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TribologyLaboratoryatLehighUniversity:

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TheTribology
LaboratoryatLehigh
University

Research
MaterialSystems
POLYMERS,POLYMERCOMPOSITESANDPOLYMERNANOCOMPOSITESFOR
TRIBOLOGICALAPPLICATIONS

OnematerialstudiedintheTribologyLaboratoryisultralowwear,lowfriction
hierarchicalandmultifunctionalnanocompositesbasedonPTFE(Teflonlowest
frictioncoefficientofanybulkpolymer)thatreduceitswearbymorethan10,000
timeswiththeinclusionofafewvolumepercentfiller.

Polytetrafluoroethyleneisauniqueandfascinatingmaterialthathasbeenclosely
studiedbyresearcherssinceitsaccidentaldiscoveryin1938[930].Itischemically
inert,vacuumcompatible,stableathightemperaturesandhasalowfriction
coefficient[9,10,12,14,15].PTFEconsistsofafullyfluorinatedsinglebondedcarbon
backbone(Fig.21).TheCFbondsareverystrongandservetoprotectthepolymer
fromchemicalattack.ThemolecularweightofPTFEcanbemorethan30,000,000.
ThestructureofPTFEleadstoitsnumerousadvantagesanddisadvantages.
PolytetrafluoroethyleneasaTribologicalMaterial
Intheearly1940s,PTFEwasreportedashavingafrictioncoefficientof0.1,thelowest
frictioncoefficientofanybulkpolymer[10].Inthe1950s,thisextremelylowfriction,
incombinationwithPTFEsotherpromisingproperties,promptedasparkofinterest
amongmanyresearchersinthetribologyandpolymercommunities[1114,3133].In
thesestudies,frictioncoefficientswerereportedbetween.04and0.4.Itwas
hypothesizedthatPTFEmakesathin,molecularlyalignedtransferfilmonthecounter
surfacethatitslidesagainst[34].Asaresult,therelativeslidingoccursataninterface
betweenPTFEandthePTFEtransferfilm,whichproducesalow,consistentfriction
coefficientforPTFEwhenpairedwithalargevarietyofcountersurfacematerials.
PooleyandTaborfoundthatthefrictioncoefficientofPTFEwaslowwhenslidingin
thedirectionoftheorientedPTFEmolecules,however,increasedsignificantlywhen
slidingperpendiculartothemolecularorientation[16,35].Fromthisobservationthey
concludedthatthelowfrictioninPTFEiscausedbyfullyfluorineencasedrigidchains
slidingoveroneanother.
PTFEdoessufferfromonemajordownfall:ahighwearrateaveragingaroundmuchas
1x104to1x103mm3/Nmundercommonengineeringslidingconditions[17,34,36].
ThishighwearratelimitstheuseofPTFEasabulksolidlubricant.Thehighwearrate
andthewearmechanismsofPTFEalsoleadstolarge,flakeyweardebris,whichcan
alsobeverydisadvantageous.
LowwearrateshavebeenobservedinPTFEatlowcontactpressuresandsliding
speeds[17,34].However,undertypicalengineeringslidingspeedsandloads,wear
ratesareoftenveryhighatasmuchas1x103mm3/Nm.Tanakamappedoutthewear
ofPTFEasafunctionoftemperatureandslidingspeed.Thistransitioninwearrate
suggestsathresholdbetweenmultiplewearmechanisms.Tanakaproposedthatthe
bandedstructure[14,15]ofPTFEisresponsibleforthislargescale,flakeyweardebris
andcomparedittoadeckofcards.Atlowerslidingspeedsandcontactpressures,the
wearofPTFEisextremelylow.

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Variationsofwearrateandcoefficientoffrictionwithspeedattemperaturesbelow
100CasreportedbyTanaka[17].ReprintedfromK.Tanaka,Y.Uchiyama,S.
Toyooka,Mechanismofwearofpolytetrafluoroethylene,Wear23(1973)153172.
ElsevierLimited,Oxford.
StudiesbyBlanchetandKennedysuggestadifferentsourceoftheflakeyweardebris.
Theysuggestthatathigherslidingspeeds,adelaminationwearisinitiatedduetothe
kineticfrictioncoefficientreachingathreshold[20].Atthisthreshold,subsurface
shearingofthepolymerbecomespreferentialastheshearstressattheinternal
interfacesofthePTFEbecomelowerthantheshearstressattheinterface.This
promotessubsurfacecrackpropagation,joining,anddelaminationwear[37].

SubsurfacecrackpropagationanddelaminationwearinPTFEasdescribedby
BlanchetandKennedy[20]
PolytetrafluoroethyleneComposites
PTFEisusedasbothamatrixandfillerincompositesfortribologicalapplications[17,
1923,2528,36,3863](Figure24).BothPTFEfilledcompositesandPTFEmatrix
compositeshaveextremesuccessstorieswithwearrateslessthan1x107mm3/Nm
[27,28,56,61](approximatelythreetofourordersofmagnitudelessthanbulkPTFE).
Asafiller,PTFEsprimarypurposeistoreducefriction,althoughitdoeshavethe
effectofreducingwear[28].Incontrast,whenfillersareaddedtoPTFEasamatrixto
reducethewear,thereisoftenanincreaseinfrictioncoefficient[61].

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Wearratevs.frictioncoefficientfortribologicalcompositesofPTFEandaseveral
othertribologicalengineeringpolymersfromseveralsources.APTFE2,BPI
[64],CPAI[64],DPEEK[64],EUHMWPE[64],FPET[64],G
PFA,HRulonGold1,IRulonMaroon2,JSP2112,KPTFE
Al2O31,LPTFEDGAl2O31,MTorlon4275,NTorlon43013,O
Torlon46302,PVictrexPEEK/PTFE1,QPTFEZnO[23],RPTFEcarbon
nanotube[52]
ConventionalFilledPolytetrafluoroethyleneComposites
AlmosteverythingimaginablehasbeenincludedasafillermaterialinPTFE.Most
fillersservetoreducewearwhileincreasingfriction.Fillersservetoreducethewearby
typicallyoneortwoordersofmagnitude.Severalhypothesisexistastowhyfillers
servetoreducethewearofPTFE[18,20,23,25,3841,52,61,6567].Preferential
loadsupport[39,68]andarrestingcrackpropagation[20,66]areamongthetwo
mostpopulartheories.FillersarrestsubsurfacecracksandpreventthePTFEfrom
delaminatingatthesurface.

Shuttingdownthesubsurfacecrackpropagationanddelaminationwearmechanism
inPTFE.Cracksarearrestedbyvariousfillersizesandgeometriesincluding1)
microparticles,2)fibers,3)nanoparticlesand4)Compositenetworksoffillerand
PTFEmatrix.
Traditionally,hardmicroandnanoparticlesandfibers/networksofglass,polymers
andothermaterialsandmetalsareusedasfillersinPTFE.BlanchetandKennedy
proposedthatfillersservetoshutdownthedelaminationwearofPTFE[45].Through
experimentswithhighdensityandlowdensitypolyethylene,Briscoeproposedthat
fillerspromotethegenerationofthin,welladheredtransferfilmsthatreducewearby
slowingtheremovalandsubsequentreplacementoftransferfilms[38].
WiththesefilledPTFEcomposites,thewearratescanbecommonlyreducedtoaround
1x105mm3/Nm(andaslowas1x106mm3/Nm).Insystemswherethewearrateis
closetothewearrateofPTFEatslowslidingconditions,theprimaryfunctionofthe
filleristoprovideloadsupport[39]andarrestsubsurfacecracksandhalt
delaminationwear[45].Asfillervolumeconcentrationsincrease,itispossiblethatthe
slidingisnolongeroccurringbetweenthePTFEandthecountersample,butis
occurringbetweenthefillerandthecountersample,thefillerandthetribofilm,the
sampleandthetribofilm,thesampleandthefillerorsomedynamiccombinationof
thesepossiblematerialinteractions.
Fornanoparticlefilledsystemsthatproducelowwearatlowfillerpercent,Lietal.
agreedwiththetheoryofBriscoethatthin,robust,welladheredtransferfilmsbondto
thecountersampleandprotectthesamplefromfurtherwear[23,38].Others
suggestedthatnanoparticlespreventthecrystallinestructureofthePTFEfrombeing
destroyedduringsliding[52].Tanaka,however,foundthatnanoparticlesthataretoo
smallarenolongerabletoadequatelypreventthelargescaledestructionofthe
bandedstructureofPTFEtosuccessfullyslowdownthewearofPTFE[39].
ManyPTFEcompositesshowsomeappreciableruninbehaviorinwhichtheinitial

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ManyPTFEcompositesshowsomeappreciableruninbehaviorinwhichtheinitial
wearrateishigherthanthatofthesteadystatewearrate.Thisruninsuggeststhereis
aninitialtransientprocessoccurringthatleadstolowerwearsystems.Itcouldbethat
enoughofthepolymermustbewornawaytogeneratesomecriticalamountoffillerat
thesurface.Itcouldalsobetheformationofawelladhered,protectivetransferfilm
thatthepolymerslidesoverthetransferfilm.
UltraLowWearPolytetrafluoroethyleneandAl2O3Nanocomposites

Wearratevs.fillervolumepercentforPTFEmatrixcomposites.Thefillersinclude
ZnO[23],carbonnanotubes(CNT)[52],DGAl2O3[25],andirradiatedFEP[47].
Somefillermaterialsprovidearemarkablereductioninwear(over1000xincreasein
wearresistance)atverylowvolumepercent(lessthan2).Alphaphasedaluminaisone
ofthosefillers.Atlowloadingfractionsitisbetterthansomeoftheothercomposites
byseveralordersofmagnitude.Thesematerialsrelyonnewmechanismsfortheir
ultralowwearperformance.Throughenvironmentalstudies,weshowedthatthereisa
tribochemicalmechanismresponsibleforthisultralowwearbehavior.

B.A.Krick,J.J.Ewin,G.S.Blackman,C.P.JunkandW.G.Sawyer,UnpublishedPTFE
andcomposites,(2011).
A.BennettandW.G.Sawyer,Unpublishedpolymerweartesting,(2011).
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4.Stachowiak,G.W.andA.W.Batchelor,Engineeringtribology.2005,Oxford:
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5.Williams,J.A.,Engineeringtribology.1994,Oxford:OxfordUniversityPress,Inc.

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5.Williams,J.A.,Engineeringtribology.1994,Oxford:OxfordUniversityPress,Inc.
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polytetrafluoroethylene.Journalofpolymerscience,1958.28(117):p.365376.
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polytetrafluoroethylene.JournalofAppliedPhysics,1962.33(5):p.1871&.
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19.Gong,D.L.,Q.J.Xue,andH.L.Wang,ESCAstudyontribochemicalcharacteristics
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polytetrafluoroethylene(PTFE)andPTFEcomposites.Wear,1992.153(1):p.229
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irradiation.LubricationEngineering,1996.52(6):p.489495.
22.Zhang,Z.Z.,etal.,Frictionandwearcharacteristicsofmetalsulfidesand
graphitefilledPTFEcompositesunderdryandoillubricatedconditions.Journalof
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23.Li,F.,etal.,ThefrictionandwearcharacteristicsofnanometerZnOfilled
polytetrafluoroethylene.Wear,2001.249(1011):p.877882.
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pressuredependenceoftheroomtemperaturetransitioninPTFE.POLYMER,2003.
44(3):p.783791.
25.Sawyer,W.G.,etal.,AstudyonthefrictionandwearbehaviorofPTFEfilledwith
aluminananoparticles.Wear,2003.254(56):p.573580.
26.McCook,N.L.,etal.,WearresistantsolidlubricantcoatingmadefromPTFEand
epoxy.TribologyLetters,2005.18(1):p.119124.
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nanocompositeswithirregularshapednanoparticles.Wear,2006.260(78):p.915
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composite.Wear,2006.261(34):p.410418.
29.Burris,D.L.,S.S.Perry,andW.G.Sawyer,Macroscopicevidenceofthermally
activatedfrictionwithpolytetrafluoroethylene.TribologyLetters,2007.27(3):p.
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30.Burris,D.L.,Investigationofthetribologicalbehaviorofpolytetrafluoroethylene
atcryogenictemperatures.Tribology&LubricationTechnology,2008.64(5):p.40
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andthefrictionofplastics.ProceedingsofthePhysicalSocietyofLondonSectionB,
1953.66(405):p.728736.
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frictionofteflononteflon.Nature,1955.175(4459):p.682682.
33.Flom,D.G.,Noteonthewearofteflonslidingonteflon.JournalofApplied
Physics,1957.28(11):p.13611362.
34.Makinson,K.R.andD.Tabor,Frictionandtransferofpolytetrafluoroethylene.
Nature,1964.201(491):p.464&.
35.Pooley,C.M.andD.Tabor,Frictionandmolecularstructure:thebehaviourof
somethermoplastics.ProceedingsoftheRoyalSocietyofLondon.SeriesA,
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onthetribologicalbehaviorofPTFEandselectedPTFEbasedselflubricating
composites.TribologyTransactions,1991.34(3):p.327334.
37.Suh,N.P.,Thedelaminationtheoryofwear.Wear,1973.25(1):p.111124.
38.Briscoe,B.J.,A.K.Pogosian,andD.Tabor,Thefrictionandwearofhighdensity
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polytetrafluoroethylenebasedcomposites.Wear,1982.79(2):p.221234.
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polytetrafluoroethylene.Wear,1989.134(2):p.283295.
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tribologicalbehaviorofpolymers.Wear,1992.158(12):p.4159.
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filledPTFEmicroandnanocomposites.TribologyTransactions,2008.51(3):p.247
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News
ExperimentsbackfromtheInternationalSpace
Station
SPACETRIBOMETERSANDSAMPLESBACKFOR
ANALYSIS

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MaterialsontheInternationalSpaceStation
Experiments(MISSE)SpaceTribometerswerethe
firsteveractivetribometersdirectlyexposedtothe
LowEarthOrbitEnvironment

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