MostlowMWsubstancesmaybein2maincondensedphasestates,SandL.
StoLtransitionoccursduetocompetitionbetweenmolecularinteractions
( andentropy( thatmakeuptheGibbsenergy
=
Thetransition(meltingorcrystallization)occurssharplyatthetemperature
SandLdifferinpresenceoflongrangeorderinSand
itsabsenceinL.Solidsarethenelastic(G)andliquids
areviscous( >0but G= 0).DensityofSisusuallylarger
thanforL(entropy).
kT
Ifcrystallizationkineticsisslow(lowmobilityofmolecules),
aliquidmaybesupercooled andformanamorphoussolid
orglass(G> 0).
kineticlimitations(largemolecules,highviscosity)
difficultytokeeplongrangeorder(bendingandrotationsofbonds)
packinglimitations(branching,tacticity,sidegroups,backbone
stiffness)
Thisresultsinanunusualthermalbehavior
Amorphoustocrystalline transition
(crystallizationormelting)
Semicrystallinity
Glasstorubber transition
Polymer Crystallization
=
Low ,
High
High ,
Low
Onewaytodeterminedegreeofcrystallinity
Amorphousregionsinliquidstate(Tg <roomtemperature)
Crystallitesactasphysicalcrosslinks
Prerequisite:MW highenoughtoincorporatechainsintoseveral
crystallites(tiemolecules)
crystallite
tiemoleculeconnectingtwocrystallites
Strengthandstiffnessincreasewithincreasingcrystallinefraction
Amorphousregionsprovideimpactstrength(toughness)
Highfreevolumefrac onincreasedmobilityenergydissipa on
overalargerregion
t =lamellathickness(cm)
Crystallizable Polymers
Tm isaffectedbysidegroupsandchainpacking,backbonestiffness,
stereoregularity,interchaininteractions.
Backbone Stiffness
Atactic PP
iPP
Lackofregularity amorphous
sPP
Highlyregularstructure
Highequilibriumcrystallinity
Statistical(random)PEcoPP
Typically amorphous
AtmoderatePformsPEcrystallites
AtlowEformsiPPandsPPcrystals
kT
T<Tg
T>Tg
Aruleofthumb
(ifthereisaTm):
Tg 2/3Tm
0.45Tm <Tg <Tm
(allcrystalizable polymers)
Tg (0.67 0.05)Tm
(55%polymers).
weakinteractionbetweenchain
easyrotationaboutmainchainbonds
largefreevolumeVF
Effectofsidegroups(hinderedrotationandtranslation)
Determination of Tg : Dilatometry
vanderWaals
volume
These resultsmaybeobtainedbyimmersingpolymerinaninertliquid.
physical aging
a finite Cp jump
at glass transition
Cold crystallization
Hc jump
Cp sharply drops
Crystallite melting
Hm jump
Cp sharply rises