Phase States of Matter

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).

Thermal Transitions in Polymers

PolymersaredifferentfromlowMWcompoundsinseveralaspects:

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

Spacial Arrangement and Growth of Crystallites

Effect of Crystallinity on Mechanical Properties

Semicrystalline engineeringplastics:

Amorphousregionsinliquidstate(Tg <roomtemperature)
Crystallitesactasphysicalcrosslinks

Prerequisite:MW highenoughtoincorporatechainsintoseveral
crystallites(tiemolecules)

crystallite
tiemoleculeconnectingtwocrystallites

Strengthandstiffnessincreasewithincreasingcrystallinefraction
Amorphousregionsprovideimpactstrength(toughness)

Highfreevolumefrac onincreasedmobilityenergydissipa on
overalargerregion

Effect of Crystal Size on Tm

t =lamellathickness(cm)

TmSm =Hf0 +2t/c

Crystallizable Polymers

Tm isaffectedbysidegroupsandchainpacking,backbonestiffness,
stereoregularity,interchaininteractions.

Backbone Stiffness

Stereo-regularity and Tacticity

PE

Atactic PP

iPP

Lackofregularity amorphous

sPP

Highlyregularstructure
Highequilibriumcrystallinity

Statistical(random)PEcoPP
Typically amorphous
AtmoderatePformsPEcrystallites
AtlowEformsiPPandsPPcrystals

Strength of Interchain Interactions

Content of Interacting Groups

Glass Transition in Polymers (Tg)

Glassy stateisanonequilibriumstateofpolymerwhere
translational/rotationaldegreesoffreedomofindividual
segmentsmotionarefrozenoutofequilibrium.
AboveglasstransitiontemperatureTg thesegmentalmotion
isactivatedandpolymerbecomesrubbery (viscoelastic).
ThisisNOTaphasetransition!
Tg maybefoundfrom3typesofmeasurements:
Mechanicalproperties(G,)
ThermalcapacityCp (e.g.,byDSC)
Thermalexpansion(dilation)

kT
T<Tg

T>Tg

Relation between Tg and Tm

Aruleofthumb
(ifthereisaTm):
Tg 2/3Tm
0.45Tm <Tg <Tm
(allcrystalizable polymers)
Tg (0.67 0.05)Tm
(55%polymers).

PolymerstructureusuallyaffectsTg andTm inasimilarmanner

Effects of chemical structure on Tg

Onsetofmolecularmobility(~1030mers)atTg isencouragedby

weakinteractionbetweenchain

easyrotationaboutmainchainbonds

largefreevolumeVF

Effectofsidegroups(hinderedrotationandtranslation)

Determination of Tg : Dilatometry

vanderWaals
volume
These resultsmaybeobtainedbyimmersingpolymerinaninertliquid.

Kinetic Nature of Glass Transition

Tg dependsonthecooling(quenching)rate
Thecharacteristicsofaglassypolymermayalsoslowly
change(physicalaging)

physical aging

Tg , Tm and Elastic Modulus

Thermal-Mechanical Analysis (TMA)

Tg , Tm and Elastic Modulus (cntd.)

Tg , Tm and Thermal Characteristics

DSC and Its Interpretation

Thermodynamic Changes at Tg and Tm

a finite Cp jump
at glass transition

Cold crystallization
Hc jump
Cp sharply drops

Crystallite melting
Hm jump
Cp sharply rises

Useful relations for Tg

Fox equation describes fully or partially miscible blends with one Tg
(including low-MW low-Tg additives)

where is the mass fraction.

William, Lendel and Ferry (WLF) relation expresses dependence
of relaxation processes on temperature (e.g., viscosity) above Tg

These expressions are one example of the use of time-temperature

superposition (TTS) principle .

Controlling Tg with small molecule additives

Plasticizers:
LowmolarmassadditivesoflowTg
Actmainlyaslubricants:reducefrictionandaddfreevolume
Bis (2ehtylhexyl)phthalate(DOP)
(newcarsmell)
Tg,PVC =70oC
Tg,DOP = 80oC
Antiplasticizers:
Smallmoleculeadditiveswhichfitcloselybetweenchains
loweringtheoverallfreevolumeandraisingTg