双语课件聚合物科学与工程导论

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,欣赏,判断

schematicdiagram示意图，difunctionalmonomer双官能团单体，ascalemodel成比例的模型，assume假设，呈现，承担Graftcopolymer接枝共聚物nakedeyeBondinginpolymersP21Typesofbonds:primarybonds-covalentbonds;hydrogenbond;vanderWaals--dipoleinteraction;ionic—secondarybondsInlinearandbranchedpolymers,secondarybondsholdtheindividualchainstogether,canflowuponheating-thermoplastics.4:PolymerMorphology-形态,聚集态结构,高分子链的几何排列P24Anordered,regularchainsaremorelikelythanirregularonestopackintocrystallattice.Hydrogenbondinganddipoleinteractionpromotecrystallinity.Contrasttocrystalis

amorphous,likecookedspaghetti,orwrigglingsnakesSinglecrystal:

folded-chainmodel---regularreentrymodelandirregularreentrymodel/switchboardreentrymodel.Lamellaethichness:10nm/0.01umor50-60carbonatoms.AmorphouspolymermodelCookedSpaghettiAmorphouspolymer:ReptationmodelCrystallinepolymer:Reptationmodel5:TransitionsinpolymersP38TheglasstransitiontemperatureTg:GlassystateexistsbelowTg,rubberystate(橡胶态或高弹态)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（连锁聚合）---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（悬浮聚合）BulkPolymerization（本体聚合）Solutionpolymerization(溶液聚合)Thecategoriesofpolymericmaterialsbiologicalsystemssuchasthehumanbody-proteins,andthelikearenotdiscussedFigure2SpectrumofpolymericmaterialsNaturalpolymersNaturalrubberfromHeveatreeswasbeingusedbytheAmericanIndianswhenColumbusarrivedin1492.Cellulose(纤维素)indifferentforms,starch(淀粉)andcollagen(胶原蛋白)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(酚醛树脂)3.whatledtoanoverwhelmingvolumeofnewplastics?Examplesofthistypeofplastics.ThermoplasticMaterialsP93Polyethylene=PE,oneofpolyolefinesEthylenegascanbeobtainedfromnaturegasorpetroleumrefinery.PEisproducedintwo/threeformsintermsofdensity.Lowdensity:short/longchainswithhigh/lowdegreeofsidebranching,65%/85%crytallinity.Highdensity:longerlinearchainswithfewsidebranches,85%crystallinityDoesPEfilmtransmitgassesorresistthem?Stresscrack:asurfacechangewhenexposedtooils,gasolineandotherhydrocarbon.(环境应力开裂,应力与环境介质的共同影响)WhatformsarePEproducedintermsofshape?PEPolyolefin:聚烯烃.由乙烯、丙烯、1-丁烯、1-戊烯、1-己烯、1-辛烯等α-烯烃聚合成的,单体多个碳,但只有一个双键在链端.Vinyl

resin=两个碳，一个双键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(全同立构）,easier,improved,methylgroup,opaque,translucent,

transparent.-[-CH2—CH-]-nCH3RepeatUnitofPP:PVCiscompounded(混炼)with_plasticizers___,_filler__,_stabilizers___togetanydegreeof_flexibility____infinalproducts.PVC:_slightly___crystallineduetoits__atactic(不规则)_moleculararrangementwhichprovides_goodclarity___clarity.TwofactorsthatmakePVCuniquelydifferentfromotherplasticsareits__widerangeofproperties__andbeing_self-extinguishing__.性能范围，从硬制品到软制品，与其他材料所不同的特点，硬管和软管，软片，侧基，仿革制品，汽车座罩，主要性能，好的透明度，利用…的优势PVCisusedforpipe,tube,simulatedleather,automobileseatcover,showercurtains,clothorpapercoatedsheet,raincoats,wirecoatings,storagetanks,packaging,blownbottles.Vinylresin---PP,PVC，PSP99_Plasticizers(可塑性),fillers（填料）andstabilizers（稳定）Flexibility,slightly,atactic(无规立构）

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发泡制品.Vinylresin---PP,PVC,PS

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

（酚醛树脂）

P119SyntheticFibers

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

ClassChemicalDescriptionExamplesMRubberswithfullysaturatedmainchain(polymethylene亚甲基

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

BR----Butadiene-Rubber=polybutadiene（顺丁胶）

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

CM----ChlorinatedPolyethylene（氯化聚乙烯）

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

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

ENR----EpoxidisedNaturalRubber（环氧化天然胶）

IR---SyntheticPolyisoprene（异戊胶）

IIR----Butylrubber（丁基胶）

NR----NaturalRubber（天然胶）

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

SBR----Styrene-Butadiene-Rubber（丁苯胶）

(E-SBRandS-SBR)（乳聚和溶聚）

TgsofPolymerswithanUnsaturatedC=CMainChainPolybutadiene-115℃

(100%1,4-cis)(顺-1,4结构）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（应变诱导结晶）Negative:

1.Poorresistancetoswellingwithhydrocarbons(fuels,oilsandgrease)

2.Needformastication（塑炼）

priortocompounding

3.Badwetskidperformance

4.Poorresistancetoheatageing

NR:ApplicationAreasThemajorapplicationofNRisintrucktiresComparisonofIRandNRNRshowsstraininducedcrystallizationEmulsion-SBR(ESBR)-structurePolychloroprene(CR)PositiveAspects:HighloadabilityAdjustablecrystallizationrateGoodvulcanizatepropertiesGooddynamicpropertiesHighweatherandozoneresistancepropertiesExcellentfireresistanceLowgaspermeability（透过性）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（滞后损失低）Improvementofwetskid（抗湿滑性）ReductionofabrasionlossFKM/FPMcontainingmonomersPerformanceprofilecomparisonofvulcanizatesQ,HNBR,FKM,EVMChapter4RubberProcessing

--------MixingofRubberMixingEquipmentDiscontinuousMixingBatchMixingTwo-RollMill（双辊开炼机）InternalMixer（密炼机）wellestablishedStateoftheArt？？？？CanuseeveryformoftherawmaterialsRotorGeometriesTangential(切线的)Rotors（剪切型）1.---Therotorsdonotoverlap2.---Twocurvedflights（转子翼）whichpumpinoppositedirection3.---Mosteffectivemixingbetweentherotorflightsandthewall4.---Shortincorporation(混合）time5.---largerbatchvolume适用周期短，分段混炼Intermeshing(交互重叠)Rotors啮合型转子（生热低）适用硬胶和一段混炼ContinuousMixing--MixingEquipmentTwinScrewExtruder（双螺杆挤出机）RingExtruderPlanetaryRollerExtruder

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

Molding:largequantitiesofsingleitemorlowvolumeofmanyitems.Fabricating:beginwithsheetorstockplastics(rod,tubing)DecorationcompaniessupplyingmaterialsandservicetothedecorationoffinishedplasticsproductsMoldingpowderorgranulesareconveyeddownanelectricallyoroil-heatedbarrelbyarotatingscrew.Extrusion（重点）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（烧结碳化物）

andothercermets(金属陶瓷）

CeramicMatrixComposites(CMCs)‑Al2O3andSiCimbeddedwithfiberstoimproveproperties,especiallyinhightemperatureapplicationsTheleastcommoncompositematrixPolymerMatrixComposites

(PMCs)‑thermosettingresinsarewidelyusedinPMCsExamples:epoxyandpolyesterwithfiberreinforcement,andphenolicwithpowders

FunctionsoftheMatrixMaterial

(PrimaryPhase)ProvidesthebulkformofthepartorproductmadeofthecompositematerialHoldstheimbeddedphaseinplace,usuallyenclosing（封闭的）

andoftenconcealing（隐藏的）

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

phaseinaskeletalorporous（多孔）

matrix

Example:apowdermetallurgy（冶金）partinfiltratedwithpolymerFiberOrientation–ThreeCasesOne‑dimensional

reinforcement,inwhichmaximumstrengthandstiffnessareobtainedinthedirectionofthefiberPlanar

（平面的）reinforcement,insomecasesintheformofatwo‑dimensionalwoven（weave编织）

fabricRandomorthree‑dimensionalinwhichthecompositematerialtendstopossessisotropicpropertiesMaterialsforFibersFibermaterialsinfiber‑reinforcedcomposites:Glass–mostwidelyusedfilamentCarbon–highelasticmodulusBoron（硼）–veryhighelasticmodulusPolymers–Kevlar（美国杜邦（Dupont）公司研制的一种芳纶纤维材料的商品名称，材料原名叫”聚对苯二甲酰对苯二胺“）

Ceramics–SiCandAl2O3Metals-steelThemostimportantcommercialuseoffibersisinpolymercompositesParticlesandFlakesAsecondcommonshapeofimbeddedphaseisparticulate,ranginginsizefrommicroscopictomacroscopic

Flakesarebasicallytwo‑dimensionalparticles-‑smallflatplateletsThedistributionofparticlesinthecompositematrixisrandom,andthereforestrengthandotherpropertiesofthecompositematerialareusuallyisotropicStrengtheningmechanismdependsonparticlesizeTheInterfaceThereisalwaysaninterface（界面）

betweenconstituentphasesinacompositematerialForthecompositetooperateeffectively,thephasesmustbondwheretheyjoinattheinterfaceFigure9.4‑Interfacesbetweenphasesinacompositematerial:(a)directbondingbetweenprimaryandsecondaryphasesPropertiesofCompositeMaterialsInselectingacompositematerial,anoptimumcombinationofpropertiesisusuallysought（寻求）,ratherthanoneparticularpropertyExample:fuselage（机身）

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