012Influence of granular carbons on the pyrolysis behaviour of coal tar pitches

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JournalofAnalyticalandAppliedPyrolysis58–59(2001)825–840

Influenceofgranularcarbonsonthepyrolysisbehaviourofcoal-tarpitches

A.Me´ndez,R.Santamarı´a,R.Mene´ndez*,J.BermejoInstitutoNacionaldelCarbo´n,INCAR,CSIC,LaCorredorias/n,Apartado73,33080O6iedo,Spain

AbstractThepyrolysisbehaviourofpitchesdependsontheirchemicalcompositionwhichinturndependsontheprocessingconditionsusedintheirpreparation.Whenusedasaprecursorofcarbonmatrixcomposites,pitchesareveryoftenpre-treated(air-blowing,thermaltreatment)toimprovetheirpropertiesandconsequentlythoseofthefinalmaterial.Thepyrolysisbehaviouroftreatedpitchescanbeverydifferenttothatoftheparentpitches,anditcanalsovarywhenmixedwithdifferenttypesofcarbonsforthepreparationofcomposites.Thisworkdealswiththepyrolysisbehaviouroffourpitchesofverydifferentcharacteristics(acommercialimpregnatingpitch,anair-blownpitchandtwopitchesobtainedbythermaltreatment)whentheyaremixedwithfourgranularcarbons(anthracite,petroleumcoke,foundrycokeandgraphite).Thethermalanalysis(TG/DTGandDSC)ofpitchesandpitch/carbonsystems,opticalmicroscopyandthetolueneinsolublecontentoftheirpyrolysisproductsareusedtomonitorpossibleinteractionsbetweenthetwocomponentsduringpyrolysis.©2001ElsevierScienceB.V.Allrightsreserved.

Keywords:Coal-tarpitch;Treatedpitch;Granularcarbon;Pyrolysis

www.elsevier.com/locate/jaap1.IntroductionCarboncompositeshaveanimportantapplicationinbrakesystemsduetotheiruniquepropertiessuchasalowcoefficientofthermalexpansion,highheatcapacity,goodthermalshockresistance,lowweightandexceptionalwearrates[1].However,thehighcostofthesematerials,mainlyderivedfromacomplexmanufac-turingprocess,restrictstheirusetocriticalapplicationswherenoothermaterials

*Correspondingauthor.Fax:+34-98-5297662.E-mailaddress:rosmenen@incar.csic.es(R.Mene´ndez).

0165-2370/01/$-seefrontmatter©2001ElsevierScienceB.V.Allrightsreserved.PII:S0165-2370(00)00168-6826A.Me´ndezetal./J.Anal.Appl.Pyrolysis58–59(2001)825–840aresuitablei.e.racingcars,aeronautics,militaryindustry.Theutilisationofmoresimpletechnologiesandcheaperprecursorscouldreducethecostofcarboncompositesandmakethemcompetitiveinconventionalapplications.Granularcarbonscouldbeanalternativetocarbonfibres(asreinforcingmaterial),whennoextremespecificationsarerequired,becauseofthewiderangeofproductsofdifferentcharacteristicsthatcouldbeproducedandtheirlowerprice[2].Moreover,coal-tarpitcheshaveproventobeexcellentcandidatesascarbonmatrixprecursorsduetotheirabilitytogenerategraphitisablecarbonsandtheirrelativelyhighcarbonyieldonpyrolysis[3].Pitchesarecomplexmixturesofmanydifferentaromaticcompoundsthatundergoseveretransformationonpyrolysis,throughpolymerisation,dehydrogena-tionandcyclationreactions[4].Themostimportanteventduringpitchpyrolysis,fromthepointofviewofthestructureandpropertiesofthefinalcarbonmaterial,istheformationofaliquidcrystalphasei.e.thesocalledmesophase[5].Aseriousproblemwhenusingofcommercialpitchesasamatrixprecursoristhedevelopmentofporosityduringpyrolysisduetothereleaseofvolatiles.Pitchcarbonyieldcanbeimprovedandconsequentlytheporosityofthecarbonmaterialreducedbypre-treatmentssuchasair-blowingandthermaltreatment[6,7].Thesetreatmentscausethepolymerisationandcondensationofthepitchcomponentsincreasingtheirmolecularweight.Pitchesshowdifferentcompositionsdependingonthetreatmentapplied.Consequentlytheirpyrolysisbehaviourcanvaryleadingtocokeswithadifferentmicrostructure[8].Theopticaltextureofthematrixanditsinteractionwiththecarbonsubstrate(fillerorreinforcement)playanimportantroleinthepropertiesofthecomposite.Theaimofthisworkistoinvestigatethethermalbehaviourofvariouspitchesindifferentpitch–fillersystems.Toachievethis,coke,anthraciteandgraphitewereusedasfillers,withfourcoal-tarpitches(acommercialimpregnatingpitch,anair-blownpitchandtwothermallytreatedpitches).Thebehaviourofthemixtures(pitch/granularcarbon)onpyrolysiswasmonitoredbydifferentialscanningcalorimetry(DSC)andthermogravimetricanalysis(TGAandDTG).Opticalmicroscopic(OM)examinationofthepyrolysisproductsofthemixturesandtheevolutionoftheirtolueneinsolublecontent(TI),asameasureofthepolymerisationofpitchcomponents,wasalsocarriedout.

2.Experimental2.1.Rawmaterials

Acommercialimpregnatingcoal-tarpitch(IndustrialQuı´micadelNalo´n,SA)wasusedasrawmaterial.Anewpitch(G18)waspreparedbyair-blowingofthecommercialpitch,andtwootherpitches(D3andD5)bythermaltreatment.Air-blowingwascarriedouton1500gofparentpitchina2-lstainlesssteelreactor,at275°C,underanairflowof40lh−1andmaintainedfor18hundercontinuous