CHEG589:PolymerNanocomposites

Chapter1:NanotechnologyandNanocomposites
Dr.VikasMittal,Summer2015

TheBeginning

In1959,PhysicsNobelLaureateRichardFeynmansuggested:WhatIwant
totalkaboutistheproblemofmanipulatingandcontrollingthingsona
smallscale...Whatarethelimitationsastohowsmallathinghastobe
beforeyoucannolongermoldit?

Thetermnanotechnologywasfirstusedin1974byNorioTaniguchito
refertothepreciseandaccuratetolerancesrequiredformachiningand
finishingmaterials.

In1981,K.E.Drexlerdescribedanew"bottomup"approach,insteadof
thetopdownapproachdiscussedearlierbyFeynmanandTaniguchi.The
bottomupapproachinvolvedmolecularmanipulationandmolecular
engineeringtobuildmolecularmachinesandmoleculardeviceswith
atomicprecision.

WhatisNanotechnology?

Thetermnano derivesfromtheGreekwordfordwarf.Itisusedasaprefix
foranyunitsuchasasecondorameter,anditmeansabillionthofthatunit.
Hence,ananometer(nm)isabillionthofameter,or109meters.

Nanotechnologymeansanytechnologyonananoscale thathasapplications
intherealworld.Nanotechnologyencompassestheproductionand
applicationofphysical,chemical,andbiologicalsystemsatscalesranging
fromindividualatomsormoleculestosubmicrondimensions,aswellasthe
integrationoftheresultingnanostructuresintolargersystems.

WhatisNanotechnology?

Despitethewideuseofthewordnanotechnology,thetermhasbeen
misleadinginmanyinstances.Thisisbecausesomeofthetechnology
dealswithsystemsonthemicrometerrangeandnotonthenanometer
range(1100nm).

Nanomaterials arealsonotundiscoveredmaterials.Itisimportanttokeep
inmindthatsomepasttechnologysuchas,forexample,nanoparticlesof
carbonusedtoreinforcetiresaswellasnature'sphotosynthesisare
alreadyaformofnanotechnology.

ApproachestoNanotechnologies

topdownapproach:Anoperatorfirstdesignsandcontrolsamacroscale
entitytoproduceanexactcopyofitself,butsmallerinsize.Subsequently,
thisdownscaledentity,willmakeareplicaofitself,butalsoafewtimes
smallerinsize.Thisprocessofreducingthescalecontinuesuntila
nanosize entityisproducedandiscapableofmanipulating
nanostructures.

Oneoftheemergingfieldsbasedonthistopdownapproachisthefieldof
nanoandmicroelectromechanicalsystems(NEMSandMEMS,
respectively).MEMSresearchhasalreadyproducedvariousmicro
mechanicaldevices,smallerthan1mm2,whichareabletoincorporate
microsensors,cantilevers,microvalves,andmicropumps.

Aninterestingexampleisthemicrocar fabricatedbyNippondenso Co.

ApproachestoNanotechnologies

Thetopdownapproachisnotafriendly,inexpensive,andrapidwayof
producingnanostructures.Therefore,abottomupapproachneedstobe
considered.

Theconceptofthebottomupapproachisthatonestartswithatomsor
molecules,whichbuilduptoformlargerstructures.

Inthiscontext,therearethreeimportantenablingbottomup
technologies,namely(1)supramolecular andmolecularchemistry,(2)
scanningprobes,and(3)biotechnology.

LengthScale

Lengthscalesranging
fromsubatomicthrough
molecular,human,and
terrestrialtoastronomic

WhyisNanoScaleImportant?
Bycreatingnanoscalestructures,itispossibletocontrolthe
fundamentalpropertiesofmaterials,suchastheirmelting
temperature,magneticproperties,chargecapacity,andeventheir
color,withoutchangingthematerialschemicalcomposition.
Makinguseofthispotentialleadstonew,highperformance
productsandtechnologiesthatwerenotpossiblebefore.
Nanoscale structuressuchasnanoparticlesandnanolayers have
veryhighsurfacetovolumeratios,makingthemidealforusein
polymericmaterials.

NanotechnologyinNature
Abalone
Abalonebuildstheshellfromtraditional
materials,namelycalciumcarbonate(CaCO3)
andaprotein,formingalayered
nanocompositethatisstrongandresilient
Lookingattheshellunderanelectron
microscopeathighmagnifications,theshell
lookslikeabrickwall,withcalciumcarbonate"bricks"separatedbytheprotein
"glue"
Theformationoftheabaloneshellstartswithproteins,whichselfassembleinto
"roomwalls"withadistributionofnegativelychargedsites.Insideeach"room"
thereisseawaterfilledwithcalciumandcarbonateions,whichareattractedto
thewallsandeventuallyformcrystalsofCaCO3

NanotechnologyinNature
SpiderWeb

Thecombinedstrengthandflexibilityofaspiderwebresultsfromthe
arrangementofnanocrystalline reinforcementsembeddedinapolymer
matrix.
Acloserlookatthespiderwebmicrostructurerevealstheexistenceof
stronglyorientednanocrystals,whichadheretotheproteinthatcomposes
theirsurroundingpolymericmatrix.Inotherwords,thespiderwebisa
nanocompositematerialcomposedofrelativelystiffnanocrystals dispersed
withinastretchymatrix

NanotechnologyinNature
RhinocerosHorn
Thehornisacompositemadeoftwotypesof
keratin.
Onetypeisintheformoftubulesthataredensely
packed.Thesetubules,whichrangefrom300to
500m,comprisearound40layersofcells.
Surroundingthesetubulesisanothertypeof
keratinthatiscontinuousandactsasamatrix.
Becausethematrixandthetubulesarethesame
material,theinterfacialstrengthisverygood,which
leadstoarigidmaterialthatisverytoughtobreak.

ClassesofMaterials

Nanomaterials:Thenanomaterialclassofmaterialsisextremelybroad
becauseitcanincludeallthepreviousclassesofmaterials,providedthey
arecomposedofastructuralcomponentatthenanoscale ortheyexhibit
oneofthedimensionsatthenanoscale.

Nanomaterials aretypicallycategorizedaccordingtothenumberof
dimensionsthatarenotatthenanoscale
0D(nanoparticles),
1D(nanowires,nanotubes,andnanorods),
2D(nanofilms andnanocoatings),
3D(bulk)

ClassificationofNanomaterials

Themosttypicalwayofclassifying
nanomaterials istoidentifythem
accordingtotheirdimensions.

Nanomaterials canbeclassifiedas(1)
zerodimensional(0D),(2)one
dimensional(1D),(3)two
dimensional(2D),and(4)three
dimensional(3D).

Thisclassificationisbasedonthe
numberofdimensions,whicharenot
confinedtothenanoscale range(<100
nm).

ClassificationofNanomaterials
0D
Themostcommonrepresentationofzerodimensional
nanomaterials arenanoparticles.Thesenanoparticles
can:

Beamorphousorcrystalline
Besinglecrystallineorpolycrystalline
Becomposedofsingleormultichemical elements
Exhibitvariousshapesandforms
Existindividuallyorincorporatedinamatrix
Bemetallic,ceramic,orpolymeric

ClassificationofNanomaterials
1D
1Dnanomaterials differfrom0Dnanomaterials inthat
theformerhaveonedimensionthatisoutsidethe
nanoscale.Thisdifferenceinmaterialdimensionsleadsto
needleshapednanomaterials.Onedimensional
nanomaterials includenanotubes,nanorods,and
nanowires.1Dnanomaterials canbe:
Amorphousorcrystalline
Singlecrystallineorpolycrystalline
Chemicallypureorimpure
Standalonematerialsorembeddedinwithinanother
medium
Metallic,ceramic,orpolymeric

ClassificationofNanomaterials
2D
2Dnanomaterials arematerialsinwhichtwoofthe
dimensionsarenotconfinedtothenanoscale.Asaresult,
2Dnanomaterials exhibitplatelike shapes.Two
dimensionalmaterialscanbe:

Amorphousorcrystalline
Madeupofvariouschemicalcompositions
Usedasasinglelayerorasmultilayerstructures
Depositedonasubstrate
Integratedinasurroundingmatrixmaterial
Metallic,ceramic,orpolymeric

ClassificationofNanomaterials
3D
Thesematerialshavethreedimensionsabove100nm.
Despitetheirbulkdimensions,thesematerialspossessa
nanocrystalline structureorinvolvethepresenceoffeatures
atthenanoscale.Withrespecttothepresenceoffeaturesat
thenanoscale,3Dnanomaterials cancontaindispersionsof
nanoparticles,bundlesofnanowires,andnanotubesaswell
asmultinanolayers.Threedimensionalnanomaterials canbe:

Amorphousorcrystalline
Chemicallypureorimpure
Compositematerials
Composedofmultinanolayers
Metallic,ceramic,orpolymeric

ClassificationofNanomaterials

The2Dnanomaterialmaybecalleda
nanocrystalline filmbecauseoftwofeatures:
(1)thematerialexhibitsanoverallexterior
thicknesswithnanoscale dimensions,and(2)
itsinternalstructureisalsoatthenanoscale.
Thoughthisexamplehelpsillustratetwo
possiblewaysofcategorizingof2D
nanomaterials,boththeserestrictionsdonot
needtobeinplaceforthematerialtobe
consideredananomaterial.
Infact, iftheexteriorthicknessremainsatthe
nanoscale,itispossibleforthesamefilmto
havealarger(above100nm)internalgrain
structureandstillqualifytheentirematerial
asananoscale material.

ClassificationofNanomaterials

Generally,2Dnanomaterials,aredepositedon
asubstrateorsupportwithtypicaldimensions
abovethenanoscale.Inthesecases,theoverall
samplethicknessdimensionsbecomea
summationofthefilm'sandsubstrate's
thickness.Whenthisoccurs,the2D
nanomaterialcanbeconsideredananocoating.

Whenthesubstratethicknessdoeshave
nanoscale dimensionsorwhenmultiplelayers,
withthicknessesatthenanoscale aredeposited
sequentially,the2Dnanomaterialcanbe
classifiedasamultilayer2Dnanomaterial.
Withineachlayer,theinternalstructurecanbe
atthenanoscale oraboveit.

ClassificationofNanomaterials

For3Dnanomaterials:fromourprevious
definition,bulknanomaterials are
materialsthatdonothaveanydimension
atthenanoscale.However,bulk
nanomaterials stillexhibitfeaturesatthe
nanoscale.Bulknanomaterials with
dimensionslargerthanthenanoscale can
becomposedofcrystallitesorgrainsatthe
nano scale.Thesematerialsarethencalled
nanocrystalline materials.

ClassificationofNanomaterials
Anothergroupof3Dnanomaterials arecallednanocomposites.These
materialsareformedoftwoormorematerialswithverydistinctive
propertiesthatactsynergisticallytocreatepropertiesthatcannotbe
achievedbyeachsinglematerialalone.Thematrixofthenanocomposite,
whichcanbepolymeric,metallic,orceramic,hasdimensionslargerthanthe
nanoscale,whereasthereinforcingphaseiscommonlyatthenanoscale.

ClassificationofNanomaterials

WhatisaPolymer?
AGIANTmolecule
Madeupofunits
calledmonomers
Ifacarbonatomwas
thesizeofatennis
ball:
PE =30km
DNA=70,000km

UsesofPolymers

Petrochemical Value Chain based on Cracker

Source: Linde

Definitions
Monomer simplemolecularunitwhichwhenreacted
togetherformsapolymer.

Oligomer lowmolecularweightcompoundwith
severalrepeatunitsjoinedtogether.

Polymer substancecomposedofmoleculeswitha
largemolecularweightformedfromrepeatingunits
covalentlybondedtogether.

TypesofPolymers

natural polymers
- cellulose
- proteins
- DNA
- natural rubber
- shellac
- amber

synthetic polymers
- polyethylene
- polypropylene
- poly(vinylchloride)
- synthetic rubber
- polyamides
- polyurethanes
- melamine resins

Importance of DP
The dimer of ethylene is a gas, but
oligomers with a DP of 3 or more are
liquids, with the liquid viscosity increasing
with the chain length.
Polyethylenes with DPs of
about 30 are grease like, and those with
DPs around 50 are waxes.
As the DP value exceeds 400 or the
molecular weight exceeds about 10,000,
polyethylenes become hard resins with
softening points about 100C. The increase
in softening point with chain length in the
higher-molecular-weight range is small.

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Importance of Molecular Weight

Tensile strength properties
increase rapidly first as the chain length
increases and then level off
The melt viscosity continues to increase
rapidly with molecular weight
Polymers with very high molecular
weights have superior mechanical
properties but are difficult to process and
fabricate due to their high melt viscosities.
The range of molecular weights chosen
for commercial polymers represents a
compromise between maximum properties
and processability.

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UniquenessofNanostructured
Materials
Whatisuniquetonanofillers comparedtomicrometerscale
traditionalfillers,andhowdothecompositescompareto
theirmacroscopiccounterparts?
Smallsizeoffillerparticles(opticalclarity)
Nostressconcentration
Exceptionallylargeinterfacialarea

UniquenessofNanostructured
Materials

UniquenessofNanostructured
Materials

Nanocomposites

Nanocompositesareaclassofmaterialsinwhichoneormorephaseswith
nanoscale dimensions(0D,1D,and2D)areembeddedinametal,
ceramic,orpolymermatrix.

Thegeneralideabehindtheadditionofthenanoscale secondphaseisto
createasynergybetweenthevariousconstituents,suchthatnovel
propertiescapableofmeetingorexceedingdesignexpectationscanbe
achieved.

Thepropertiesofnanocompositesrelyonarangeofvariables,particularly
thematrixmaterial,loading,degreeofdispersion,size,shape,and
orientationofthenanoscale secondphaseandinteractionsbetweenthe
matrixandthesecondphase.

Nanocomposites
Polymermatrixnanocomposites

Polymertype:thermoset,thermoplastic,elastomer
Reinforcement:nanoparticles(0D),nanotubes(1D)andnanoplates (2D)

Polymermatrixnanocompositeswith0Dmaterials

Dependingonthetypeofnanoparticlesadded,themechanical,electrical,
optical,andthermalpropertiescanbealtered
Inthecaseofmechanicalproperties,modulusandstrengthdependonthe
degreeofinteractionbetweentheparticleandthepolymer.Forexample,
inpoly(methylmethacrylate)(PMMA)nanocompositesreinforcedwith
alumina,themodulusdecreasesduetotheweakinteraction,whereasin
polystyrenenanocompositesreinforcedwithsilicananoparticles,the
modulusincreasesduetoastrongbonding.

Nanocomposites
Polymermatrixnanocompositeswith1Dmaterials

Carbonnanotubes(CNTs)arewidelyusedasreinforcement.

Severalcriticalfactorsneedtobeaddressed:
(1) uniformdispersionofcarbonnanotubeswithinthepolymermatrix,
(2) alignmentofCNTsinthenanocomposite,
(3) goodinterfacialbondingbetweentheCNTsandthepolymermatrix.

WithrespecttothedispersionofCNTs,they
exhibitsmoothsurfacesandintrinsicVanderWaals
interactions,whichtendtopromoteclusteringwhen
dispersedinapolymermatrix

Nanocomposites
Polymermatrixnanocompositeswith2Dmaterials

Platelikelayeredmaterials(layeredsilicates)
withathicknessontheorderof1nmbutwith
anaspectratioof25orabove.

Significantimprovementsindifferentproperties

Fortheselayeredsilicatestobeusefulin
nanocomposites,thelayersmustbeseparated
anddispersedwithinthepolymermatrix.
However,theselayersarehighlyhydrophilic,and
thusindividuallayersdonoteasilydispersein
relativelyhydrophobicspecies,suchasan
organicpolymer.

Nanocomposites

Theresultingnanocompositescanexhibit
variousmicrostructures.

Intercalatednanocomposites,whenthe
polymerdiffusesintotheclaylayers,thereby
expandingthedistancebetweentheclaylayers,
buttheorder(orperiodicity)isstillmaintained

Exfoliatednanocompositeswhenindividual
delaminatedsilicatelayersaredispersedina
polymermatrix,thuscompletelydisturbingthe
orderoftheclaylayers.

MechanicalProperties

MechanicalProperties

RoleofAspectRatioonProperties

OtherProperties
Apartfrommechanicalandpermeationproperties,other
propertiesattributedtopolymernanocompositesare:
improvedthermalresistance
improvedflameresistance
improvedmoistureresistance
improvedchargedissipation
improvedchemicalresistance

SizeEffects:SurfacetoVolume
RatioVersusShape

Propertiesoflargescaletraditionalmaterialsaredeterminedbythe
propertiesoftheirbulk,duetotherelativelysmallcontributionofasmall
surfacearea,however,fornanomaterials thissurfacetovolumeratiois
inverted.

ananomaterial'sshapeisofgreatinterest
becausevariousshapeswillproduce
distinctsurfacetovolumeratiosand
thereforedifferentproperties.
SphereA/V=3/r
CylinderA/V=2/r
CubeA/V=6/L

SizeEffects:SurfacetoVolume
RatioVersusShape
Howmuchofanincreaseinsurfaceareawillresultfromasphericalparticle
of10mdiametertobereducedtoagroupofparticleswithdiameterof10
nanometer,assumingthatthevolumeremainsconstant?