钢中夹杂物的常规定性分析

第27卷第4期 2007年4月 冶金分析 MetallurgicalAnalysis V01．27．No．4 April，2007 文章编号：1000—7571(2007)04—0001—06 RoutinequalitatiVeanalysisof inclusionsinsteel TORTOREToGiampietro‘，SCIABOLETTADomenico， ROTICIANISilvio (ThyssenKruppAcciaiSpecialiTemi，Temi，Italy) Abstr舵t：MoStinvestigationsofinclusionsandprecipitateswere，andstillare，donebyoptical microscopyonpolishedsteelsurfaces．Improvementoftheresolutionofpulsediscriminationanal— ysis-opticalemiSsionspectrometry(PDA—OES)isexpectedinthe∞mingyearS．Size，numberand spatialdistributioncanberecorded．Duringautomaticrnonitoring，combinedwitheitherelectron probemicro—analysis(EPMA)orPDA-OES，ap01ishedsteelsurfaceisscanned．Althou曲areaand perimeteroftheinclusionsisrecorded，derivationoftheirshapesisnotevident．Theinclusion’s shapeanditssurfacecharacteristicsteUthehistoryofaparticularinclusion．Thereforebeingable toreadthehistorymayresultinadditionalinfomationaboutinclusionfo瑚ation，growthand evolution．TheaimofthisworkwastofindacorrelationbetweenSEM／EDSanalysisandOES／ PDAtechniques．ThePDA—oEStechniqueswereusedtoanalyzequalitativelytheinclusionsin staillleSssteel，aSwellaSincarbonsteel．Onthebaseofthisstudy，Semi—quantitativeorquantita— tiveanalysisoftheinclusionswillbeexpectedtorealizebyconsideringtheheightandtheintensity ofthepeakswithpropercompa“SOntoreferencematerials． Keywords：stainlesssteel；pulSediscriminationanalysis；opticalemissionspectroscopy；non— meta¨icinclusions CLCnumber：0657．63D0cumentcode：A ThesteelindustryisfacedwiththechaUenge ofproducinghigherqualityandcleanersteel，while increasingproductivity．onthisbasesignificant progresshasbeenmadeintheanalySisofironand steel：sampleanalysistime，sensitivity，precision andaccuracyhaveallbeensubstantiaUyimpt．oved inthelastyears． Adl旧noedsClftwareapplicatjoninopticalerlliSsliCln spectrometry，、ⅣitlltheaoquiSitionoft11e1ightintensity 鲥ttedbyeachsin西esparkoft11ediScharge，opens newgoalsintheapplicationofthiStEdlmque．Optical 蹦SSionSple(=t1_cIⅡ1eterscoddnotodydisplay，withina fewSeamds，thed戚calO(mlp商tionofmetal蛐一 ples，butaLts0，inreal6meandonthesaIlleprintout， valllableinfbtTnationab珈lt小ejrindl】siono()ntentand 也eirdeannessindex． Mostim怪缸gatiOnsofineIusionsa11dprecipitates were，aJldstiUare，dDnebyopticalmicI唧yonpol— iShedsteels1】rfaoes．FH瑚1960on啪rdselec臼Dnmi— clDscopybecamewid爱pread．Thisnotodye陇出lesin一 嘣i野monatlaIgerm碰；mfications，butitcaneasilybe O(m=1：bined、^，ith删yticaltec：h11iques，calledelec旬Dn p出rni静砌灿(EP凇)[1-2]．InEPMAthe small6ktmnb哪，whichiSinScarulingrIⅪDdeuSed forimaging，西v签riSet0“sSiImofX-myS谢th wavelen戥hScharacteristicfbrt11eeleInentSpr爱蛇nt． Theapplic撕onofanEM厄PMAcallchamctedSeH】ost of出ep；lrmnetersdescribingt11eSteddediness．USing back_scatteredelectronsfbrimagingtheinduSionSshaw Si鲥ficallt00ntrastto乱pohsheds渊“缸．The Reoeiveddate：2006一09—16 Bio呻phy：GianlpietroTortoreto(1947一)。male。Ph．D。LaboratoriesManager，ThyssenKruppAcciaiSpecialiTerni。E— mail：gi锄tof@1ibem．it． 一1一 峻鼍睾睾謦睾睾鼍睾睾弗睾带 {II 研究与试验报告 蒂≯睾带鬻鬻土_鬻睾鬻鱼_鬻带凑 万方数据 第27卷第4期 冶 金 分 析 V0l·27·No·4 2007年4月 MetauurgicalAnalysiS April，2007 largec0咖aStbetweens乜eelm缸xa11dinclusionsen— ablesautomaticmom幻ringifasanlpkm0、唧mentsys— t锄isattached．Number，diameterandpedm酏erd indusionscc疽TIbined、耐thrnicrpanalyses咖bereoDrd— ed．Despiteiheauto姐ticmom砸ngthemetllodiSrd— ativdvSlowduetotheti雠nec联；s奶7f6faccLlrate删一 ysis． Spark—S0urceoptical“ssionSpec心mleny ((娅S)，wmchiSs协dardforbulkstedanal姆s，∞m— binedwithpulsedbcri耐nationanalysis(PDA)haSre— cendybeendevelopedandismuchfaSterthanE~P— MA[3—4|．In()ESPlDA，theplaSnlacreatesernissiC憷 ofli{出t、^，ithwavden础scharactedsticfortheeIanents pn葛ent．Theplaslmisproducedduringelectricdis— char_ge．Sincet11eareaaffectedbythepl猢is1arger than吐眦ofandectmnb咖forEPⅣ睑，雠resolu— tionofOESPDAiS舢chless妇forEPMA，e．g． 30一50脚and1—5pm，re{；pectivd，5q]．Inlp聊e— m∞tdd旋Te9011】tiond(黔PDAis镪【pe魄edhthe ∞mingyears．Size，mmiberandSpa6aldis试butioncan bere咖dod【9—10j． AnalySisareperformedonasingleinstrument atclearlylowercosts，incomparisontoexisting techniauesforsteelcleannesswhicharetimecon— sumingandexpensive(SEM／EDSMicrograph)． AnOESmethodtoanalyseindusionsinstain— lesssteelispresentedinthispaper，acr．ossastudy ofthelightemittedbyeachsinglespark．Graphsof theoverlappingofthelightsofelements，con— stituentoftheinclusions，areshowed． Theaimofour、∞rkwaStoanalySeexpected differentphasesofoxides，carbidesandnitritesin steelinafaStway，togivemoreinfomationtothe productionandqualitycontr01．Atthemomentitis notpossibleaquantitativeanalySis，wedonothave referencematerialswithacertifiedvalueofinctu— sions，nevertheleSsa qualitativedeteminationof themcanbealsouseful． TheanalyticalprogramscanbeconfiguredaS wellasclaSSicalpro罾rams，eachelementcanbecal— ibratedanddriftcorrected，theirresultscanbedis- played，stored，printedanddistributed，datahan— dlingakorithmscanbeeasilyselectedorplugged intothesoftware． 一2— 1 Experimental IncIusiondetectionandanalysisweredoneun— dera scanningelectronmicroscopeSEM／EDS CambridgeMod．withtungstenwiretodetectand analyseallsecondphaseparticlesthatwereVisible atamagnificationof1，000×． S涵ark—inducedopticalemissionspectroscopyis ∞mmonlvusedtodeterminethenominalchemistry ofconductivesolidspecimens．Inthiswork，an opticalEmissionSpectrometerARL4460ofThe卜 rno(乃rp．wasused． Cbrrespondingopticalemissionintensityspec— tracanberepresentedasdensityfunctionsobtained byaccumulatingthenumberofpulSeSineachclass ofintenSityallowedbythephotomultiplierSandaS· sociatedelectronicchain． Thesespectraareusuallyverynoisybecauseof svstemresolutionandanalysedpulsenumber (1，500)limitations．Asa consequence，theyex。 hibitimportantfillingdefectsatSomeintenSityleV。 els，alongwithexceSSfillingsatotherleVels． 2 Inclusionsprecipitation The{irstst印doⅢre辩archwas幻ve《y，byop— ticalandscandngdect姒1icalmidⅨ∞py，theinclusions instajnIessSteelSaI]啊es．‰of伽dd删 oOilS，afbera sellsitizingthem】altri舭nte)c成utedm la_bOfat。fyt0predpi协tethephases，areshowed． ADhotoofchromiumcarbides，obtainedafter SenSitisingat675℃for1handatamagnification of200X，isreportedinF谵．1： Fig．1se瞄iti髓dmicr憾tr眦ture(at675℃for1h) Ofatypic蚰austeniticstainlesss“埒l (withtheevidence0fchmmiumc盯bid髂 M23c6p陀cipitat酋) 万方数据 Thefollowingfigure(Fig．2)referStoan austeniticstainlesssteelwhereit ispossibletosee inclusionswhoseanalysis，performedbySEM／ EDS，areprinted．Fromtheresultswecansay thatthemaincompositionoftheinclusionspresent isbasedonoxidesofA1，(、aandSi． Fig．2oxid鹤inclusionsina吣teniticstainIesssteeIarIdEI'sanaIysis Fig．3oxid鹤incIusionsinausteniticstainIe蟠st∞landEDS蛆alysis Thesameconclusionscanbedroppeddownfromthefollowingsample． InF培．4，anausteniticstainlesssteelstabilized withTiisreported，inthissamplewefoundinclu— sionsofTiNaccordingtoSEM／EDSanalySis。 l耗．4 nt蛐i哪疵ridei眦I璐io璐in卸姚litic咖IIle略 steeIstabilizedbytitaniumandEDSanalysis Inconclusionthedistributionoftheindusions indifferentsampleswereanalysedbySEM厄DS micrOgraph．Fromtheanalysisobtained，wecan understandthatthefollowingoxidesandnitrideS arethemaincomponentsoftheinclusions：Cao， Si02，A1203，TiN． WedidnotconsiderthepresenceofFeandCr oxidesbecausetheyarethemainconstituentsofthe steelanalvsedandcouldinterfereonSEM／EDS analysis． 一3 万方数据 第27卷第4期 冶 金分析v文27，No．4 2007年4月 MetallurgicalAnalysis April，2007 3 IncIusionsanalysisbyoES onceidentifiedthephases，bySEM／EDSand opticalMicroscopy，westartedthedetermination ofthembyOpticalEmissionSpectrometry． Fmmthefollowinggraphs，whereeachsingle sparkisreported，wecanassumethattheinclu． sionsreadinthesampl毛sbySEM厄DSarealSo readbyOES． Thelowintensitypulsescorrespondtothere． sponseofelementsinsolutioninthemetalandthe 4 60∞ 55∞ 50∞ 4S∞ ●—∞0 3册 3∞D 2枷 2∞O 15∞ 1脚 5∞ highintensitypulsescouldcorrespondtoelements containedininclusionswhenthevarenotdueto anykindofLABpollution．Thechosenparameter toindicatehighintensitypulsesistheaveragevalue addedbythreetimesofstandarddeviationofthe onesofansparks．Anindicationof1argersizeof theinclusionsisgivenoⅣerthisreferencevalue(or— derofsixorninetimesofstandarddeviation)．In Fig．5agraphindicating业03inclusionsinan austeniticstainlesssteelisreported．Theoverlaps of02and趾pulseSindicatethepresenceof砧203． L ．{f．IJ|lJL』血I队，。u}J～一，“。⋯．．．。。LL血lu止．L止．-l～ ⋯-”。’r1’ ’’⋯rT⋯。n“⋯■⋯1-’r1Tr’r_P。r’-⋯'■’叮l‘■’⋯”’1●’'。’1—111I 湖 枷 嘲8∞ ’肋 1抽 ’椭 1枷 1枷 2彻 灿山 “I山II111山 』 柚 idlI山。-．ILk|I|-川．1．山洲 ”r_⋯。‘1j’胛T"l’I”，’『r’1’I"’_ rI7Hn■ r。1-。-1啊'T-r’1I『-'_’’’’叩1”1■ 伽 晰8∞ Fig．6Typical粕alysisoftit粕iumnitrideincI晒io璐inf电州ticstainI嘟 steelstabili跹dbytit粕iumbyoES(TiupNdown) || h 一 ^ i || |||||||||||||||| 万方数据 专；万馨铲T昧T。R啪Qam。tetro，etd．勋utineauatt圳vea砌粥ts甜inc-us岫stnstee- V01．27．No．4ADril，2007 Ina sampleofferriticstainlesssteel，aS showedinFig．6，itisalsopossibletoseethepres— enceofTiN． 12脚 11咖 10咖 9J啪 8埘 7∞0 6．O∞ 5．0∞ ●．∞O 3脚 2脚 ’脚 InF遮．7，、Vecallsee，twodjfferemoverhpping ofthepea：I【sofsdiO。nandoxygenat也elowersideof sparkmmiberst11at朗叩hasizeSthepresenoeofsiQ． Jr池L从1．IJl|⋯lI-ILI．。lJj¨ll也“⋯I虬．L。h。l。。．：。|【J 枷 枷 咖 鲫 '脚 1瑚 1枷 1枷 1枷 2咖 再电．7 PDA蛐alysis0fCa锄旧们碘}啪si弘蚰pIottedvs． sparknumber(Caupodown) Wedidn’texactlyknowifaggregatesofox— idescouldbepresentintheinclusions．Fbrthis reaS0nweexaminedthereSponseofoursamples andinsomeofthem，itwaspossibletofoundan overlappingofthepeaksofAlandSithatcould suggestthepresenceofanaggregateorclusterof sihcates(withstoichoiometryA12()3一Si()2)． 枷 蜘e∞ 嘲 Fig．8TypicaI粕alysisofchr帅iumc盯bideobtainedbythesignaIof c盯boninoES蛐aIysis(evidenceofIargerinte璐itypeab)andpu№in- te砸itydistribution(hisbogram)ofc盯bonsignalsofPDA帆st∞1with ehromiumcarbidesindusiO璐 FinanyinF谵．8，fI．omthesignalofcarbonof anausteniticstainlesssteel18／8sensitised，thefre— quencyofpeaksofCovertheaverageplusthree standarddeviationcouldjustifythepresenceof 5—— 日6‘2 D e 6●2 瑚狮抛抛伽伽懈伽仰∞∞帕∞。 万方数据 第27卷第4期 2007年4月 冶金分析 MetaUurgicalAnalySis V。1．27．No．4 APril，2007 chromiumcarbide(Cr23C6)．Aboutthehigher sparknumberpeaks，theycouldrepresenta poSsi— bleevidenceofanaggregatesofcarbide．Instain— lesssteelscarbonitridesaswellascarbidescouldbe present，wearestillinvestigatingontheiridentifi— cationbothbySEM／EDSandbyOES． 4 ConclusiOns onthebaseoftheresultsobtaineditispossi— bletosaythattheoEScanbeusedtoanalyse，ina firststep，theinclusionspresentinstainlesssteel， aswenasincarbonsteel[1]． OfcourSethemethod，abSOlutelyfast，isonly qualitative．Cbnsideringtheheightandtheintedsi— tyofthepeaks，afterapropercompariSonwithref— erencematerialsadhocprepared，thesecondstep ofthisstudy，couldbeasemi—quantitativeorquan— titativeanalysisoftheinclusions． References [1]MullerE，ZuberC，B?hlenJ M．on—Linespark—DAT fbrultimateeIementalanalvsisandadditionalmetalschar— acterizationwith0pticalEmissionSpectroscopy[Z]． ThermoARLAppliedResearchLaboratories，2006． [2]MullerG，StahnkeF，BleinerD，Faststeel—cleanness characterizationbymeansofIaser—assistedplasmaspec— trametricmeth()ds[J]．Talanta，2006，70(5)：991— 995． [3]PissenbergerA，PissenbergerE． AutomaticCleanness DeteminationofPmductionSampleswith0ES／’PDA， J．Angeli(ed．)：Proceedings7thInternat[c]．work— shopPmgresSinAnal”icalChemistryintheSteeland MetalIndustries，2006． [4]H哪merlinM，MeillandaR，FalkbH，eta1．Applica— tionofvacuumultmvioletlaSer—inducedbreaklownspec— trometryforsteelanalysiscompariSon谢thspark—optical 锄iSSiollspectr㈨etry[J]．SpectrochimicaActa：PartB， 2001，56(6)：661—669． [5]RocaboisP，LehmannJ，GayeH，eta1．Kineticsofpre— cipitationofnon—metallicinclusionsduringSolidificationof steeI[J]。JoumaIofCryStaIGrowth，1999，198／199： 838—843． [6]FalkH，WintjensP．EvaluationofSingle．Sparksandits ApplicationstotheEvaluationofInclusions[J]．Joumal 0fCrystalGro叭h，1999，413—419． [7]MeillandR，eta1．RapidCharacterisationofHetero— geneities(InclusionsandSegregation)bySpectralTech— niques[J]．JournalofCrystalGfowth，1999，420一427． [8]Jo谢ttR．RapidDeteminationofsteelCleanliness[C]． ECSCProject72lO—GD／806FinalReport，1994． [9]MathyH，TusSetV，LamberigtsM．AnEvaluationof SulphideIndusionContentAssessmentMethodsIn、，ac— uum—ProcessedSteels，2006． [10]10。staA，silva．Th咖10dynamjcaspectSofinduSilm∞画一 ne刮119insteels[J]．RareMetais，2006，25(5)：412— 419． 钢中夹杂物的常 规定 关于下班后关闭电源的规定党章中关于入党时间的规定公务员考核规定下载规定办法文件下载宁波关于闷顶的规定 性分析 TORTORETOGiampietro，SCIABoLETTADomenico，RoTICIANISilvio (ThyssenKruppAcciaiSpecialiTerni，Temi，Italy) 摘 要：对于钢中夹杂物的研究，目前大多数工作是采用光学显微镜测量抛光的钢样表面的方 法实现的。今后若干年里，脉冲分布解析原子发射光谱法(PDA-oES)的分辩率有望得到提 高，可以获得夹杂物的尺寸、颗粒数以及空间分布的信息。在应用电子探针微区分析(EPMA) 或PD瓜OES技术的自动监控过程中，是对抛光的钢表面进行扫描分析。虽然可以获得夹杂 物的截面面积及其边界信息，但是这些夹杂物形状的成因却不明显。由于夹杂物的形状和表 面特性可以揭示出某类夹杂物的形成过程，因此获知夹杂物的形成过程就可以得到夹杂物的 形成、生长和演变等相关信息。本文的目的就是研究钢中夹杂物分析中SEM侄DS技术和0ES／ PI)A技术的相关性。应用PD艮OES技术对不锈钢及碳钢中夹杂物进行了定性分析。在此基础 上，通过峰高和峰强度与参考物质的比较，将有望实现对夹杂物的半定量或定量分析。 关键词：不锈钢；脉冲分布解析；原子发射光谱；非金属夹杂物 6 万方数据 钢中夹杂物的常规定性分析 作者： TORTORETO Giampietro， SCIABOLETTA Domenico， ROTICIANI Silvio 作者单位： ThyssenKrupp Acciai Speciali Terni, Terni, Italy 刊名： 冶金分析 英文刊名： METALLURGICAL ANALYSIS 年，卷(期)： 2007,27(4) 参考文献(10条) 1.Mathy H;Tusset V;Lamberigts M An Evaluation Of Sulphide Inclusion Content Assessment Methods In Vacuum-Processed Steels 2006 2.Jowitt R Rapid Determination of Steel Cleanliness[ECSC Project 7210-GD/806 Final Report] 1994 3.Meilland R Rapid Characterisation of Heterogeneities (Inclusions and Segregation) by Spectral Techniques 1999 4.Falk H;Wintjens P Evaluation of Single-Sparks and its Applications to the Evaluation of Inclusions 1999 5.Rocabois P;Lehmann J;Gaye H Kinetics of precipitation of non-metallic inclusions duringsolidification of steel 1999 6.Hemmerlin M;Meillanda R;Falkb H Application of vacuum ultraviolet laser-induced breakdown spectrometry for steel analysis comparison with spark-optical emission spectrometry 2001(06) 7.Muller E;Zuber C;B? hlen J M On-Line Spark-DAT for ultimate elemental analysis and additional metals characterization with Optical Emission Spectroscopy 2006 8.Costa A Silva Thermodynamic aspects of inclusion engineering in steels[外文期刊] 2006(05) 9.Pissenberger A;Pissenberger E Automatic Cleanness Determination of Production Samples with OES/PDA 2006 10.Muller G;Stahnke F;Bleiner D Fast steel-cleanness characterization by means of laser-assisted plasma spectrometric methods[外文期刊] 2006(05) 本文链接：http://d.g.wanfangdata.com.cn/Periodical_yjfx200704001.aspx