BiographySheＧmingJIANGDoctorProfessor　EＧmailjiangsheming２６３1049008net　ReceivedDateSeptember６２０１３

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JOURNALOFIRONANDSTEELRESEARCHINTERNATIONAL1049008２０１４２１(１１)１０５９Ｇ１０６４10512731051273105127310512731051273105127310512731051273105127310512731051273105127310512731051273105127310512731051273105127310512731051273105127310512731051273105127310512731051273105127310512731051273105127310512731051273105127310512731051273105127310512731051273105127310512731051273105127310512731051273105127310512731051273105127310512731051273105127310512731051273105127310512731051273105127310512731051273105127310512731051273105127310512731051273105127310512731051273

InfluenceofOxideMorphologiesonGalvanizabilityofThirdGenerationAutomotiveSteel

SheＧmingJIANG１　ShiＧjieFENG１２　XunＧhuaYUAN１　YuanＧpengLI１ZhenＧhuaLI２　QiＧfuZHANG１

(１NationalEngineeringLaboratoryofAdvancedCoatingTechnologyforMetalMaterialsCentralIronandSteelResearchInstituteBeijing１０００８１China　２FacultyofMaterialScienceandEngineeringKunmingUniversityofScienceandTechnologyKunming６５００９３YunnanChina)

AbstractFocusingonimprovingthegalvanizabilityofthethirdgenerationautomotivesteeltheeffectofsurfaceoxＧidemorphologiesonthegalvanizabilitywasstudiedTheresultsshowthatthesurfaceoxidetypesofsamplesteelsbyXＧrayphotoelectronspectroscopy(XPS)analysisafterannealingindifferentconditionsarethesameOnlyMnOMnO２andCr２O３weredetectedandnocomplexoxideexistsonthesurfaceMorphologiesofsurfaceoxidescangreatＧlyinfluencethegalvanizabilityofthethirdgenerationautomotivesteelNoduleＧlikeoxidesurfacecancontributetobetterwettabilityandinhibitionlayerthanvitreousfilmＧlikeoxidesurfaceGalvanizedpanelsofnoduleＧlikeoxidesurＧfacesteelsonlyshowpinholeＧsizedbarespotswhilepanelsgalvanizedfromvitreousfilmＧlikeoxidesurfacesteelsreＧveallargerareasofbarespotsanduncoatedareasInhibitionlayerobservedingalvanizedpanelsofnoduleＧlikeoxidesurfacesteelsiscompactbutnothomogeneoussomeinhibitionlayergrainsarefineandothersarecoarsewhiletheinhibitionlayergrainsofpanelsgalvanizedfromvitreousfilmＧlikeoxidesurfacesteelshaveanonＧcompactmorＧphologywithsomeparticularlyfineequiaxedcrystalswhichdevelopeddeficientlyKeywordsgalvanizingthirdgenerationautomotivesteeloxidemorphologygalvanizability

　　HighstrengthsteelsarecurrentlythesubjectofintenseinterestoftheautomotiveindustrywiththeobjectofimprovinglightweightperformancethefuelefficiencyandthecrushresistancethushigherrequirementsfortheautomotivesteelsareputforＧwardleadingtothedevelopmentofautomotivesteelsAccordingtoRmtimesA (theproductoftensilestrengthandelongation)interstitialfree(IF)dualphase(DP)transformationＧinducedplasticity(TRIP)andmartensitic(MART)steelsarenamedasthefirstgenerationautomotivesteelswhoseRmtimesAare１０－２０GPa1048944butthelowRmtimesAcannotsatisfythereＧquirementsofbothlightweightandhighsafetyinthefuturedevelopmentoftheautomotiveindustryThesecond generation automotivesteelsincludeaustenitic steels and twinningＧinduced plasticity(TWIP)steelswhoseRmtimesAare５０－７０GPa1048944BecauseofthehighcontentsofalloyingelementssuchasCrNiMnSiandAlthesecondgeneraＧtionautomotivesteelsareusuallyofhighcostand

poortechnologyperformancesForthesakeofsavＧingresourcesreducingcostslightweightandimproＧvingthesafetyoftheautomobilesteelsthethirdgenＧerationautomotivesteelshavebeendevelopedwithlowcostandhighRmtimesA[１２]InordertobeappliedinautomotiveproductionthethirdgenerationautoＧmotivesteelsmusthaveagoodcorrosionresistanceandhotＧdipgalvanizingisthemosteconomicalandeffectivemethodtoachievethisobjective　　ItiswellknownthatalloyingelementssuchasMnCrandSicanbeselectivelyoxidizedduringanＧnealing[３－５]Theselectiveoxidationofthesealloyingelementshasadetrimentaleffectonthereactivewettingofthesteelsurfaceduringgalvanizingandresultsinbarespotdefects[６]whilethestripgalvaＧnizingbehaviorcanbedirectlyrelatedtotheamountofexternaloxidationandthesurfaceoxidemorpholＧogies[７８]Inordertoimprovethegalvanizabilityofthethirdgenerationautomotivesteelitisnecessarytoinvestigatetheeffectofoxidemorphologiesonthe

wettingbehaviorSointhepresentworktheinfluＧenceofoxidemorphologiesonthegalvanizabilityofthethirdgenerationautomotivesteelwasstudied

１　ExperimentalMaterialandMethod　　ThestudywascarriedoutusingthethirdgenＧerationautomotivesteelsuppliedby CentralIronandSteelResearchInstitute(CISRI)ThechemicalcompositionoftheteststeelsisgiveninTable１Allsteelsweresuppliedintheform offullＧhardcoldsheetandwereshearedintospecimenswiththediＧmensionsof２２０mmtimes１２０mmtimes１1049008８mm

Table１　Chemicalcompositionoftheteststeels　 mass

C Si Mn P S Cr Fe

０1049008０９６ ０1049008０２３ ４1049008５０ ０1049008００９１ ０1049008００２１ ０1049008０４６ Balance

　　AnnealingandhotＧdippingtrialswereperformedinaCAGＧ２０１０hotＧdipsimulatormanufacturedbyCISRIFig1049008１showstheschematicdiagramofthecontinuousannealingandgalvanizingprocessforthesteelsinhotＧdip galvanizing simulatorAllsamples wereheatＧtreatedbyheatingto６７５ataheatingrateof１２sandsoakingfor１８０sAftersoakingthesampleswerecooleddownattherateof１５ stodippingtemperaturewhichis４８０foreachsamＧpleAllsamplesweredippedinbathfor３sthencooledinairtoroomtemperatureThezincbathcontained０1049008２massdissolvedAlandwassaturatedwithironSample１wasannealedunderconditionsofaN２Ｇ５H２atmospherewithdewpointof－３０andsample２wasannealedunderconditionsofaN２Ｇ３H２atmospherewithdewpointof０　　ToobservethesteelcoatinginterfacethetopcoＧ

Fig1049008１　SchematicofcontinuousannealingandgalvanizingprocessforsteelsinhotＧdipgalvanizingsimulator

ating layer was removed by fuming nitric acid(HNO３)and１０ H２SO４FumingHNO３and１０H２SO４allowremovingonlyZn(η)ＧmixcrystalbutdoesnotattackFe２Al５andFeＧZnphase　　Scanningelectronmicroscopy (SEM)analysiswasperformedusinganFEIQuantaFEG６５０toobＧservethesurfaceoxidemorphologiesafterannealingandinterfaceFe２Al５ofallsamples　 　 XＧrayphotoelectron microscopy (XPS)wasperformedtoidentifytheoxidesonthesurfacesoftheannealedsteelsamplesXPSanalysiswasperＧformedusingaPHIＧ５３００ESCAXPSwithanAlKαXＧraysource(１４８６1049008６eV)Thespotsizeusedwas１００μmandthetakeoffanglewas４５degThebindingenergyvaluesobtainedusingtheXPSwereaccuratewithinplusmn０1049008４eV

２　Results２1049008１　Surfaceoxidemorphologiesoftheannealedsteels　　Fig1049008２showsmorphologiesofsurfaceoxidesonthesteelsamplesafterannealingindifferentatmosＧ

(a)Dewpointof－３０N２Ｇ５H２atmosphere　 (b)Dewpointof０N２Ｇ３H２atmosphereFig1049008２　Morphologiesofsurfaceoxidesonthesteelsamplesafterannealingunderdifferentconditions

０６０１ 　　　　JournalofIronandSteelResearchInternational　　　　　　　　　　　　　　Vol1049008２１　

phereAsshowninFig1049008２(a)afterannealingatdewpointof－３０ inN２Ｇ５H２atmospheretheunＧcoatedsamplesurfaceiscoveredbylotsofnoduleＧlikeoxidesbuttherearestillmostbaresubstrateHoweverthesurfaceofsample２annealedatdewpointof０ in N２Ｇ３ H２ atmosphereiscoveredwithalayerofvitreousfilmＧlikeoxide　　InordertoclarifythechemicalelementsofthesurfaceoxidesandbindingstatewithoxygenaddiＧtionalXPSanalysiswasperformedInXPSanalysisonlythecharacteristicpeaksofMnCrandOweredetectedFig1049008３showstheMnandCrXPSnarrowspectraofsamples１and２obtainedfromthesurfaceoxidesXPSspectraofMn(Fig1049008３(a))ofsample１

showthatoxidizedMnispresentinformoftwodifferＧentcomponentsOnecomponenthasthe Mn２p３２peakat６４０1049008８eVandthesecondpeakisat６４２1049008２eVcorrespondingtoMninMnOandMnO２respectively　　Maximumintensity(Fig1049008３(b))oftheCr２p３２peakofsample１isat５７６1049008５eVindicatingthepresＧenceofCr２O３XPSspectraofMn (Fig1049008３(c))ofsample２showthatoxidized MnisalsopresentinformoftwodifferentcomponentsOnecomponenthastheMn２p３２peakat６４１1049008５eVandthesecondpeakisat６４３1049008４eVcorrespondingtoMnin MnOandMnO２respectivelyMaximumintensity(Fig1049008３(d))oftheCr２p３２peakofsample２isat５７６1049008５eVindicatingthepresenceofCr２O３

(a)Mn２pofsample１　 (b)Cr２pofsample１　 (c)Mn２pofsample２　 (d)Cr２pofsample２Fig1049008３　XPSspectraofthesurfaceoxidesonthesamplesafterannealingunderdifferentannealingconditions

２1049008２　Appearancesofthegalvanizingpanels　　Fig1049008４showstheappearanceofthesamplepanＧ

elsgalvanizedinZnbathafterannealingunderdifＧferentannealingconditionswhichrevealsthatbare

(a)Dewpointof－３０N２Ｇ５H２atmosphere　 (b)Dewpointof０N２Ｇ３H２atmosphereFig1049008４　AppearanceofthesamplepanelsgalvanizedinZnbathafterannealingunderdifferentannealingconditions

１６０１Issue１１　　　　InfluenceofOxideMorphologiesonGalvanizabilityofThirdGenerationAutomotiveSteel　

spotsanduncoatedareasoccurredinallsamplesbutthebarespotsanduncoatedareasareobviouslylessinsample１annealedatdewpointof－３０inN２Ｇ５H２atmospherethansample２whichwasanＧnealedatdewpointof０inN２Ｇ３H２atmosphere

２1049008３　Morphologiesofinhibitionlayer　 　 The morphologiesofinhibitionlayerdeterＧminedbySEMareshowninFig1049008５forsamplesanＧ

nealedindifferentannealingconditionsItcanbeseenthattheinhibitionlayerofsample１annealedatdewpointof －３０ in N２Ｇ５H２ atmosphereiscompactbutnothomogenouswhereastheinhibiＧtionlayerformedinsample２annealedatdewpointof０inN２Ｇ３H２atmospherehasanonＧcompactmorphology withsomeparticularlyfineequiaxedcrystalsItisobviousthatthegrainsinsample２deＧvelopeddeficiently

(a)Dewpointof－３０N２Ｇ５H２atmosphere　 (b)Dewpointof０N２Ｇ３H２atmosphereFig1049008５　Morphologiesofinhibitionlayerofthesamplesgalvanizedafterannealingunderdifferentannealingconditions

２1049008４　MorphologiesofFeＧZnphase　　TheFeＧZnphasesonthegalvanizedpanelswere

exposedbystrippingthezincoverlayusing１０H２SO４AsshowninFig1049008６allhotＧdipcoatingplate

(a)Dewpointof－３０N２Ｇ５H２atmosphere　 (b)Dewpointof０N２Ｇ３H２atmosphereFig1049008６　MorphologiesofFeＧZnphasesofthesamplesgalvanizedafterannealingunderdifferentannealingconditions

specimenshaveinterfacegenerationofζphase

３　Discussion　　FornoduleＧlikeoxidesurfaceofsample１anＧnealedatdewpointof－３０inN２Ｇ５H２atmosＧpheretherearelotsofoxidenodulesandbaresubＧ

stratebuttheoxidedensitydistributionisnotuniＧformInsomeregionsoxidenodulesgathertogethＧertoformoxideaggregationandthesizeofoxidenodulesrangesfrom１００to２００nmWithregardtovitreousfilmＧlikeoxidesurfaceofsample２annealedatdewpointof０ inN２Ｇ３H２atmospherethe

２６０１ 　　　　JournalofIronandSteelResearchInternational　　　　　　　　　　　　　　Vol1049008２１　

oxidelayerappearstobecontinuousandvitreousItisthedifferenceofoxygenpotentialthatleadstodifＧferentsurfacemorphologies[９－１１]　　Thesurfaceoxidetypesofsamples１and２byXPSanalysisarethesameandonly MnOMnO２

andCr２O３ weredetectedandnocomplexoxideexＧistsonthesurface　　Fig1049008４showstheappearanceofthesamplepanＧelsgalvanizedinbathSample１onlyshowspinholeＧsizedbarespotsandisobviouslybetterreactivelywettedthansample２whichrevealslargerareasofbarespotsanduncoatedareasThesecoatingdefectsoccurduetotheappearanceofnonＧwettableexternalMnOxlayer[１２]MnOx onthesteelsurfacecouldbeinＧsitureducedbythebathdissolvedAlButifMncontentinthesteelishighenoughandtheformedMnOxareingreatnumberthereductionofMnOx

willbedifficultandcannotbedeoxidizedcompleteＧly[１１１３]SurfacemorphologieswerefoundtostrongＧlyaffectsteelgalvanizability[１４]WhengalvanizingsteelsitisverylikelythatthesurfaceoxidescanbeliftedoffthroughtheFedissolutionfromthesubＧstrateandnoduleＧlikeoxidesshouldbeliftedoffmorereadilythanvitreousfilmＧlikeoxides[１４]BellＧhouse[６]everindicatedthatreactivewettingoccurredbytwo methodswhengalvanizinghigh AlＧlow SiTRIPsteelsreductionofMnObythedissolvedAlintheZn(AlFe)bathandbyZnbridgingoftheoxＧideparticlesThemechanism wasdependentonthesurfacestructurepriortogalvanizingIftheoxidecoversthesurfaceofsteelthebridgingeffectwillnothappen[６]VitreousfilmＧlikeoxidecanhamperthediffusionofzincandaluminumwhichisnecessaryforthemtoreactwithmetalliciron[１５]andresultsinbarespot　　OnthebasisoftheabovedescriptionthereacＧtivewettingisstronglylinkedtothemorphologiesofsurfaceoxidesandnoduleＧlikeoxidesurfacecanbemoreadvantageoustogalvanizingthanvitreousfilmＧlikeoxidesurface　　TwokindsofinhibitionlayergrainswereobＧservedAsshowninFig1049008５(a)someregionsarefineandothersarecoarseAsshowninFig1049008２(a)inadditiontooxideparticlesthereis mostbaresubstrateThebaresubstratecancreateacleansteelsurfacefornucleationofFeＧAlphaseandtheFeＧAlnucleatesinagreatnumberleadingtotheformaＧtionoffineFeＧAlinhibitionlayergrainThenoduleＧlikeoxidecanbethermodynamicallyreducedbythebathAlbecauseofaveryshortgalvanizingtimeof３sTherewasalimittothesizeofoxidesthatcouldbe

completelyreducedIntheprocessofhotdipgalvaniＧzingbigoxideparticlesexistedinthesteelsurfaceandtheFeＧAlgrainscouldonlynucleateoncleanspotsbetweenbigoxidesThustheformedFeＧAlgrainswerescatteredandsparseInadditionbeＧcausetheamountofnucleationsiteswasloweredforperunitareathedissolvedAlwassufficientforthegrowthofFeＧAlgrainsintobiggerones[１３]　　TheinhibitionlayerformedinFig1049008５(b)hasanonＧcompactmorphologywithsomeparticularlyfineequiaxedcrystalsItisobviousthatthegrainsweredevelopeddeficientlyVitreousfilmＧlikeoxidescouldhamperthediffusionofFeandAltoreactwitheachothertoforminhibitionlayerandthusinfluencethereactivewetting　　AsseenfromFig1049008６allsamplepanelshaveinＧterfacegenerationofζphaseInadditiontothealuＧminothermicreductionofmanganeseoxidesthatledtothedecreaseofAlcontentinzincbathandcausedtheformationofζ phase[６１６]Blumenauetal1049008[１７]

explainedthegrowthofFeＧZnphasewithanalterＧnativemechanismAstheFeＧZnphaseisformedduetoAldepletionatthesteelＧzincinterfaceareactionhastooccurconsumingtheAlpresentatthisposiＧtionThehighaffinityofMnandAlcanleadtotheformationofMnＧAlphaseInthisworkBlumenauetalassumedthatAldidnotreduceanymanganeseoxidesandnoaluminothermicreductionoccurredbutMnwasdissolvedoutofthesteelsurfaceintothezincbathandaMnＧAlcompoundwasformedviathereＧactionofMnZn＋６AlZnrarrMnAl６uarr[１７－１９]　　BecauseofthehighcontentofMninthethirdgenerationautomotivesteelwhetherthetheoryproposedbyBlumenauetaltookeffectornotinthisexperimentalsoneedstobefurtherconfirmed

４　Conclusion　　MorphologiesofsurfaceoxidescangreatlyinＧfluencethegalvanizabilityofthethirdgenerationauＧtomotivesteelNoduleＧlikeoxidesurfaceshowbetＧter wettabilityandinhibitionlayerthan vitreousfilmＧlikeoxidesurfaceGalvanizedpanelsofnoduleＧlikeoxidesurfacesteelsonlyshowpinholeＧsizedbarespotswhilepanelsgalvanizedfrom vitreousfilmＧlikeoxidesurfacesteelsreveallargerareasofbarespotsanduncoatedareasInhibitionlayergrainsobＧservedingalvanizedpanelsofnoduleＧlikeoxidessurＧfacesteelsarecompactandcomposedoftwokindsofinhibitionlayergrainssomeregionsarefineandothersarecoarsebuttheinhibitionlayergrainsofpanelsgalvanizedfromvitreousfilmＧlikeoxidesurＧ

３６０１Issue１１　　　　InfluenceofOxideMorphologiesonGalvanizabilityofThirdGenerationAutomotiveSteel　

facesteelshaveanonＧcompact morphology withsomeparticularlyfineequiaxedcrystalswhicharedevelopeddeficiently

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[１]　W1049008QCaoCWangC1049008YWangJShiM1049008QWangHDongY1049008QWengSciChinaTechSci５５(２０１２)１８１４Ｇ１８２２

[２]　HDongW1049008QCaoJShiC1049008YWangM1049008QWangY1049008QWengIronandSteel４６(２０１１)No1049008６１Ｇ１１

[３]　IOlefjordWLeijonUJelvestamApplSurfaceSci６(１９８０)２４１Ｇ２５５

[４]　H1049008JGrabkeVLeroyHViefhausISIJInt３５(１９９５)９５Ｇ１１３

[５]　PDrilletZZermoutDBouleauJMataigneSClaessensRevMetall１０１(２００４)８３１Ｇ８３７

[６]　E1049008MBellhouseJ1049008RMcDermidMaterSciEngA４９１(２００８)３９Ｇ４６

[７]　JMakiJMahieuB1049008CDeCoomanSClaessensMaterSciTechnol１９(２００３)１２５Ｇ１３１

[８]　LBordignonJCrahayinGalvatechprime０１BrusselsBelgium２００１pp５７３Ｇ５８０

[９]　 MNordenMBlumenauTWuttkeK1049008JPetersApplSurfSci２７１(２０１３)１９Ｇ３１

[１０]　MBlumenauABarnoushIThomasHHofmannHVehoffSurfCoatTechnol２０６(２０１１)５４２Ｇ５５２

[１１]　SAlibeigiRKavithaR1049008JMeguerianJ1049008RMcDermidActaMater５９(２０１１)３５３７Ｇ３５４９

[１２]　MBlumenauMNordenFFriedelKPetersSurfCoatTechnol２０６(２０１１)５５９Ｇ５６７

[１３]　YLiSJiangXYuanBChenQZhangSurfInterfaceAnal４４(２０１２)４７２Ｇ４７７

[１４]　NGaoD1049008Y1049008HLiuN1049008YTangR1049008BParkM1049008SKiminGalvatechprime１１AssociazioneItalianadiMetallurgiaGenoＧvaItaly２０１１pp１２３Ｇ１３０

[１５]　X1049008VEyndeJ1049008PServaisMLamberigtsinGalvatechprime２００４AISTChicagoUSApp３６１Ｇ３７２

[１６]　E1049008MBellhouseA1049008I1049008MMertensJ1049008RMcDermidMaterSciEngA４６３(２００７)１４７Ｇ１５６

[１７]　MBlumenauMNordenFFriedelKPetersSurfCoatTechnol２０５(２０１１)３３１９Ｇ３３２７

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４６０１ 　　　　JournalofIronandSteelResearchInternational　　　　　　　　　　　　　　Vol1049008２１　

wettingbehaviorSointhepresentworktheinfluＧenceofoxidemorphologiesonthegalvanizabilityofthethirdgenerationautomotivesteelwasstudied

１　ExperimentalMaterialandMethod　　ThestudywascarriedoutusingthethirdgenＧerationautomotivesteelsuppliedby CentralIronandSteelResearchInstitute(CISRI)ThechemicalcompositionoftheteststeelsisgiveninTable１Allsteelsweresuppliedintheform offullＧhardcoldsheetandwereshearedintospecimenswiththediＧmensionsof２２０mmtimes１２０mmtimes１1049008８mm

Table１　Chemicalcompositionoftheteststeels　 mass

C Si Mn P S Cr Fe

０1049008０９６ ０1049008０２３ ４1049008５０ ０1049008００９１ ０1049008００２１ ０1049008０４６ Balance

　　AnnealingandhotＧdippingtrialswereperformedinaCAGＧ２０１０hotＧdipsimulatormanufacturedbyCISRIFig1049008１showstheschematicdiagramofthecontinuousannealingandgalvanizingprocessforthesteelsinhotＧdip galvanizing simulatorAllsamples wereheatＧtreatedbyheatingto６７５ataheatingrateof１２sandsoakingfor１８０sAftersoakingthesampleswerecooleddownattherateof１５ stodippingtemperaturewhichis４８０foreachsamＧpleAllsamplesweredippedinbathfor３sthencooledinairtoroomtemperatureThezincbathcontained０1049008２massdissolvedAlandwassaturatedwithironSample１wasannealedunderconditionsofaN２Ｇ５H２atmospherewithdewpointof－３０andsample２wasannealedunderconditionsofaN２Ｇ３H２atmospherewithdewpointof０　　ToobservethesteelcoatinginterfacethetopcoＧ

Fig1049008１　SchematicofcontinuousannealingandgalvanizingprocessforsteelsinhotＧdipgalvanizingsimulator

ating layer was removed by fuming nitric acid(HNO３)and１０ H２SO４FumingHNO３and１０H２SO４allowremovingonlyZn(η)ＧmixcrystalbutdoesnotattackFe２Al５andFeＧZnphase　　Scanningelectronmicroscopy (SEM)analysiswasperformedusinganFEIQuantaFEG６５０toobＧservethesurfaceoxidemorphologiesafterannealingandinterfaceFe２Al５ofallsamples　 　 XＧrayphotoelectron microscopy (XPS)wasperformedtoidentifytheoxidesonthesurfacesoftheannealedsteelsamplesXPSanalysiswasperＧformedusingaPHIＧ５３００ESCAXPSwithanAlKαXＧraysource(１４８６1049008６eV)Thespotsizeusedwas１００μmandthetakeoffanglewas４５degThebindingenergyvaluesobtainedusingtheXPSwereaccuratewithinplusmn０1049008４eV

２　Results２1049008１　Surfaceoxidemorphologiesoftheannealedsteels　　Fig1049008２showsmorphologiesofsurfaceoxidesonthesteelsamplesafterannealingindifferentatmosＧ

(a)Dewpointof－３０N２Ｇ５H２atmosphere　 (b)Dewpointof０N２Ｇ３H２atmosphereFig1049008２　Morphologiesofsurfaceoxidesonthesteelsamplesafterannealingunderdifferentconditions

０６０１ 　　　　JournalofIronandSteelResearchInternational　　　　　　　　　　　　　　Vol1049008２１　

phereAsshowninFig1049008２(a)afterannealingatdewpointof－３０ inN２Ｇ５H２atmospheretheunＧcoatedsamplesurfaceiscoveredbylotsofnoduleＧlikeoxidesbuttherearestillmostbaresubstrateHoweverthesurfaceofsample２annealedatdewpointof０ in N２Ｇ３ H２ atmosphereiscoveredwithalayerofvitreousfilmＧlikeoxide　　InordertoclarifythechemicalelementsofthesurfaceoxidesandbindingstatewithoxygenaddiＧtionalXPSanalysiswasperformedInXPSanalysisonlythecharacteristicpeaksofMnCrandOweredetectedFig1049008３showstheMnandCrXPSnarrowspectraofsamples１and２obtainedfromthesurfaceoxidesXPSspectraofMn(Fig1049008３(a))ofsample１

showthatoxidizedMnispresentinformoftwodifferＧentcomponentsOnecomponenthasthe Mn２p３２peakat６４０1049008８eVandthesecondpeakisat６４２1049008２eVcorrespondingtoMninMnOandMnO２respectively　　Maximumintensity(Fig1049008３(b))oftheCr２p３２peakofsample１isat５７６1049008５eVindicatingthepresＧenceofCr２O３XPSspectraofMn (Fig1049008３(c))ofsample２showthatoxidized MnisalsopresentinformoftwodifferentcomponentsOnecomponenthastheMn２p３２peakat６４１1049008５eVandthesecondpeakisat６４３1049008４eVcorrespondingtoMnin MnOandMnO２respectivelyMaximumintensity(Fig1049008３(d))oftheCr２p３２peakofsample２isat５７６1049008５eVindicatingthepresenceofCr２O３

(a)Mn２pofsample１　 (b)Cr２pofsample１　 (c)Mn２pofsample２　 (d)Cr２pofsample２Fig1049008３　XPSspectraofthesurfaceoxidesonthesamplesafterannealingunderdifferentannealingconditions

２1049008２　Appearancesofthegalvanizingpanels　　Fig1049008４showstheappearanceofthesamplepanＧ

elsgalvanizedinZnbathafterannealingunderdifＧferentannealingconditionswhichrevealsthatbare

(a)Dewpointof－３０N２Ｇ５H２atmosphere　 (b)Dewpointof０N２Ｇ３H２atmosphereFig1049008４　AppearanceofthesamplepanelsgalvanizedinZnbathafterannealingunderdifferentannealingconditions

１６０１Issue１１　　　　InfluenceofOxideMorphologiesonGalvanizabilityofThirdGenerationAutomotiveSteel　

spotsanduncoatedareasoccurredinallsamplesbutthebarespotsanduncoatedareasareobviouslylessinsample１annealedatdewpointof－３０inN２Ｇ５H２atmospherethansample２whichwasanＧnealedatdewpointof０inN２Ｇ３H２atmosphere

２1049008３　Morphologiesofinhibitionlayer　 　 The morphologiesofinhibitionlayerdeterＧminedbySEMareshowninFig1049008５forsamplesanＧ

nealedindifferentannealingconditionsItcanbeseenthattheinhibitionlayerofsample１annealedatdewpointof －３０ in N２Ｇ５H２ atmosphereiscompactbutnothomogenouswhereastheinhibiＧtionlayerformedinsample２annealedatdewpointof０inN２Ｇ３H２atmospherehasanonＧcompactmorphology withsomeparticularlyfineequiaxedcrystalsItisobviousthatthegrainsinsample２deＧvelopeddeficiently

(a)Dewpointof－３０N２Ｇ５H２atmosphere　 (b)Dewpointof０N２Ｇ３H２atmosphereFig1049008５　Morphologiesofinhibitionlayerofthesamplesgalvanizedafterannealingunderdifferentannealingconditions

２1049008４　MorphologiesofFeＧZnphase　　TheFeＧZnphasesonthegalvanizedpanelswere

exposedbystrippingthezincoverlayusing１０H２SO４AsshowninFig1049008６allhotＧdipcoatingplate

(a)Dewpointof－３０N２Ｇ５H２atmosphere　 (b)Dewpointof０N２Ｇ３H２atmosphereFig1049008６　MorphologiesofFeＧZnphasesofthesamplesgalvanizedafterannealingunderdifferentannealingconditions

specimenshaveinterfacegenerationofζphase

３　Discussion　　FornoduleＧlikeoxidesurfaceofsample１anＧnealedatdewpointof－３０inN２Ｇ５H２atmosＧpheretherearelotsofoxidenodulesandbaresubＧ

stratebuttheoxidedensitydistributionisnotuniＧformInsomeregionsoxidenodulesgathertogethＧertoformoxideaggregationandthesizeofoxidenodulesrangesfrom１００to２００nmWithregardtovitreousfilmＧlikeoxidesurfaceofsample２annealedatdewpointof０ inN２Ｇ３H２atmospherethe

２６０１ 　　　　JournalofIronandSteelResearchInternational　　　　　　　　　　　　　　Vol1049008２１　

oxidelayerappearstobecontinuousandvitreousItisthedifferenceofoxygenpotentialthatleadstodifＧferentsurfacemorphologies[９－１１]　　Thesurfaceoxidetypesofsamples１and２byXPSanalysisarethesameandonly MnOMnO２

andCr２O３ weredetectedandnocomplexoxideexＧistsonthesurface　　Fig1049008４showstheappearanceofthesamplepanＧelsgalvanizedinbathSample１onlyshowspinholeＧsizedbarespotsandisobviouslybetterreactivelywettedthansample２whichrevealslargerareasofbarespotsanduncoatedareasThesecoatingdefectsoccurduetotheappearanceofnonＧwettableexternalMnOxlayer[１２]MnOx onthesteelsurfacecouldbeinＧsitureducedbythebathdissolvedAlButifMncontentinthesteelishighenoughandtheformedMnOxareingreatnumberthereductionofMnOx

willbedifficultandcannotbedeoxidizedcompleteＧly[１１１３]SurfacemorphologieswerefoundtostrongＧlyaffectsteelgalvanizability[１４]WhengalvanizingsteelsitisverylikelythatthesurfaceoxidescanbeliftedoffthroughtheFedissolutionfromthesubＧstrateandnoduleＧlikeoxidesshouldbeliftedoffmorereadilythanvitreousfilmＧlikeoxides[１４]BellＧhouse[６]everindicatedthatreactivewettingoccurredbytwo methodswhengalvanizinghigh AlＧlow SiTRIPsteelsreductionofMnObythedissolvedAlintheZn(AlFe)bathandbyZnbridgingoftheoxＧideparticlesThemechanism wasdependentonthesurfacestructurepriortogalvanizingIftheoxidecoversthesurfaceofsteelthebridgingeffectwillnothappen[６]VitreousfilmＧlikeoxidecanhamperthediffusionofzincandaluminumwhichisnecessaryforthemtoreactwithmetalliciron[１５]andresultsinbarespot　　OnthebasisoftheabovedescriptionthereacＧtivewettingisstronglylinkedtothemorphologiesofsurfaceoxidesandnoduleＧlikeoxidesurfacecanbemoreadvantageoustogalvanizingthanvitreousfilmＧlikeoxidesurface　　TwokindsofinhibitionlayergrainswereobＧservedAsshowninFig1049008５(a)someregionsarefineandothersarecoarseAsshowninFig1049008２(a)inadditiontooxideparticlesthereis mostbaresubstrateThebaresubstratecancreateacleansteelsurfacefornucleationofFeＧAlphaseandtheFeＧAlnucleatesinagreatnumberleadingtotheformaＧtionoffineFeＧAlinhibitionlayergrainThenoduleＧlikeoxidecanbethermodynamicallyreducedbythebathAlbecauseofaveryshortgalvanizingtimeof３sTherewasalimittothesizeofoxidesthatcouldbe

completelyreducedIntheprocessofhotdipgalvaniＧzingbigoxideparticlesexistedinthesteelsurfaceandtheFeＧAlgrainscouldonlynucleateoncleanspotsbetweenbigoxidesThustheformedFeＧAlgrainswerescatteredandsparseInadditionbeＧcausetheamountofnucleationsiteswasloweredforperunitareathedissolvedAlwassufficientforthegrowthofFeＧAlgrainsintobiggerones[１３]　　TheinhibitionlayerformedinFig1049008５(b)hasanonＧcompactmorphologywithsomeparticularlyfineequiaxedcrystalsItisobviousthatthegrainsweredevelopeddeficientlyVitreousfilmＧlikeoxidescouldhamperthediffusionofFeandAltoreactwitheachothertoforminhibitionlayerandthusinfluencethereactivewetting　　AsseenfromFig1049008６allsamplepanelshaveinＧterfacegenerationofζphaseInadditiontothealuＧminothermicreductionofmanganeseoxidesthatledtothedecreaseofAlcontentinzincbathandcausedtheformationofζ phase[６１６]Blumenauetal1049008[１７]

explainedthegrowthofFeＧZnphasewithanalterＧnativemechanismAstheFeＧZnphaseisformedduetoAldepletionatthesteelＧzincinterfaceareactionhastooccurconsumingtheAlpresentatthisposiＧtionThehighaffinityofMnandAlcanleadtotheformationofMnＧAlphaseInthisworkBlumenauetalassumedthatAldidnotreduceanymanganeseoxidesandnoaluminothermicreductionoccurredbutMnwasdissolvedoutofthesteelsurfaceintothezincbathandaMnＧAlcompoundwasformedviathereＧactionofMnZn＋６AlZnrarrMnAl６uarr[１７－１９]　　BecauseofthehighcontentofMninthethirdgenerationautomotivesteelwhetherthetheoryproposedbyBlumenauetaltookeffectornotinthisexperimentalsoneedstobefurtherconfirmed

４　Conclusion　　MorphologiesofsurfaceoxidescangreatlyinＧfluencethegalvanizabilityofthethirdgenerationauＧtomotivesteelNoduleＧlikeoxidesurfaceshowbetＧter wettabilityandinhibitionlayerthan vitreousfilmＧlikeoxidesurfaceGalvanizedpanelsofnoduleＧlikeoxidesurfacesteelsonlyshowpinholeＧsizedbarespotswhilepanelsgalvanizedfrom vitreousfilmＧlikeoxidesurfacesteelsreveallargerareasofbarespotsanduncoatedareasInhibitionlayergrainsobＧservedingalvanizedpanelsofnoduleＧlikeoxidessurＧfacesteelsarecompactandcomposedoftwokindsofinhibitionlayergrainssomeregionsarefineandothersarecoarsebuttheinhibitionlayergrainsofpanelsgalvanizedfromvitreousfilmＧlikeoxidesurＧ

３６０１Issue１１　　　　InfluenceofOxideMorphologiesonGalvanizabilityofThirdGenerationAutomotiveSteel　

facesteelshaveanonＧcompact morphology withsomeparticularlyfineequiaxedcrystalswhicharedevelopeddeficiently

References

[１]　W1049008QCaoCWangC1049008YWangJShiM1049008QWangHDongY1049008QWengSciChinaTechSci５５(２０１２)１８１４Ｇ１８２２

[２]　HDongW1049008QCaoJShiC1049008YWangM1049008QWangY1049008QWengIronandSteel４６(２０１１)No1049008６１Ｇ１１

[３]　IOlefjordWLeijonUJelvestamApplSurfaceSci６(１９８０)２４１Ｇ２５５

[４]　H1049008JGrabkeVLeroyHViefhausISIJInt３５(１９９５)９５Ｇ１１３

[５]　PDrilletZZermoutDBouleauJMataigneSClaessensRevMetall１０１(２００４)８３１Ｇ８３７

[６]　E1049008MBellhouseJ1049008RMcDermidMaterSciEngA４９１(２００８)３９Ｇ４６

[７]　JMakiJMahieuB1049008CDeCoomanSClaessensMaterSciTechnol１９(２００３)１２５Ｇ１３１

[８]　LBordignonJCrahayinGalvatechprime０１BrusselsBelgium２００１pp５７３Ｇ５８０

[９]　 MNordenMBlumenauTWuttkeK1049008JPetersApplSurfSci２７１(２０１３)１９Ｇ３１

[１０]　MBlumenauABarnoushIThomasHHofmannHVehoffSurfCoatTechnol２０６(２０１１)５４２Ｇ５５２

[１１]　SAlibeigiRKavithaR1049008JMeguerianJ1049008RMcDermidActaMater５９(２０１１)３５３７Ｇ３５４９

[１２]　MBlumenauMNordenFFriedelKPetersSurfCoatTechnol２０６(２０１１)５５９Ｇ５６７

[１３]　YLiSJiangXYuanBChenQZhangSurfInterfaceAnal４４(２０１２)４７２Ｇ４７７

[１４]　NGaoD1049008Y1049008HLiuN1049008YTangR1049008BParkM1049008SKiminGalvatechprime１１AssociazioneItalianadiMetallurgiaGenoＧvaItaly２０１１pp１２３Ｇ１３０

[１５]　X1049008VEyndeJ1049008PServaisMLamberigtsinGalvatechprime２００４AISTChicagoUSApp３６１Ｇ３７２

[１６]　E1049008MBellhouseA1049008I1049008MMertensJ1049008RMcDermidMaterSciEngA４６３(２００７)１４７Ｇ１５６

[１７]　MBlumenauMNordenFFriedelKPetersSurfCoatTechnol２０５(２０１１)３３１９Ｇ３３２７

[１８]　RSaglAJarosikDStifterGAngeliCorrosSci７０(２０１３)２６８Ｇ２７５

[１９]　RKavithaJ1049008RMcDermidSurfCoatTechnol２１２(２０１２)１５２Ｇ１５８

４６０１ 　　　　JournalofIronandSteelResearchInternational　　　　　　　　　　　　　　Vol1049008２１　

phereAsshowninFig1049008２(a)afterannealingatdewpointof－３０ inN２Ｇ５H２atmospheretheunＧcoatedsamplesurfaceiscoveredbylotsofnoduleＧlikeoxidesbuttherearestillmostbaresubstrateHoweverthesurfaceofsample２annealedatdewpointof０ in N２Ｇ３ H２ atmosphereiscoveredwithalayerofvitreousfilmＧlikeoxide　　InordertoclarifythechemicalelementsofthesurfaceoxidesandbindingstatewithoxygenaddiＧtionalXPSanalysiswasperformedInXPSanalysisonlythecharacteristicpeaksofMnCrandOweredetectedFig1049008３showstheMnandCrXPSnarrowspectraofsamples１and２obtainedfromthesurfaceoxidesXPSspectraofMn(Fig1049008３(a))ofsample１

showthatoxidizedMnispresentinformoftwodifferＧentcomponentsOnecomponenthasthe Mn２p３２peakat６４０1049008８eVandthesecondpeakisat６４２1049008２eVcorrespondingtoMninMnOandMnO２respectively　　Maximumintensity(Fig1049008３(b))oftheCr２p３２peakofsample１isat５７６1049008５eVindicatingthepresＧenceofCr２O３XPSspectraofMn (Fig1049008３(c))ofsample２showthatoxidized MnisalsopresentinformoftwodifferentcomponentsOnecomponenthastheMn２p３２peakat６４１1049008５eVandthesecondpeakisat６４３1049008４eVcorrespondingtoMnin MnOandMnO２respectivelyMaximumintensity(Fig1049008３(d))oftheCr２p３２peakofsample２isat５７６1049008５eVindicatingthepresenceofCr２O３

(a)Mn２pofsample１　 (b)Cr２pofsample１　 (c)Mn２pofsample２　 (d)Cr２pofsample２Fig1049008３　XPSspectraofthesurfaceoxidesonthesamplesafterannealingunderdifferentannealingconditions

２1049008２　Appearancesofthegalvanizingpanels　　Fig1049008４showstheappearanceofthesamplepanＧ

elsgalvanizedinZnbathafterannealingunderdifＧferentannealingconditionswhichrevealsthatbare

(a)Dewpointof－３０N２Ｇ５H２atmosphere　 (b)Dewpointof０N２Ｇ３H２atmosphereFig1049008４　AppearanceofthesamplepanelsgalvanizedinZnbathafterannealingunderdifferentannealingconditions

１６０１Issue１１　　　　InfluenceofOxideMorphologiesonGalvanizabilityofThirdGenerationAutomotiveSteel　

spotsanduncoatedareasoccurredinallsamplesbutthebarespotsanduncoatedareasareobviouslylessinsample１annealedatdewpointof－３０inN２Ｇ５H２atmospherethansample２whichwasanＧnealedatdewpointof０inN２Ｇ３H２atmosphere

２1049008３　Morphologiesofinhibitionlayer　 　 The morphologiesofinhibitionlayerdeterＧminedbySEMareshowninFig1049008５forsamplesanＧ

nealedindifferentannealingconditionsItcanbeseenthattheinhibitionlayerofsample１annealedatdewpointof －３０ in N２Ｇ５H２ atmosphereiscompactbutnothomogenouswhereastheinhibiＧtionlayerformedinsample２annealedatdewpointof０inN２Ｇ３H２atmospherehasanonＧcompactmorphology withsomeparticularlyfineequiaxedcrystalsItisobviousthatthegrainsinsample２deＧvelopeddeficiently

(a)Dewpointof－３０N２Ｇ５H２atmosphere　 (b)Dewpointof０N２Ｇ３H２atmosphereFig1049008５　Morphologiesofinhibitionlayerofthesamplesgalvanizedafterannealingunderdifferentannealingconditions

２1049008４　MorphologiesofFeＧZnphase　　TheFeＧZnphasesonthegalvanizedpanelswere

exposedbystrippingthezincoverlayusing１０H２SO４AsshowninFig1049008６allhotＧdipcoatingplate

(a)Dewpointof－３０N２Ｇ５H２atmosphere　 (b)Dewpointof０N２Ｇ３H２atmosphereFig1049008６　MorphologiesofFeＧZnphasesofthesamplesgalvanizedafterannealingunderdifferentannealingconditions

specimenshaveinterfacegenerationofζphase

３　Discussion　　FornoduleＧlikeoxidesurfaceofsample１anＧnealedatdewpointof－３０inN２Ｇ５H２atmosＧpheretherearelotsofoxidenodulesandbaresubＧ

stratebuttheoxidedensitydistributionisnotuniＧformInsomeregionsoxidenodulesgathertogethＧertoformoxideaggregationandthesizeofoxidenodulesrangesfrom１００to２００nmWithregardtovitreousfilmＧlikeoxidesurfaceofsample２annealedatdewpointof０ inN２Ｇ３H２atmospherethe

２６０１ 　　　　JournalofIronandSteelResearchInternational　　　　　　　　　　　　　　Vol1049008２１　

oxidelayerappearstobecontinuousandvitreousItisthedifferenceofoxygenpotentialthatleadstodifＧferentsurfacemorphologies[９－１１]　　Thesurfaceoxidetypesofsamples１and２byXPSanalysisarethesameandonly MnOMnO２

andCr２O３ weredetectedandnocomplexoxideexＧistsonthesurface　　Fig1049008４showstheappearanceofthesamplepanＧelsgalvanizedinbathSample１onlyshowspinholeＧsizedbarespotsandisobviouslybetterreactivelywettedthansample２whichrevealslargerareasofbarespotsanduncoatedareasThesecoatingdefectsoccurduetotheappearanceofnonＧwettableexternalMnOxlayer[１２]MnOx onthesteelsurfacecouldbeinＧsitureducedbythebathdissolvedAlButifMncontentinthesteelishighenoughandtheformedMnOxareingreatnumberthereductionofMnOx

willbedifficultandcannotbedeoxidizedcompleteＧly[１１１３]SurfacemorphologieswerefoundtostrongＧlyaffectsteelgalvanizability[１４]WhengalvanizingsteelsitisverylikelythatthesurfaceoxidescanbeliftedoffthroughtheFedissolutionfromthesubＧstrateandnoduleＧlikeoxidesshouldbeliftedoffmorereadilythanvitreousfilmＧlikeoxides[１４]BellＧhouse[６]everindicatedthatreactivewettingoccurredbytwo methodswhengalvanizinghigh AlＧlow SiTRIPsteelsreductionofMnObythedissolvedAlintheZn(AlFe)bathandbyZnbridgingoftheoxＧideparticlesThemechanism wasdependentonthesurfacestructurepriortogalvanizingIftheoxidecoversthesurfaceofsteelthebridgingeffectwillnothappen[６]VitreousfilmＧlikeoxidecanhamperthediffusionofzincandaluminumwhichisnecessaryforthemtoreactwithmetalliciron[１５]andresultsinbarespot　　OnthebasisoftheabovedescriptionthereacＧtivewettingisstronglylinkedtothemorphologiesofsurfaceoxidesandnoduleＧlikeoxidesurfacecanbemoreadvantageoustogalvanizingthanvitreousfilmＧlikeoxidesurface　　TwokindsofinhibitionlayergrainswereobＧservedAsshowninFig1049008５(a)someregionsarefineandothersarecoarseAsshowninFig1049008２(a)inadditiontooxideparticlesthereis mostbaresubstrateThebaresubstratecancreateacleansteelsurfacefornucleationofFeＧAlphaseandtheFeＧAlnucleatesinagreatnumberleadingtotheformaＧtionoffineFeＧAlinhibitionlayergrainThenoduleＧlikeoxidecanbethermodynamicallyreducedbythebathAlbecauseofaveryshortgalvanizingtimeof３sTherewasalimittothesizeofoxidesthatcouldbe

completelyreducedIntheprocessofhotdipgalvaniＧzingbigoxideparticlesexistedinthesteelsurfaceandtheFeＧAlgrainscouldonlynucleateoncleanspotsbetweenbigoxidesThustheformedFeＧAlgrainswerescatteredandsparseInadditionbeＧcausetheamountofnucleationsiteswasloweredforperunitareathedissolvedAlwassufficientforthegrowthofFeＧAlgrainsintobiggerones[１３]　　TheinhibitionlayerformedinFig1049008５(b)hasanonＧcompactmorphologywithsomeparticularlyfineequiaxedcrystalsItisobviousthatthegrainsweredevelopeddeficientlyVitreousfilmＧlikeoxidescouldhamperthediffusionofFeandAltoreactwitheachothertoforminhibitionlayerandthusinfluencethereactivewetting　　AsseenfromFig1049008６allsamplepanelshaveinＧterfacegenerationofζphaseInadditiontothealuＧminothermicreductionofmanganeseoxidesthatledtothedecreaseofAlcontentinzincbathandcausedtheformationofζ phase[６１６]Blumenauetal1049008[１７]

explainedthegrowthofFeＧZnphasewithanalterＧnativemechanismAstheFeＧZnphaseisformedduetoAldepletionatthesteelＧzincinterfaceareactionhastooccurconsumingtheAlpresentatthisposiＧtionThehighaffinityofMnandAlcanleadtotheformationofMnＧAlphaseInthisworkBlumenauetalassumedthatAldidnotreduceanymanganeseoxidesandnoaluminothermicreductionoccurredbutMnwasdissolvedoutofthesteelsurfaceintothezincbathandaMnＧAlcompoundwasformedviathereＧactionofMnZn＋６AlZnrarrMnAl６uarr[１７－１９]　　BecauseofthehighcontentofMninthethirdgenerationautomotivesteelwhetherthetheoryproposedbyBlumenauetaltookeffectornotinthisexperimentalsoneedstobefurtherconfirmed

４　Conclusion　　MorphologiesofsurfaceoxidescangreatlyinＧfluencethegalvanizabilityofthethirdgenerationauＧtomotivesteelNoduleＧlikeoxidesurfaceshowbetＧter wettabilityandinhibitionlayerthan vitreousfilmＧlikeoxidesurfaceGalvanizedpanelsofnoduleＧlikeoxidesurfacesteelsonlyshowpinholeＧsizedbarespotswhilepanelsgalvanizedfrom vitreousfilmＧlikeoxidesurfacesteelsreveallargerareasofbarespotsanduncoatedareasInhibitionlayergrainsobＧservedingalvanizedpanelsofnoduleＧlikeoxidessurＧfacesteelsarecompactandcomposedoftwokindsofinhibitionlayergrainssomeregionsarefineandothersarecoarsebuttheinhibitionlayergrainsofpanelsgalvanizedfromvitreousfilmＧlikeoxidesurＧ

３６０１Issue１１　　　　InfluenceofOxideMorphologiesonGalvanizabilityofThirdGenerationAutomotiveSteel　

facesteelshaveanonＧcompact morphology withsomeparticularlyfineequiaxedcrystalswhicharedevelopeddeficiently

References

[１]　W1049008QCaoCWangC1049008YWangJShiM1049008QWangHDongY1049008QWengSciChinaTechSci５５(２０１２)１８１４Ｇ１８２２

[２]　HDongW1049008QCaoJShiC1049008YWangM1049008QWangY1049008QWengIronandSteel４６(２０１１)No1049008６１Ｇ１１

[３]　IOlefjordWLeijonUJelvestamApplSurfaceSci６(１９８０)２４１Ｇ２５５

[４]　H1049008JGrabkeVLeroyHViefhausISIJInt３５(１９９５)９５Ｇ１１３

[５]　PDrilletZZermoutDBouleauJMataigneSClaessensRevMetall１０１(２００４)８３１Ｇ８３７

[６]　E1049008MBellhouseJ1049008RMcDermidMaterSciEngA４９１(２００８)３９Ｇ４６

[７]　JMakiJMahieuB1049008CDeCoomanSClaessensMaterSciTechnol１９(２００３)１２５Ｇ１３１

[８]　LBordignonJCrahayinGalvatechprime０１BrusselsBelgium２００１pp５７３Ｇ５８０

[９]　 MNordenMBlumenauTWuttkeK1049008JPetersApplSurfSci２７１(２０１３)１９Ｇ３１

[１０]　MBlumenauABarnoushIThomasHHofmannHVehoffSurfCoatTechnol２０６(２０１１)５４２Ｇ５５２

[１１]　SAlibeigiRKavithaR1049008JMeguerianJ1049008RMcDermidActaMater５９(２０１１)３５３７Ｇ３５４９

[１２]　MBlumenauMNordenFFriedelKPetersSurfCoatTechnol２０６(２０１１)５５９Ｇ５６７

[１３]　YLiSJiangXYuanBChenQZhangSurfInterfaceAnal４４(２０１２)４７２Ｇ４７７

[１４]　NGaoD1049008Y1049008HLiuN1049008YTangR1049008BParkM1049008SKiminGalvatechprime１１AssociazioneItalianadiMetallurgiaGenoＧvaItaly２０１１pp１２３Ｇ１３０

[１５]　X1049008VEyndeJ1049008PServaisMLamberigtsinGalvatechprime２００４AISTChicagoUSApp３６１Ｇ３７２

[１６]　E1049008MBellhouseA1049008I1049008MMertensJ1049008RMcDermidMaterSciEngA４６３(２００７)１４７Ｇ１５６

[１７]　MBlumenauMNordenFFriedelKPetersSurfCoatTechnol２０５(２０１１)３３１９Ｇ３３２７

[１８]　RSaglAJarosikDStifterGAngeliCorrosSci７０(２０１３)２６８Ｇ２７５

[１９]　RKavithaJ1049008RMcDermidSurfCoatTechnol２１２(２０１２)１５２Ｇ１５８

４６０１ 　　　　JournalofIronandSteelResearchInternational　　　　　　　　　　　　　　Vol1049008２１　

spotsanduncoatedareasoccurredinallsamplesbutthebarespotsanduncoatedareasareobviouslylessinsample１annealedatdewpointof－３０inN２Ｇ５H２atmospherethansample２whichwasanＧnealedatdewpointof０inN２Ｇ３H２atmosphere

２1049008３　Morphologiesofinhibitionlayer　 　 The morphologiesofinhibitionlayerdeterＧminedbySEMareshowninFig1049008５forsamplesanＧ

nealedindifferentannealingconditionsItcanbeseenthattheinhibitionlayerofsample１annealedatdewpointof －３０ in N２Ｇ５H２ atmosphereiscompactbutnothomogenouswhereastheinhibiＧtionlayerformedinsample２annealedatdewpointof０inN２Ｇ３H２atmospherehasanonＧcompactmorphology withsomeparticularlyfineequiaxedcrystalsItisobviousthatthegrainsinsample２deＧvelopeddeficiently

(a)Dewpointof－３０N２Ｇ５H２atmosphere　 (b)Dewpointof０N２Ｇ３H２atmosphereFig1049008５　Morphologiesofinhibitionlayerofthesamplesgalvanizedafterannealingunderdifferentannealingconditions

２1049008４　MorphologiesofFeＧZnphase　　TheFeＧZnphasesonthegalvanizedpanelswere

exposedbystrippingthezincoverlayusing１０H２SO４AsshowninFig1049008６allhotＧdipcoatingplate

(a)Dewpointof－３０N２Ｇ５H２atmosphere　 (b)Dewpointof０N２Ｇ３H２atmosphereFig1049008６　MorphologiesofFeＧZnphasesofthesamplesgalvanizedafterannealingunderdifferentannealingconditions

specimenshaveinterfacegenerationofζphase

３　Discussion　　FornoduleＧlikeoxidesurfaceofsample１anＧnealedatdewpointof－３０inN２Ｇ５H２atmosＧpheretherearelotsofoxidenodulesandbaresubＧ

stratebuttheoxidedensitydistributionisnotuniＧformInsomeregionsoxidenodulesgathertogethＧertoformoxideaggregationandthesizeofoxidenodulesrangesfrom１００to２００nmWithregardtovitreousfilmＧlikeoxidesurfaceofsample２annealedatdewpointof０ inN２Ｇ３H２atmospherethe

２６０１ 　　　　JournalofIronandSteelResearchInternational　　　　　　　　　　　　　　Vol1049008２１　

oxidelayerappearstobecontinuousandvitreousItisthedifferenceofoxygenpotentialthatleadstodifＧferentsurfacemorphologies[９－１１]　　Thesurfaceoxidetypesofsamples１and２byXPSanalysisarethesameandonly MnOMnO２

andCr２O３ weredetectedandnocomplexoxideexＧistsonthesurface　　Fig1049008４showstheappearanceofthesamplepanＧelsgalvanizedinbathSample１onlyshowspinholeＧsizedbarespotsandisobviouslybetterreactivelywettedthansample２whichrevealslargerareasofbarespotsanduncoatedareasThesecoatingdefectsoccurduetotheappearanceofnonＧwettableexternalMnOxlayer[１２]MnOx onthesteelsurfacecouldbeinＧsitureducedbythebathdissolvedAlButifMncontentinthesteelishighenoughandtheformedMnOxareingreatnumberthereductionofMnOx

willbedifficultandcannotbedeoxidizedcompleteＧly[１１１３]SurfacemorphologieswerefoundtostrongＧlyaffectsteelgalvanizability[１４]WhengalvanizingsteelsitisverylikelythatthesurfaceoxidescanbeliftedoffthroughtheFedissolutionfromthesubＧstrateandnoduleＧlikeoxidesshouldbeliftedoffmorereadilythanvitreousfilmＧlikeoxides[１４]BellＧhouse[６]everindicatedthatreactivewettingoccurredbytwo methodswhengalvanizinghigh AlＧlow SiTRIPsteelsreductionofMnObythedissolvedAlintheZn(AlFe)bathandbyZnbridgingoftheoxＧideparticlesThemechanism wasdependentonthesurfacestructurepriortogalvanizingIftheoxidecoversthesurfaceofsteelthebridgingeffectwillnothappen[６]VitreousfilmＧlikeoxidecanhamperthediffusionofzincandaluminumwhichisnecessaryforthemtoreactwithmetalliciron[１５]andresultsinbarespot　　OnthebasisoftheabovedescriptionthereacＧtivewettingisstronglylinkedtothemorphologiesofsurfaceoxidesandnoduleＧlikeoxidesurfacecanbemoreadvantageoustogalvanizingthanvitreousfilmＧlikeoxidesurface　　TwokindsofinhibitionlayergrainswereobＧservedAsshowninFig1049008５(a)someregionsarefineandothersarecoarseAsshowninFig1049008２(a)inadditiontooxideparticlesthereis mostbaresubstrateThebaresubstratecancreateacleansteelsurfacefornucleationofFeＧAlphaseandtheFeＧAlnucleatesinagreatnumberleadingtotheformaＧtionoffineFeＧAlinhibitionlayergrainThenoduleＧlikeoxidecanbethermodynamicallyreducedbythebathAlbecauseofaveryshortgalvanizingtimeof３sTherewasalimittothesizeofoxidesthatcouldbe

completelyreducedIntheprocessofhotdipgalvaniＧzingbigoxideparticlesexistedinthesteelsurfaceandtheFeＧAlgrainscouldonlynucleateoncleanspotsbetweenbigoxidesThustheformedFeＧAlgrainswerescatteredandsparseInadditionbeＧcausetheamountofnucleationsiteswasloweredforperunitareathedissolvedAlwassufficientforthegrowthofFeＧAlgrainsintobiggerones[１３]　　TheinhibitionlayerformedinFig1049008５(b)hasanonＧcompactmorphologywithsomeparticularlyfineequiaxedcrystalsItisobviousthatthegrainsweredevelopeddeficientlyVitreousfilmＧlikeoxidescouldhamperthediffusionofFeandAltoreactwitheachothertoforminhibitionlayerandthusinfluencethereactivewetting　　AsseenfromFig1049008６allsamplepanelshaveinＧterfacegenerationofζphaseInadditiontothealuＧminothermicreductionofmanganeseoxidesthatledtothedecreaseofAlcontentinzincbathandcausedtheformationofζ phase[６１６]Blumenauetal1049008[１７]

explainedthegrowthofFeＧZnphasewithanalterＧnativemechanismAstheFeＧZnphaseisformedduetoAldepletionatthesteelＧzincinterfaceareactionhastooccurconsumingtheAlpresentatthisposiＧtionThehighaffinityofMnandAlcanleadtotheformationofMnＧAlphaseInthisworkBlumenauetalassumedthatAldidnotreduceanymanganeseoxidesandnoaluminothermicreductionoccurredbutMnwasdissolvedoutofthesteelsurfaceintothezincbathandaMnＧAlcompoundwasformedviathereＧactionofMnZn＋６AlZnrarrMnAl６uarr[１７－１９]　　BecauseofthehighcontentofMninthethirdgenerationautomotivesteelwhetherthetheoryproposedbyBlumenauetaltookeffectornotinthisexperimentalsoneedstobefurtherconfirmed

４　Conclusion　　MorphologiesofsurfaceoxidescangreatlyinＧfluencethegalvanizabilityofthethirdgenerationauＧtomotivesteelNoduleＧlikeoxidesurfaceshowbetＧter wettabilityandinhibitionlayerthan vitreousfilmＧlikeoxidesurfaceGalvanizedpanelsofnoduleＧlikeoxidesurfacesteelsonlyshowpinholeＧsizedbarespotswhilepanelsgalvanizedfrom vitreousfilmＧlikeoxidesurfacesteelsreveallargerareasofbarespotsanduncoatedareasInhibitionlayergrainsobＧservedingalvanizedpanelsofnoduleＧlikeoxidessurＧfacesteelsarecompactandcomposedoftwokindsofinhibitionlayergrainssomeregionsarefineandothersarecoarsebuttheinhibitionlayergrainsofpanelsgalvanizedfromvitreousfilmＧlikeoxidesurＧ

３６０１Issue１１　　　　InfluenceofOxideMorphologiesonGalvanizabilityofThirdGenerationAutomotiveSteel　

facesteelshaveanonＧcompact morphology withsomeparticularlyfineequiaxedcrystalswhicharedevelopeddeficiently

References

[１]　W1049008QCaoCWangC1049008YWangJShiM1049008QWangHDongY1049008QWengSciChinaTechSci５５(２０１２)１８１４Ｇ１８２２

[２]　HDongW1049008QCaoJShiC1049008YWangM1049008QWangY1049008QWengIronandSteel４６(２０１１)No1049008６１Ｇ１１

[３]　IOlefjordWLeijonUJelvestamApplSurfaceSci６(１９８０)２４１Ｇ２５５

[４]　H1049008JGrabkeVLeroyHViefhausISIJInt３５(１９９５)９５Ｇ１１３

[５]　PDrilletZZermoutDBouleauJMataigneSClaessensRevMetall１０１(２００４)８３１Ｇ８３７

[６]　E1049008MBellhouseJ1049008RMcDermidMaterSciEngA４９１(２００８)３９Ｇ４６

[７]　JMakiJMahieuB1049008CDeCoomanSClaessensMaterSciTechnol１９(２００３)１２５Ｇ１３１

[８]　LBordignonJCrahayinGalvatechprime０１BrusselsBelgium２００１pp５７３Ｇ５８０

[９]　 MNordenMBlumenauTWuttkeK1049008JPetersApplSurfSci２７１(２０１３)１９Ｇ３１

[１０]　MBlumenauABarnoushIThomasHHofmannHVehoffSurfCoatTechnol２０６(２０１１)５４２Ｇ５５２

[１１]　SAlibeigiRKavithaR1049008JMeguerianJ1049008RMcDermidActaMater５９(２０１１)３５３７Ｇ３５４９

[１２]　MBlumenauMNordenFFriedelKPetersSurfCoatTechnol２０６(２０１１)５５９Ｇ５６７

[１３]　YLiSJiangXYuanBChenQZhangSurfInterfaceAnal４４(２０１２)４７２Ｇ４７７

[１４]　NGaoD1049008Y1049008HLiuN1049008YTangR1049008BParkM1049008SKiminGalvatechprime１１AssociazioneItalianadiMetallurgiaGenoＧvaItaly２０１１pp１２３Ｇ１３０

[１５]　X1049008VEyndeJ1049008PServaisMLamberigtsinGalvatechprime２００４AISTChicagoUSApp３６１Ｇ３７２

[１６]　E1049008MBellhouseA1049008I1049008MMertensJ1049008RMcDermidMaterSciEngA４６３(２００７)１４７Ｇ１５６

[１７]　MBlumenauMNordenFFriedelKPetersSurfCoatTechnol２０５(２０１１)３３１９Ｇ３３２７

[１８]　RSaglAJarosikDStifterGAngeliCorrosSci７０(２０１３)２６８Ｇ２７５

[１９]　RKavithaJ1049008RMcDermidSurfCoatTechnol２１２(２０１２)１５２Ｇ１５８

４６０１ 　　　　JournalofIronandSteelResearchInternational　　　　　　　　　　　　　　Vol1049008２１　

oxidelayerappearstobecontinuousandvitreousItisthedifferenceofoxygenpotentialthatleadstodifＧferentsurfacemorphologies[９－１１]　　Thesurfaceoxidetypesofsamples１and２byXPSanalysisarethesameandonly MnOMnO２

andCr２O３ weredetectedandnocomplexoxideexＧistsonthesurface　　Fig1049008４showstheappearanceofthesamplepanＧelsgalvanizedinbathSample１onlyshowspinholeＧsizedbarespotsandisobviouslybetterreactivelywettedthansample２whichrevealslargerareasofbarespotsanduncoatedareasThesecoatingdefectsoccurduetotheappearanceofnonＧwettableexternalMnOxlayer[１２]MnOx onthesteelsurfacecouldbeinＧsitureducedbythebathdissolvedAlButifMncontentinthesteelishighenoughandtheformedMnOxareingreatnumberthereductionofMnOx

willbedifficultandcannotbedeoxidizedcompleteＧly[１１１３]SurfacemorphologieswerefoundtostrongＧlyaffectsteelgalvanizability[１４]WhengalvanizingsteelsitisverylikelythatthesurfaceoxidescanbeliftedoffthroughtheFedissolutionfromthesubＧstrateandnoduleＧlikeoxidesshouldbeliftedoffmorereadilythanvitreousfilmＧlikeoxides[１４]BellＧhouse[６]everindicatedthatreactivewettingoccurredbytwo methodswhengalvanizinghigh AlＧlow SiTRIPsteelsreductionofMnObythedissolvedAlintheZn(AlFe)bathandbyZnbridgingoftheoxＧideparticlesThemechanism wasdependentonthesurfacestructurepriortogalvanizingIftheoxidecoversthesurfaceofsteelthebridgingeffectwillnothappen[６]VitreousfilmＧlikeoxidecanhamperthediffusionofzincandaluminumwhichisnecessaryforthemtoreactwithmetalliciron[１５]andresultsinbarespot　　OnthebasisoftheabovedescriptionthereacＧtivewettingisstronglylinkedtothemorphologiesofsurfaceoxidesandnoduleＧlikeoxidesurfacecanbemoreadvantageoustogalvanizingthanvitreousfilmＧlikeoxidesurface　　TwokindsofinhibitionlayergrainswereobＧservedAsshowninFig1049008５(a)someregionsarefineandothersarecoarseAsshowninFig1049008２(a)inadditiontooxideparticlesthereis mostbaresubstrateThebaresubstratecancreateacleansteelsurfacefornucleationofFeＧAlphaseandtheFeＧAlnucleatesinagreatnumberleadingtotheformaＧtionoffineFeＧAlinhibitionlayergrainThenoduleＧlikeoxidecanbethermodynamicallyreducedbythebathAlbecauseofaveryshortgalvanizingtimeof３sTherewasalimittothesizeofoxidesthatcouldbe

completelyreducedIntheprocessofhotdipgalvaniＧzingbigoxideparticlesexistedinthesteelsurfaceandtheFeＧAlgrainscouldonlynucleateoncleanspotsbetweenbigoxidesThustheformedFeＧAlgrainswerescatteredandsparseInadditionbeＧcausetheamountofnucleationsiteswasloweredforperunitareathedissolvedAlwassufficientforthegrowthofFeＧAlgrainsintobiggerones[１３]　　TheinhibitionlayerformedinFig1049008５(b)hasanonＧcompactmorphologywithsomeparticularlyfineequiaxedcrystalsItisobviousthatthegrainsweredevelopeddeficientlyVitreousfilmＧlikeoxidescouldhamperthediffusionofFeandAltoreactwitheachothertoforminhibitionlayerandthusinfluencethereactivewetting　　AsseenfromFig1049008６allsamplepanelshaveinＧterfacegenerationofζphaseInadditiontothealuＧminothermicreductionofmanganeseoxidesthatledtothedecreaseofAlcontentinzincbathandcausedtheformationofζ phase[６１６]Blumenauetal1049008[１７]

explainedthegrowthofFeＧZnphasewithanalterＧnativemechanismAstheFeＧZnphaseisformedduetoAldepletionatthesteelＧzincinterfaceareactionhastooccurconsumingtheAlpresentatthisposiＧtionThehighaffinityofMnandAlcanleadtotheformationofMnＧAlphaseInthisworkBlumenauetalassumedthatAldidnotreduceanymanganeseoxidesandnoaluminothermicreductionoccurredbutMnwasdissolvedoutofthesteelsurfaceintothezincbathandaMnＧAlcompoundwasformedviathereＧactionofMnZn＋６AlZnrarrMnAl６uarr[１７－１９]　　BecauseofthehighcontentofMninthethirdgenerationautomotivesteelwhetherthetheoryproposedbyBlumenauetaltookeffectornotinthisexperimentalsoneedstobefurtherconfirmed

４　Conclusion　　MorphologiesofsurfaceoxidescangreatlyinＧfluencethegalvanizabilityofthethirdgenerationauＧtomotivesteelNoduleＧlikeoxidesurfaceshowbetＧter wettabilityandinhibitionlayerthan vitreousfilmＧlikeoxidesurfaceGalvanizedpanelsofnoduleＧlikeoxidesurfacesteelsonlyshowpinholeＧsizedbarespotswhilepanelsgalvanizedfrom vitreousfilmＧlikeoxidesurfacesteelsreveallargerareasofbarespotsanduncoatedareasInhibitionlayergrainsobＧservedingalvanizedpanelsofnoduleＧlikeoxidessurＧfacesteelsarecompactandcomposedoftwokindsofinhibitionlayergrainssomeregionsarefineandothersarecoarsebuttheinhibitionlayergrainsofpanelsgalvanizedfromvitreousfilmＧlikeoxidesurＧ

３６０１Issue１１　　　　InfluenceofOxideMorphologiesonGalvanizabilityofThirdGenerationAutomotiveSteel　

facesteelshaveanonＧcompact morphology withsomeparticularlyfineequiaxedcrystalswhicharedevelopeddeficiently

References

[１]　W1049008QCaoCWangC1049008YWangJShiM1049008QWangHDongY1049008QWengSciChinaTechSci５５(２０１２)１８１４Ｇ１８２２

[２]　HDongW1049008QCaoJShiC1049008YWangM1049008QWangY1049008QWengIronandSteel４６(２０１１)No1049008６１Ｇ１１

[３]　IOlefjordWLeijonUJelvestamApplSurfaceSci６(１９８０)２４１Ｇ２５５

[４]　H1049008JGrabkeVLeroyHViefhausISIJInt３５(１９９５)９５Ｇ１１３

[５]　PDrilletZZermoutDBouleauJMataigneSClaessensRevMetall１０１(２００４)８３１Ｇ８３７

[６]　E1049008MBellhouseJ1049008RMcDermidMaterSciEngA４９１(２００８)３９Ｇ４６

[７]　JMakiJMahieuB1049008CDeCoomanSClaessensMaterSciTechnol１９(２００３)１２５Ｇ１３１

[８]　LBordignonJCrahayinGalvatechprime０１BrusselsBelgium２００１pp５７３Ｇ５８０

[９]　 MNordenMBlumenauTWuttkeK1049008JPetersApplSurfSci２７１(２０１３)１９Ｇ３１

[１０]　MBlumenauABarnoushIThomasHHofmannHVehoffSurfCoatTechnol２０６(２０１１)５４２Ｇ５５２

[１１]　SAlibeigiRKavithaR1049008JMeguerianJ1049008RMcDermidActaMater５９(２０１１)３５３７Ｇ３５４９

[１２]　MBlumenauMNordenFFriedelKPetersSurfCoatTechnol２０６(２０１１)５５９Ｇ５６７

[１３]　YLiSJiangXYuanBChenQZhangSurfInterfaceAnal４４(２０１２)４７２Ｇ４７７

[１４]　NGaoD1049008Y1049008HLiuN1049008YTangR1049008BParkM1049008SKiminGalvatechprime１１AssociazioneItalianadiMetallurgiaGenoＧvaItaly２０１１pp１２３Ｇ１３０

[１５]　X1049008VEyndeJ1049008PServaisMLamberigtsinGalvatechprime２００４AISTChicagoUSApp３６１Ｇ３７２

[１６]　E1049008MBellhouseA1049008I1049008MMertensJ1049008RMcDermidMaterSciEngA４６３(２００７)１４７Ｇ１５６

[１７]　MBlumenauMNordenFFriedelKPetersSurfCoatTechnol２０５(２０１１)３３１９Ｇ３３２７

[１８]　RSaglAJarosikDStifterGAngeliCorrosSci７０(２０１３)２６８Ｇ２７５

[１９]　RKavithaJ1049008RMcDermidSurfCoatTechnol２１２(２０１２)１５２Ｇ１５８

４６０１ 　　　　JournalofIronandSteelResearchInternational　　　　　　　　　　　　　　Vol1049008２１　

facesteelshaveanonＧcompact morphology withsomeparticularlyfineequiaxedcrystalswhicharedevelopeddeficiently

References

[１]　W1049008QCaoCWangC1049008YWangJShiM1049008QWangHDongY1049008QWengSciChinaTechSci５５(２０１２)１８１４Ｇ１８２２

[２]　HDongW1049008QCaoJShiC1049008YWangM1049008QWangY1049008QWengIronandSteel４６(２０１１)No1049008６１Ｇ１１

[３]　IOlefjordWLeijonUJelvestamApplSurfaceSci６(１９８０)２４１Ｇ２５５

[４]　H1049008JGrabkeVLeroyHViefhausISIJInt３５(１９９５)９５Ｇ１１３

[５]　PDrilletZZermoutDBouleauJMataigneSClaessensRevMetall１０１(２００４)８３１Ｇ８３７

[６]　E1049008MBellhouseJ1049008RMcDermidMaterSciEngA４９１(２００８)３９Ｇ４６

[７]　JMakiJMahieuB1049008CDeCoomanSClaessensMaterSciTechnol１９(２００３)１２５Ｇ１３１

[８]　LBordignonJCrahayinGalvatechprime０１BrusselsBelgium２００１pp５７３Ｇ５８０

[９]　 MNordenMBlumenauTWuttkeK1049008JPetersApplSurfSci２７１(２０１３)１９Ｇ３１

[１０]　MBlumenauABarnoushIThomasHHofmannHVehoffSurfCoatTechnol２０６(２０１１)５４２Ｇ５５２

[１１]　SAlibeigiRKavithaR1049008JMeguerianJ1049008RMcDermidActaMater５９(２０１１)３５３７Ｇ３５４９

[１２]　MBlumenauMNordenFFriedelKPetersSurfCoatTechnol２０６(２０１１)５５９Ｇ５６７

[１３]　YLiSJiangXYuanBChenQZhangSurfInterfaceAnal４４(２０１２)４７２Ｇ４７７

[１４]　NGaoD1049008Y1049008HLiuN1049008YTangR1049008BParkM1049008SKiminGalvatechprime１１AssociazioneItalianadiMetallurgiaGenoＧvaItaly２０１１pp１２３Ｇ１３０

[１５]　X1049008VEyndeJ1049008PServaisMLamberigtsinGalvatechprime２００４AISTChicagoUSApp３６１Ｇ３７２

[１６]　E1049008MBellhouseA1049008I1049008MMertensJ1049008RMcDermidMaterSciEngA４６３(２００７)１４７Ｇ１５６

[１７]　MBlumenauMNordenFFriedelKPetersSurfCoatTechnol２０５(２０１１)３３１９Ｇ３３２７

[１８]　RSaglAJarosikDStifterGAngeliCorrosSci７０(２０１３)２６８Ｇ２７５

[１９]　RKavithaJ1049008RMcDermidSurfCoatTechnol２１２(２０１２)１５２Ｇ１５８

４６０１ 　　　　JournalofIronandSteelResearchInternational　　　　　　　　　　　　　　Vol1049008２１