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Chapter16.Polymers.Characteristics,ApplicationsandProcessing

Chapter16.Polymers.Characteristics,
ApplicationsandProcessing
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[Chapter6.MechanicalPropertiesofMetals][Chapter7.DislocationsandStrengtheningMechanisms]
[Chapter8.Failure][Chapter9.PhaseDiagrams][Chapter10:PhaseTransformationsinMetals]
[Chapter11.ThermalProcessingofMetalAlloys][Chapter13.CeramicsStructuresandProperties]
[Chapter14.CeramicsApplicationsandProcessing][Chapter15.PolymerStructures]
[Chapter16.Polymers.Characteristics,ApplicationsandProcessing][Chapter17.Composites]
[Chapter19.ElectricalProperties]

16.1Introduction
16.2StressStrainBehavior
Thedescriptionofstressstrainbehaviorissimilartothatofmetals,butaveryimportantconsideration
forpolymersisthatthemechanicalpropertiesdependonthestrainrate,temperature,andenvironmental
conditions.
Thestressstrainbehaviorcanbebrittle,plasticandhighlyelastic(elastomericorrubberlike),seeFig.
16.1.Tensilemodulus(modulus)andtensilestrengthsareordersofmagnitudesmallerthanthoseof
metals,butelongationcanbeupto1000%insomecases.Thetensilestrengthisdefinedatthefracture
point(Fig.16.2)andcanbelowerthantheyieldstrength.
Mechanicalpropertieschangedramaticallywithtemperature,goingfromglasslikebrittlebehaviorat
lowtemperatures(likeintheliquidnitrogendemonstration)toarubberlikebehaviorathigh
temperatures(Fig.16.3).
Ingeneral,decreasingthestrainratehasthesameinfluenceonthestrainstrengthcharacteristicsas
increasingthetemperature:thematerialbecomessofterandmoreductile.
16.3DeformationofSemicrystallinePolymers
Manysemicrystallinepolymershavethespheruliticstructureanddeforminthefollowingsteps(Fig.
16.4):
elongationofamorphoustiechains
tiltingoflamellarchainfoldstowardsthetensiledirection
separationofcrystallineblocksegments
orientationofsegmentsandtiechainsinthetensiledirection
Themacroscopicdeformationinvolvesanupperandloweryieldpointandnecking.Unlikethecaseof
metals,theneckgetsstrongersincethedeformationalignsthechainssoincreasingthetensilestressleads
tothegrowthoftheneck.(Fig.16.5).
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16.4FactorsthatInfluencetheMechanicalPropertiesofPolymers
Thetensilemodulusdecreaseswithincreasingtemperatureordiminishingstrainrate.
Obstaclestothestepsmentionedin16.4strengthenthepolymer.Examplesarecrosslinking(aligned
chainshavemorevanderWaalsinterchainbonds)andalargemass(longermoleculeshavemoreinter
chainbonds).Crystallinityincreasesstrengthasthesecondarybondingisenhancedwhenthemolecular
chainsarecloselypackedandparallel.Predeformationbydrawing,analogoustostrainhardeningin
metals,increasesstrengthbyorientingthemolecularchains.Forundrawnpolymers,heatingincreases
thetensilemodulusandyieldstrength,andreducestheductilityoppositeofwhathappensinmetals.
16.5Crystallization,Melting,andGlassTransitionPhenomena
CrystallizationratesaregovernedbythesametypeofScurveswesawinthecaseofmetals(Fig.16.7).
Nucleationbecomesslowerathighertemperatures.
Themeltingbehaviorofsemicrystallinepolymersisintermediatebetweenthatofcrystallinematerials
(sharpdensitychangeatameltingtemperature)andthatofapureamorphousmaterial(slightchangein
slopeofdensityattheglasstransitiontemperature).Theglasstransitiontemperatureisbetween0.5and
0.8ofthemeltingtemperature.
Themeltingtemperatureincreaseswiththerateofheating,thicknessofthelamellae,anddependsonthe
temperatureatwhichthepolymerwascrystallized.
Meltinginvolvesbreakingoftheinterchainbonds,sotheglassandmeltingtemperaturesdependon:
chainstiffness(e.g.,singlevs.doublebonds)
size,shapeofsidegroups
sizeofmolecule
sidebranches,defects
crosslinking
Rigidchainshavehighermeltingtemperatures.
16.6ThermoplasticandThermosettingPolymers
Thermoplasticpolymers(thermoplasts)softenreversiblywhenheated(hardenwhencooledback)
Thermosettingpolymers(thermosets)hardenpermanentlywhenheated,ascrosslinkinghinderbending
androtations.Thermosetsareharder,moredimensionallystable,andmorebrittlethanthermoplasts.
16.7Viscoelasticity
Atlowtemperatures,amorphouspolymersdeformelastically,likeglass,atsmallelongation.Athigh
temperaturesthebehaviorisviscous,likeliquids.Atintermediatetemperatures,thebehavior,likea
rubberysolid,istermedviscoelastic.
Viscoelasticityischaracterizedbytheviscoelasticrelaxationmodulus
Er=(t)/0.
Ifthematerialisstrainedtoavalue0.itisfoundthatthestressneedstobereducedwithtimetomaintain
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thisconstantvalueofstrain(seefigs.16.11and16.12).
Inviscoelasticcreep,thestressiskeptconstantat0andthechangeofdeformationwithtimet)is
measured.Thetimedependentcreepmodulusisgivenby
Ec=0/(t).
16.8DeformationandElastomers
Elastomerscanbedeformedtoverylargestrainsandthespringbackelasticallytotheoriginallength,a
behaviorfirstobservedinnaturalrubber.Elasticelongationisduetouncoiling,untwistingand
straighteningofchainsinthestressdirection.
Tobeelastomeric,thepolymerneedstomeetseveralcriteria:
mustnotcrystallizeeasily
haverelativelyfreechainrotations
delayedplasticdeformationbycrosslinking(achievedbyvulcanization).
beabovetheglasstransitiontemperature
16.9FractureofPolymers
Asothermechanicalproperties,thefracturestrengthofpolymersismuchlowerthanthatofmetals.
Fracturealsostartswithcracksatflaws,scratches,etc.Fractureinvolvesbreakingofcovalentbondsin
thechains.Thermoplastscanhavebothbrittleandductilefracturebehaviors.Glassythermosetshave
brittlefractureatlowtemperaturesandductilefractureathightemperatures.
Glassythremoplastsoftensuffergrazingbeforebrittlefracture.Crazesareassociatedwithregionsof
highlylocalizedyieldingwhichleadstotheformationofinterconnectedmicrovoids(Fig.16.15).Crazing
absorbsenergythusincreasingthefracturestrengthofthepolymer.
16.10MiscellaneousCharacteristics
Polymersarebrittleatlowtemperaturesandhavelowimpactstrengths(IzodorCharpytests),anda
brittletoductiletransitionoveranarrowtemperaturerange.
Fatigueissimilartothecaseofmetalsbutatreducedloadsandismoresensitivetofrequencydueto
heatingwhichleadstosoftening.
16.11Polymerization
Polymerizationisthesynthesisofhighpolymersfromrawmaterialslikeoilorcoal.Itmayoccurby:
addition(chainreaction)polymerization,wheremonomerunitsareattachedoneatatime
condensationpolymerization,bystepwiseintermolecularchemicalreactionsthatproducethemer
units.
16.1216.14notcovered
16.15Elastomers
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Invulcanization,crosslinkingoftheelastomericpolymerisachievedbyanirreversiblechemicalreaction
usuallyathightemperatures(hencevulcan),andusuallyinvolvingtheadditionofsulfurcompounds.
TheSatomsaretheonesthatformthebridgecrosslinks.Elastomersarethermosettingduetothecross
linking.
Rubbersbecomeharderandextendlesswithincreasingsulfurcontent.Forautomobileapplications,
syntheticrubbersarestrengthenedbyaddingcarbonblack.
Insiliconerubbers,thebackboneCatomsarereplacedbyachainofalternatingsiliconandoxygen
atoms.TheseelastomersarealsocrosslinkedandarestabletohighertemperaturesthanCbased
elastomers.
16.1616.18notcovered
Terms:
Additionpolymerization
Condensationpolymerization
Elastomer
Glasstransitiontemperature
Plastic
Relaxationmodulus
Thermoplasticpolymer
Thermoplasticelastomer
Thermosettingpolymer
Ultrahighmolecularweightpolyethylene
Viscoelasticity
Vulcanization

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