangingthechemical_combinations___.Plasticshaveimportantrolesinagriculture,_application__,clothing,construction,electronics,_furniture__,_packaging__,transportationandnumerousotherareas.Todaywewouldbeutterly_lost__withoutthesyntheticmaterials.Plasticshavebecomeapartofsocietywhichacceptsandoften_takeforgranted__themajorroleofthese_fantastic__materials.Itmightappearthattheplasticsisa_manufacturing___groupunrelatedtomanyotherindustrialorganizations.Manyproductsofothermaterials_involve___theuseofplastics.Metalproductsareoftenplastic_coated____.Thereexistsinthefieldofplastics,atremendousshortageofskilledemployeesandarealneedforanexpandedprograminplasticseducationatalllevels.Syntheticpolymers---Plastics

P87DevelopmentofSyntheticpolymers

P902.Whatisthesecondsyntheticplasticmaterial?Whatarethetypicalproducts?Othername:phenolicresin(酚醛樹脂)3.whatledtoanoverwhelmingvolumeofnewplastics?Examplesofthistypeofplastics.ThermoplasticMaterialsP93Polyethylene=PE,oneofpolyolefinesEthylenegascanbeobtainedfromnaturegasorpetroleumrefinery.PEisproducedintwo/threeformsintermsofdensity.Lowdensity:short/longchainswithhigh/lowdegreeofsidebranching,65%/85%crytallinity.Highdensity:longerlinearchainswithfewsidebranches,85%crystallinityDoesPEfilmtransmitgassesorresistthem?Stresscrack:asurfacechangewhenexposedtooils,gasolineandotherhydrocarbon.(環(huán)境應力開裂,應力與環(huán)境介質的共同影響)WhatformsarePEproducedintermsofshape?PEPolyolefin:聚烯烴.由乙烯、丙烯、1-丁烯、1-戊烯、1-己烯、1-辛烯等α-烯烴聚合成的,單體多個碳,但只有一個雙鍵在鏈端.Vinyl

resin=兩個碳，一個雙鍵Forblanksgranule,powder,film,rod,tubeandsheet.RepeatUnitofPE:-[-CH2—CH2-]-nThemonomerforPPis_propylenes____,through_propylenegasaddition___polymerization,toget_high__molecularweightand_high_crystallinity,

_saturated____hydrocarbonchainswith_no__sidebranches;ThenewPPis_isotactic___instructure.PPcomparedwithPE:monomeriseasier/difficulttogetandpropertiesare_improved___,including____(rigidity,flexlife,heatdistortion,tensilestrengthandstresscrackresistance)duetohighercrystallinityandthelarger__methylgroup____.PP:easilycoloredin不透明,半透明(opaqueandtransluscent)

productsandPPis透明(clarity)inthinsection.

PPcanbeextrudedinto_____andisusedin

luggagecase,

cardfiles,cosmeticcases,automobileacceleratorpedals,blownbottles,fibersforcarpeting,housewares,electronicparts,

aviationcomponentsandthepackagingindustry.(sheet,film,pipe,wirecoatingsandfibers)Vinylresin---PP,PVC，PS

P96P99ForblanksPropylene,

Addition,high,high,saturated,no,isotactic(全同立構）,easier,improved,methylgroup,opaque,translucent,

transparent.-[-CH2—CH-]-nCH3RepeatUnitofPP:PVCiscompounded(混煉)with_plasticizers___,_filler__,_stabilizers___togetanydegreeof_flexibility____infinalproducts.PVC:_slightly___crystallineduetoits__atactic(不規(guī)則)_moleculararrangementwhichprovides_goodclarity___clarity.TwofactorsthatmakePVCuniquelydifferentfromotherplasticsareits__widerangeofproperties__andbeing_self-extinguishing__.性能范圍，從硬制品到軟制品，與其他材料所不同的特點，硬管和軟管，軟片，側基，仿革制品，汽車座罩，主要性能，好的透明度，利用…的優(yōu)勢PVCisusedforpipe,tube,simulatedleather,automobileseatcover,showercurtains,clothorpapercoatedsheet,raincoats,wirecoatings,storagetanks,packaging,blownbottles.Vinylresin---PP,PVC，PSP99_Plasticizers(可塑性),fillers（填料）andstabilizers（穩(wěn)定）Flexibility,slightly,atactic(無規(guī)立構）

goodwiderangeofproperties,self-extinguishingRepeatUnitofPVC:-[-CH2—CH-]-nClPS,aclear,odorless,tasteless,linearandamorphous,isotactic.Twomajordisadvantage:brittleness（脆性）,poorchemicalresistance.Brittlenessiscausedbytheinflexibilityandisovercomebyphysicaladditionofpolybutadiene/polyisoprene.

PSismoldedforrefrigeratorparts,housings,furniture,automobileinteriorparts,bottles,plasticopticalpieces.TherecentuseofPSisasan發(fā)泡制品.Vinylresin---PP,PVC,PS

P101ExpandedfoamRepeatUnitofPS:-[-CH2—CH-]-nThermosettingdiffersfromthermoplastic:cross-linked,rigid,strong,infusible-can’treheatedorreshaped;othertwodifferentcharacteristics:limitedmoldingmethods;scrapcan’tbereused.Mostthermosettingplasticscontainfillerstoimprovepropertiesandtoextendvolume.Typicalfillers:woodflourandglassfibers.ThermosettingMaterialsP119OutlinePhenolFormaldehydeResins

（酚醛樹脂）

P119SyntheticFibers

P135Canbeproducedfrompolyesters,polyamide,vinyls.Chapter3:ChemistryandTechnologyofRubbersUnvulcanizedRubber/VulcanizedRubber/Elastomer/TPEVulcanizedRubber(or:CrosslinkedRubberorElastomer)isobtainedbychemicallycrosslinking(vulcanization)ofunvulcanizedrubberDesignationofRubbers(DIN/ISO1629)

ClassChemicalDescriptionExamplesMRubberswithfullysaturatedmainchain(polymethylene亞甲基

typerubbers)CM,EVM,ACM,AEM(乙烯基丙烯酸酯橡膠）,EPM,EPDM,FKMRRubberswithanunsaturatedmainchain(doublebondcontainingrubbers)NR,SBR,BR,NBR,CR,IIRAbbreviationsandExamples(DIN/ISO1629)

BR----Butadiene-Rubber=polybutadiene（順丁膠）

CR----ChloropreneRubber=polychloroprene(氯丁膠）

CM----ChlorinatedPolyethylene（氯化聚乙烯）

EPM----Ethylene/Propylene-Rubber（二元乙丙膠）

EPDM----Ethylene/Propylene/Diene(二烯）-Rubber（三元乙丙膠）

ENR----EpoxidisedNaturalRubber（環(huán)氧化天然膠）

IR---SyntheticPolyisoprene（異戊膠）

IIR----Butylrubber（丁基膠）

NR----NaturalRubber（天然膠）

NBR----Nitrile-Butadiene-Rubber=Nitrilerubber（丁腈膠）

SBR----Styrene-Butadiene-Rubber（丁苯膠）

(E-SBRandS-SBR)（乳聚和溶聚）

TgsofPolymerswithanUnsaturatedC=CMainChainPolybutadiene-115℃

(100%1,4-cis)(順-1,4結構）Polyisoprene-75℃(100%1,4-cis)Polychloroprene-45℃(100%1,4-trans)NitrileRubber-50℃to-5℃

(dependingonACN-content)ApplicationAreasofSolidRubber

(rubberlatexnotincluded)PriceandVolumeofRubbers(withoutLatex)EvaluationofVulcanizatePropertiesCriteriaofEvaluation

MaximalServiceTemperatureLowTemperatureFlexibilityOilSwellMechanicalPropertiesOzoneResistanceOilandTemperatureResistanceofVulcanizatesAccordingtoASTMD2000Max.temperatureofuseDegreeofswellinginASTM-oilNr.3(vol%)AvailableVulcanizationMethodsfortheDifferentTypesofRubberNaturalRubberPositive:Significantstraininducedcrystallization（應變誘導結晶）Negative:

1.Poorresistancetoswellingwithhydrocarbons(fuels,oilsandgrease)

2.Needformastication（塑煉）

priortocompounding

3.Badwetskidperformance

4.Poorresistancetoheatageing

NR:ApplicationAreasThemajorapplicationofNRisintrucktiresComparisonofIRandNRNRshowsstraininducedcrystallizationEmulsion-SBR(ESBR)-structurePolychloroprene(CR)PositiveAspects:HighloadabilityAdjustablecrystallizationrateGoodvulcanizatepropertiesGooddynamicpropertiesHighweatherandozoneresistancepropertiesExcellentfireresistanceLowgaspermeability（透過性）BroadrangeofgradesNegativeAspects:

1.Highdensity（高密度）

(2,5g/cm3)

2.Highcompoundprice

3.Modestresistanceagainstchemicalsandoils

Fungi(fangai)CR:StructureandApplicationareasNitrileRubber(NBR)

nitrile-butadienerubberBasicFeaturesofNBRPositive:

Lowdegreeofswellinginoil,fuels,greasesandfatsHighlevelofmechanicalpropertiesHighabrasionresistanceBroadrangeofgradesLowgaspermeabilityNBR:DependenceofTgonAcrylonitrileContentPolybutadieneRubber:BRS-SBR:

Solution–StyrenebutadieneRubberFunctionofS-SBR

PartialortotalsubstitutionofactivatorImprovementofsilicadispersionImprovementofsilicareinforcementReductionofhysteresisloss（滯后損失低）Improvementofwetskid（抗?jié)窕裕㏑eductionofabrasionlossFKM/FPMcontainingmonomersPerformanceprofilecomparisonofvulcanizatesQ,HNBR,FKM,EVMChapter4RubberProcessing

--------MixingofRubberMixingEquipmentDiscontinuousMixingBatchMixingTwo-RollMill（雙輥開煉機）InternalMixer（密煉機）wellestablishedStateoftheArt？？？？CanuseeveryformoftherawmaterialsRotorGeometriesTangential(切線的)Rotors（剪切型）1.---Therotorsdonotoverlap2.---Twocurvedflights（轉子翼）whichpumpinoppositedirection3.---Mosteffectivemixingbetweentherotorflightsandthewall4.---Shortincorporation(混合）time5.---largerbatchvolume適用周期短，分段混煉Intermeshing(交互重疊)Rotors嚙合型轉子（生熱低）適用硬膠和一段混煉ContinuousMixing--MixingEquipmentTwinScrewExtruder（雙螺桿擠出機）RingExtruderPlanetaryRollerExtruder

Chapter5PolymerMoldingandProcessingIntroductionP148PlasticsindustryResinmanufactures1.Forms:granules,powders,liquids,pastes.2.Chemicaland/orpetroleumcompanies.Productsmanufactures

Molding:largequantitiesofsingleitemorlowvolumeofmanyitems.Fabricating:beginwithsheetorstockplastics(rod,tubing)DecorationcompaniessupplyingmaterialsandservicetothedecorationoffinishedplasticsproductsMoldingpowderorgranulesareconveyeddownanelectricallyoroil-heatedbarrelbyarotatingscrew.Extrusion（重點）AscrewconsistsofMeltingsection:toconveythesolidpelletsforwardCompressionsection:tocompactandmixthemoltenpolymertoprovideahomogeneousmelt.Meteringsection:topumpthemoltenpolymeroutthroughthedie.Somewords:Dieswell,meltfracture,Extrudersarenormallyspecifiedbyscrewdiameter(2.5cm-30cm)andlength-to-diameter=L/D=20/1-36/1Single-screwextruderisnotapostive-displacementpumpCounter-rotatingtwin-screwextruderisapostive-displacementpump,goodforacertainprofileapplication.Co-rotatingtwin-screwextruderisgoodforcompounding.Chapter6IntroductiontocompositematerialsCompositeMaterialDefinition

AmaterialssystemcomposedoftwoormorephysicallydistinctphaseswhosecombinationproducesaggregatepropertiesthataredifferentfromthoseofitsconstituentsExamples:PlasticmoldingcompoundscontainingfillersRubbermixedwithcarbonblackWood(anaturalcompositeasdistinguishedfromasynthesizedcomposite)WhyCompositesareImportantCompositescanbeverystrongandstiff,yetverylightinweight,soratiosofstrength?to?weightandstiffness?to?weightareseveraltimesgreaterthansteeloraluminumFatiguepropertiesaregenerallybetterthanforcommonengineeringmetalsToughnessisoftengreatertooCompositescanbedesignedthatdonotcorrodelikesteelPossibletoachievecombinationsofpropertiesnotattainablewithmetals,ceramics,orpolymersaloneComponentsinaCompositeMaterialNearlyallcompositematerialsconsistoftwophases:Primaryphase-formsthematrixwithinwhichthesecondaryphaseisimbeddedSecondaryphase-imbeddedphasesometimesreferredtoasareinforcing

agent,becauseitusuallyservestostrengthenthecompositeThereinforcingphasemaybeintheformoffibers,particles,orvariousothergeometries

OurClassificationSchemefor

CompositeMaterialsMetalMatrixComposites(MMCs)?mixturesofceramicsandmetals,suchascementedcarbides（燒結碳化物）

andothercermets(金屬陶瓷）

CeramicMatrixComposites(CMCs)?Al2O3andSiCimbeddedwithfiberstoimproveproperties,especiallyinhightemperatureapplicationsTheleastcommoncompositematrixPolymerMatrixComposites

(PMCs)?thermosettingresinsarewidelyusedinPMCsExamples:epoxyandpolyesterwithfiberreinforcement,andphenolicwithpowders

FunctionsoftheMatrixMaterial

(PrimaryPhase)ProvidesthebulkformofthepartorproductmadeofthecompositematerialHoldstheimbeddedphaseinplace,usuallyenclosing（封閉的）

andoftenconcealing（隱藏的）

itWhenaloadisapplied,thematrixsharestheloadwiththesecondaryphase,insomecasesdeformingsothatthestressisessentiallyborn（bear)bythereinforcingagentTheReinforcingPhase(SecondaryPhase)FunctionistoreinforcetheprimaryphaseImbeddedphaseismostcommonlyoneofthefollowingshapes:FibersParticlesFlakesInaddition,thesecondaryphasecantaketheformofaninfiltrated(滲透）

phaseinaskeletalorporous（多孔）

matrix

Example:apowdermetallurgy（冶金）partinfiltratedwithpolymerFiberOrientation–ThreeCasesOne?dimensional

reinforcement,inwhichmaximumstrengthandstiffnessareobtainedinthedirectionofthefiberPlanar

（平面的）reinforcement,insomecasesintheformofatwo?dimensionalwoven（weave編織）

fabricRandomorthree?dimensionalinwhichthecompositematerialtendstopossessisotropicpropertiesMaterialsforFibersFibermaterialsinfiber?reinforcedcomposites:Glass–mostwidelyusedfilamentCarbon–highelasticmodulusBoron（硼）–veryhighelasticmodulusPolymers–Kevlar（美國杜邦（Dupont）公司研制的一種芳綸纖維材料的商品名稱，材料原名叫”聚對苯二甲酰對苯二胺“）

Ceramics–SiCandAl2O3Metals-steelThemostimportantcommercialuseoffibersisinpolymercompositesParticlesandFlakesAsecondcommonshapeofimbeddedphaseisparticulate,ranginginsizefrommicroscopictomacroscopic

Flakesarebasicallytwo?dimensionalparticles-?smallflatplateletsThedistributionofparticlesinthecompositematrixisrandom,andthereforestrengthandotherpropertiesofthecompositematerialareusuallyisotropicStrengtheningmechanismdependsonparticlesizeTheInterfaceThereisalwaysaninterface（界面）

betweenconstituentphasesinacompositematerialForthecompositetooperateeffectively,thephasesmustbondwheretheyjoinattheinterfaceFigure9.4?Interfacesbetweenphasesinacompositematerial:(a)directbondingbetweenprimaryandsecondaryphasesPropertiesofCompositeMaterialsInselectingacompositematerial,anoptimumcombinationofpropertiesisusuallysought（尋求）,ratherthanoneparticularpropertyExample:fuselage（機身）

andwingsofanaircraftmustbelightweightandbestrong,stiff,andtoughSeveralfiber?reinforcedpolymerspossessthiscombinationofproperties

Example:naturalrubberaloneisrelativelyweakAddingsignificantamountsofcarbonblacktoNRincreasesitsstrengthdramaticallyFigure9.5?(a)Modelofafiber?reinforcedcompositematerialshowingdirectioninwhichelasticmodulusisbeingestimatedbytheruleofmixtures(b)Stress?strainrelationshipsforthecompositematerialanditsconstituents.Thefiberisstiffbutbrittle,whilethematrix(commonlyapolymer)issoftbutductile.Figure9.6?Variationinelasticmodulusandtensilestrengthasafunctionofdirectionofmeasurementrelativetolongitudinalaxisofcarbonfiber?reinforcedepoxycompositePolymerMatrixComposites(PMCs)Apolymerprimaryphaseinwhichasecondaryphaseisimbeddedasfibers,particles,orflakesCommercially,PMCsaremoreimportantthanMMCsorCMCsExamples:mostplasticmoldingcompounds,rubberreinforcedwithcarbonblack,andfiber?reinforcedpolymers(FRPs)FRPsaremostcloselyidentifiedwiththetermcompositeOtherPolymerMatrixCompositesInadditiontoFRPs,otherPMCscontainparticles,flakes,andshortfibersasthesecondaryphaseCalledfille