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SurfacemodificationofpureniobiumbyplasmanitridingC.Borcza,C.M.Lepienskib,S.F.Brunattoc,⁎aProgramadePós-GraduaçãoemEngenhariaMecânica(PG-Mec),UniversidadeFederaldoParaná(UFPR),81531-990,Curitiba,PR,Brazil

bDepartamentodeFísica,UniversidadeFederaldoParaná(UFPR),81531-990,Curitiba,PR,Brazil

cDepartamentodeEngenhariaMecânica,PlasmaAssistedManufacturingTechnology&PowderMetallurgyGroup,UniversidadeFederaldoParaná,81531-990,Curitiba,PR,Brazil

abstractarticleinfoArticlehistory:Received27November2012Acceptedinrevisedform10March2013Availableonline17March2013

Keywords:NiobiumPlasmanitridingPlasmaheatingSputtering

Plasmanitridingofpureniobiumwasinvestigatedusingadcsquarewaveformpulsedpowersupplyof5.0kW,aimingtochangethematerialsurfacecharacteristicsduetoheatingandphysical–chemicalreactionscausedbytheionsandfastneutralbombardmentduringthetreatment.Nitridingwasperformedfortemperaturesof500,750,915and1080°C,at90%N2+10%H2gasmixture,pressureof1200MPa(9Torr),at300sccmgasflowrateandnitridingtimeof7.2ks.CharacterizationofthesampleswascarriedoutbymeansofSEM,XRD,nanoindentationtechnique,scratchtestingandroughnessanalysis.Strongincreaseofthesurfacehardnesswasverified.Nanoindentationresultsindicatevaluesontheorderof2.5GPaforpureniobiuminthestartcon-dition(asnon-nitrided)andupto21GPaintheas-nitridedcondition.TheXRDpatternsshowthepresenceofε-NbNandβ-Nb2NhexagonalphasesinadditiontotheoriginalNbpeaks.Significantchangesonsurfacemor-

phologyandroughnessofthetreatedsampleswereobservedforthestudiedconditionsandarediscussedcon-sideringthesputteringandplasmaspeciesbombardmenteffect.©2013ElsevierB.V.Allrightsreserved.

1.IntroductionPlasmanitridingisathermochemicalsurfacetreatmentwidelyusedtotreatsteelsandalloys.Itisoneofthemostversatilenitridingprocesseswithmanyadvantagesovertheconventionalsalt-bathandgasnitriding[1].Itiswidelyusedinmanyindustrialapplications,aimingtoimprovespecificpropertiesofthetreatedsurfaces,suchaswearandfatigueresistance,surfacehardness,corrosionresistance,andreducedfriction.Ontheotherhand,nitridesandcarbidesoftransitionmetalsofgroupsIV,VandVIusuallyshowphysical–chemicalcharacteristicsofinterestinmechanicalfieldashighhardness,goodabrasionwearresis-tance,corrosionresistanceandexcellentthermalstability[2–4].Duetotheseaspects,suchmaterialsarepotentialcandidatestobeusedinspe-cialalloysascoatings,orevenasbasemetallicmaterialsforspecialap-plications,havingtheirsurfacesalteredbythermochemicaltreatments[5–10].DifferentfromverificationforMoandTibasemetalsandalloys[9–16],fewworkscomprisingplasmanitridingandtreatmentofniobi-umhavebeenpublishedinspecializedliterature[5,6,17–19].Aspresentedin[20],niobiumisarefractoryandductileb.c.c.(bodycenteredcubic)metal.Itdoesnottarnishoroxidizeatroomtempera-ture.Itsmechanicalpropertiesarehighlydependentofthecontentofinterstitialelements.Forinformationpurpose,highpurityannealedniobium(for100–200ppmofinterstitialcontaminantcontents)pre-sentshardnessof80HV,tensilestrengthof275MPa,yieldstrengthof207MPa,elasticmodulusof103GPa,andveryhighelongation

expressedin%,id.est,itsmaximumcold-workreductionbetweenan-nealsisvirtuallyunlimited[21].Initspurestate,itpromptlyoxidizesathightemperaturesinthepresenceofoxygen,but,whenconnectedwithnitrogenintheformofnitrides,markedimprovementinitsme-chanicalpropertiesandresistancetooxidationathightemperaturesisobserved[21,22].Specificallyregardingtheniobiumnitrides,itisapparentthatthesematerialsarechemicallyinerttomostoftheapplications.Duetothischaracteristic,theyhavebeenincreasinglystudiedandusedfordifferentapplicationscomprisingmicroelectron-ics,micromechanics,superconductivityandothers[19,23–26].Inthepresentwork,plasmanitridingofpureniobiumwasinvesti-gatedfordifferenttreatmenttemperaturesusingadcsquarewaveformpulsedpowersupplyof5.0kW,aimingtodeterminethechangesofthematerialsurfacecharacteristicsduetoheatingandphysical–chemicalreactionscausedbytheionsandfastneutralbombardmentduringtreatment.Specialattentionisgiventothecharacterizationofthetreat-edsurfacesbymeansofnanoindentationtechnique,scratchtesting,scanningelectronmicroscopy,androughnessanalysis,beingthatthechangesonsamplessurfacecharacteristicsarediscussedconsideringthesputteringmechanismandaspectsrelatedtothesurface–plasmainteraction.

2.ExperimentalprocedureSchematicrepresentationoftheplasmanitridingapparatusutilizedinthisworkispresentedinFig.1.Heatingofthesamplewasobtainedbyplasmaspecies(ionsandfastneutrals)bombardment.Theplasmaapparatusconsistedofadcpulsedpowersupplyandastainlesssteeldischargechamberof350mmindiameterand380mminheight,