第27卷第4期
2007年4月
冶金分析MetallurgicalAnalysis
V01.27.No.4April,2007
{II
文章编号:1000—7571(2007)04—0001—06
RoutinequalitatiVeanalysisof
inclusionsinsteel
研究与试验报告
蒂TORTOREToGiampietro‘,SCIABOLETTADomenico,
ROTICIANISilvio
(ThyssenKrupp
Acciai
SpecialiTemi,Temi,Italy)
Abstr舵t:MoSt
microscopy
on
investigationsofinclusionsandprecipitateswere,andstillare,donebyoptical
polishedsteelsurfaces.Improvementoftheresolutionofpulsediscriminationanal—
ysis-opticalemiSsionspectrometry(PDA—OES)isexpectedinthe∞mingyearS.Size,numberandspatialdistribution
can
berecorded.Duringautomaticrnonitoring,combinedwitheitherelectron
is
probemicro—analysis(EPMA)orPDA-OES,ap01ishedsteelsurface
shapeanditssurfacecharacteristicsteUthehistoryof
to
scanned.Althou曲area
not
and
perimeteroftheinclusionsisrecorded,derivationoftheirshapesis
a
evident.Theinclusion’s
particularinclusion.Thereforebeingableaboutinclusion
readthehistorymayresultinadditional
to
infomation
a
fo瑚ation,growth
and
evolution.Theaimofthisworkwasfind
correlationbetweenSEM/EDSanalysisandOES/
to
PDAtechniques.ThePDA—oEStechniqueswereusedstaillleSssteel,aSwell
aS
analyzequalitativelytheinclusionsin
or
incarbonsteel.Onthebaseofthisstudy,Semi—quantitative
quantita—
tiveanalysisoftheinclusionswillbeexpectedtorealizebyconsideringtheheightandtheintensity
ofthepeakswithpropercompa“SOnKeywords:
to
referencematerials.
opticalemissionspectroscopy;non—
stainlesssteel;pulSediscriminationanalysis;
meta¨icinclusions
CLCnumber:0657.63
D0cumentcode:A
ThesteelindustryisfacedwiththechaUengeofproducinghigherqualityandcleanersteel,while
increasing
也eirdeannessindex.
Mostim怪缸gatiOnsofineIusionsa11d
were,aJldstiUare,dDnebyoptical
productivity.
onthisbase
significant
micI唧y
can
precipitates
on
pol—
progresshasbeenmadeintheanalySisofironand
iShedsteels1】rfaoes.
FH瑚1960on啪rds
elec臼Dnmi—
steel:sampleanalysistime,sensitivity,
andaccuracy
precision
clDscopybecamewid爱pread.Thisnotodye陇出lesin一
haveallbeensubstantiaUyimpt.oved
inthelastyears.
嘣i野monlaIgerm碰;mfications,butiteasilybeO(m=1:bined、^,ith删yticaltec:h11iques,calledelec旬Dn
at
Adl旧noedsClftwareapplicatjoninopticalerlliSsliCln
spectrometry,、ⅣitlltheaoquiSitionoft11e1ightintensity
p出rni静砌灿(EP凇)[1-2].In
small
EPMAthe
6ktmn
b哪,which
iSinScarulingrIⅪDdeuSed
鲥tted
byeachsin西esparkoft11ediScharge,opensforimaging,西v签riSe
t0“sSiIm
call
ofX-myS谢th
pr爱蛇nt.
H】ost
newgoalsintheapplicationofthiStEdlmque.Optical
wavelen戥hScharacteristicfbrt11eeleInentSTheapplic撕onofof出e
p;lrmneters
an
蹦SSion
Sple(=t1_cIⅡ1eterscoddnotodydisplay,within
a
EM厄PMA
chamctedSe
fewSeamds,the
d戚cal
O(mlp商tion
of
metal蛐一
printout,
and
describingt11eSteddediness.USing
ples,butaLts0,inreal6meandonthe
valllableinfbtTnation
saIlle
back_scatteredelectronsfbrimagingtheinduSionSshaw
ab珈lt小ejrindl】sion
o()ntent
Si鲥ficallt
00ntrast
to乱pohsheds渊“缸.The
Reoeiveddate:2006一09—16
Bio呻phy:GianlpietroTortoreto(1947一)。male。Ph.D。Laboratories
万方数据
mail:gi锄tof@1ibem.it.
Manager,ThyssenKrupp
Acciai
Speciali
Terni。E—
一1一
第27卷第4期2007年4月
冶金分析
V0l・27・No・4
MetauurgicalAnalysiS
April,2007
large
c0咖aSt
betweens乜eel
m缸x
a11dinclusions
en—
ablesautomaticmom幻ringif
a
sanlpkm0、唧mentsys—
t锄is
attached.Number,diameterandpedm酏erd
indusionscc疽TIbined、耐thrnicrpanalyses咖bereoDrd—
ed.Despiteiheauto姐ticmom砸ngthemetllodiSrd—
ativdvSlowdue
to
the
ti雠nec联;s奶7
f6f
accLlrate删一
ysis.
Spark—S0urce
optical
“ssion
Spec心mleny
((娅S),wmch
iS
s协dardforbulkstedanal姆s,∞m—
binedwithpulse
dbcri耐nationanalysis(PDA)haS
re—
cendybeendevelopedandismuchfaSterthanE ̄P—
MA[3—4|.In()ESPlDA,the
plaSnlacreates
ernissiC憷
of
li{出t、^,ith
wavden础scharactedsticfortheeIanents
pn葛ent.The
plaslm
is
producedduringelectricdis—
char_ge.Sincet11e
area
affectedbythe
pl猢is1arger
than吐眦of
an
dectmn
b咖for
EPⅣ睑,雠resolu—
tionofOESPDA
iS舢ch
less妇forEPMA,e.g.
30一50脚and
1—5
pm,re{;pectivd,5q].Inlp聊e—
m∞tdd旋Te9011】tion
d(黔PDAis镪【pe魄edh
the
∞mingyears.Size,mmiberandSpa6aldis试butioncan
be
re咖dod【9—10j.
AnalySis
are
performed
on
a
singleinstrument
at
clearlylower
costs,
in
comparison
to
existing
techniauesforsteelcleannesswhichare
time
con—
sumingand
expensive(SEM/EDSMicrograph).
AnOESmethodtoanalyseindusionsinstain—
lesssteelispresentedinthis
paper,acr.oss
a
study
ofthelightemittedbyeachsinglespark.Graphsofthe
overlappingof
the
lightsofelements,
con—
stituentoftheinclusions,areshowed.
Theaimof
our、∞rk
waStoanalySeexpected
differentphasesofoxides,carbidesandnitritesin
steelin
a
faStway,togivemore
infomation
tothe
productionandqualitycontr01.Atthe
momentitis
not
possible
a
quantitativeanalySis,wedonothave
referencematerialswitha
certifiedvalueofinctu—
sions,
nevertheleSs
a
qualitative
detemination
of
them
can
bealsouseful.
Theanalyticalprogramscan
beconfigured
aS
well
as
claSSicalpro罾rams,eachelement
canbecal—ibratedanddriftcorrected,theirresults
can
bedis-
played,stored,printedanddistributed,datahan—dlingakorithms
can
beeasilyselected
or
plugged
intothesoftware.
万方数据
一2—1
Experimental
IncIusiondetectionandanalysisweredone
un—
der
a
scanning
electron
microscope
SEM/EDS
CambridgeMod.with
tungsten
wiretodetectand
analyseallsecondphaseparticlesthatwereVisible
at
a
magnificationof1,000×.S涵ark—inducedopticalemission
spectroscopy
is
∞mmonlv
usedtodeterminethenominalchemistry
ofconductivesolidspecimens.
Inthiswork,
an
opticalEmissionSpectrometerARL4460ofThe卜
rno(乃rp.wasused.
Cbrrespondingopticalemissionintensityspec—
tra
can
berepresented
as
densityfunctionsobtained
byaccumulatingthenumberofpulSeSineachclass
ofintenSityallowedbythephotomultiplierSand
aS・
sociatedelectronicchain.
Thesespectra
are
usually
very
noisybecauseofsvstem
resolutionandanalysed
pulse
number
(1,500)limitations.
As
a
consequence,they
ex。
hibitimportantfillingdefects
atSomeintenSityleV。
els,alongwith
exceSS
fillings
at
otherleVels.
2
Inclusionsprecipitation
The{irst
st印doⅢre辩archwas幻ve《y,by
op—
ticalandscandng
inclusions
instajnIess
Steel
SaI]啊es.‰of伽dd删
dect姒1ical
midⅨ∞py,theoOilS,afbera
sellsitizing
them】al
tri舭nt
e)c成utedm
la_bOfat。fy
t0
predpi协tethephases,areshowed.
ADhotoofchromiumcarbides,obtainedafter
SenSitisingat675℃for1handat
a
magnification
of200X,isreportedinF谵.1:
Fig.1
se瞄iti髓dmicr憾tr眦ture(at675℃for
1
h)
Of
a
typic蚰austeniticstainlesss“埒l
(withtheevidence0fchmmiumc盯bid髂
M23c6
p陀cipitat酋)
Thefollowingfigure(Fig.2)referS
toto
ansee
EDS,
are
printed.From
theresults
we
can
say
austeniticstainlesssteelwhereitispossibleinclusions
whose
analysis,
thatthemaincompositionoftheinclusions
isbased
on
present
performedby
SEM/oxidesofA1,(、aandSi.
Fig.2
oxid鹤inclusionsina吣teniticstainIesssteeIarIdEI'sanaIysis
Fig.3
Thesameconclusions
can
oxid鹤incIusionsinausteniticstainIe蟠st∞landEDS蛆alysisbedroppeddownfromthefollowingsample.
InF培.4,anausteniticstainlesssteelstabilizedwithTiisreported,inthissamplewefoundinclu—sionsofTiNaccordingto
SEM/EDSanalySis。
Inconclusionthedistributionoftheindusionsindifferent
sampleswereanalysedby
SEM厄DS
can
micrOgraph.
Fromtheanalysisobtained,we
understandthatthe
are
followingoxidesandnitrideS
the
maincomponentsoftheinclusions:Cao,
Si02,A1203,TiN.
Wedid
not
considerthe
are
presence
ofFeandCr
oxidesbecausethey
l耗.4
themainconstituentsofthe
on
nt蛐i哪疵ridei眦I璐io璐in卸姚litic咖IIle略
titaniumandEDSanalysis
steelanalvsedandcouldinterfereanalysis.
SEM/EDS
steeIstabilizedby
万方数据
一3
第27卷第4期2007年4月
冶金分析v文27,No.4
April,2007
MetallurgicalAnalysis
3
IncIusionsanalysisbyoES
onceidentifiedthephases,by
highintensitypulsescouldcorrespondtoelements
containedininclusionswhenthev
and
anyto
arenot
due
to
SEM/EDS
kindofLABpollution.
Thechosenparameter
optical
Microscopy,we
startedthedetermination
indicatehighintensitypulsesistheaveragevalue
ofthembyOpticalEmissionSpectrometry.
Fmmthefollowinggraphs,whereeachsingle
sparkis
reported,wein
the
can
addedbythreetimesofstandarddeviationofthe
ones
||一^ihindicationofansparks.||Anof1argersizeof
oⅣer
assumethattheinclu.
theinclusionsisgiven
derofsixFig.5
a
or
thisreference
value(or—
In
an
sionsread
sampl毛sby
SEM厄DS
are
alSoninetimesofstandarddeviation).
readbyOES.
Thelowintensitypulsescorrespondtothe
sponse
re.
graph
indicating业03
inclusionsin
austeniticstainlesssteelisreported.Theoverlaps
ofelementsinsolutioninthemetalandthe
60∞
55∞50∞4S∞●—∞0
of02and趾pulseSindicatethepresence
of砧203.
3册
3∞D
2枷
1
2∞O
1脚
5∞
L
5∞
.{f.IJ|lJL』血I队,。u}J~一,“。…...。。LL血lu止.L止.-l~
…-”。’r
1’
湖枷
’’…rT…。n“…■…1-’r1Tr’r_P。r’-…'■’叮l‘■’…”’1●’'。’1—111I
嘲8∞’肋1抽’椭1枷1枷2彻
灿山
洲
”r_…。‘1j’胛T"
“I山II111山』柚idlI山。-.ILk|I|-川.1.山
l’I”,’『r’1’I"’_
■nH7Ir
r。1-。-1啊'T-r’1I『-
'_’’’’叩1”1■
伽
Fig.6
晰8∞
of
Typical粕alysis
steel
tit粕ium
nitrideincI晒io璐in
f电州ticstainI嘟
stabili跹dbytit粕iumbyoES(TiupNdown)
4
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s
In
a
tnstee-
V01.27.No.4ADril,2007
sampleof
ferriticstainless
to
see
steel,
aS
InF遮.7,、Ve
call
see,twodjfferemoverhpping
showedinFig.6,itisalsopossible
ence
thepres—ofthepea:I【sofsdiO。nandoxygenat也elowersideof
ofTiN.
sparkmmiberst11at朗叩hasizeSthe
presenoe
of
siQ.
12脚
11咖10咖9J啪
8埘
7∞06.O∞5.0∞
3脚2脚’脚
●.∞O
J
r池L从1.IJl|…lI-ILI
枷
枷
咖
鲫
.。lJj¨ll也“…I虬.L。h。l。。.:。|【J
'脚
1瑚
1枷
1枷
1枷
2咖
再电.7
PDA蛐alysis
spark
0f
Ca锄旧们碘}啪si弘蚰pIotted
upo
vs.
number(Ca
ox—
down)
We
didn’texactlyknowifaggregatesof
present
overlappingofthe
suggest
peaksofAlandSithatcould
an
idescouldbe
reaS0n
inthe
theinclusions.Fbrthis
of
our
thepresenceof
aggregate
or
clusterof
weexamined
reSponse
samples
an
sihcates(withstoichoiometryA12()3一Si()2).
andinsomeofthem,itwaspossibletofound
日6‘2De
6●2
枷蜘e∞嘲
Fig.8c盯bon
TypicaI粕alysis
in
of
chr帅ium
c盯bide
obtained
bythesignaIof
oES蛐aIysis(evidenceofIargerinte璐itypeab)andpu№in-
te砸itydistribution(hisbogram)ofc盯bonsignalsofehromiumcarbidesindusiO璐
FinanyinF谵.8,fI.omthesignalofcarbonof
an
PDA帆st∞1
with
quency
ofpeaksofCdeviation
over
the
average
plusthree
of
austeniticstainlesssteel18/8sensitised,thefre—standardcould
justify
the
presence
万方数据
5——
第27卷第4期冶金分析V。1.27.No.42007年4月
MetaUurgicalAnalySis
APril,2007
chromiumcarbide(Cr23C6).
Aboutthehigher
995.
sparknumberpeaks,theycouldrepresent
a
poSsi—
[3]PissenbergerA,Pissenberger
E.AutomaticCleanness
bleevidenceof
an
aggregatesofcarbide.
Instain—
Detemination
of
Pmduction
Sampleswith0ES/’PDA,
lesssteelscarbonitrides
as
well
7th
as
carbidescouldbe
J.Angeli(ed.):ProceedingsInternat[c].work—
and
present,we
are
stillinvestigatingon
theiridentifi—
shopPmgresSinAnal”icalChemistryintheSteelMetalIndustries,2006.
cationbothby
SEM/EDS
andbyOES.
[4]H哪merlin
M,MeillandaR,Falkb
H,et
a1.Applica—
4ConclusiOns
tionof
vacuumultmvioletlaSer—inducedbreaklown
spec—
trometryforsteelanalysiscompariSon谢thspark—optical
onthebaseoftheresultsobtaineditispossi—
锄iSSiollspectr㈨etry[J].SpectrochimicaActa:Part
B,
ble
tosay
thattheoES
can
beusedtoanalyse,in
a
2001,56(6):661—669.firststep,theinclusionspresentinstainlesssteel,
[5]RocaboisP,LehmannJ,Gaye
H,et
a1.Kineticsofpre—
as
wen
as
incarbonsteel[1].
cipitation
ofnon—metallicinclusionsduringSolidificationof
Of
courSe
themethod,abSOlutelyfast,isonly
steeI[J]。JoumaIofCryStaI
Growth,1999,198/199:
838—843.
qualitative.Cbnsideringtheheightandtheintedsi—
[6]FalkH,Wintjens
P.Evaluationof
Single.Sparksand
its
ty
ofthepeaks,after
a
proper
compariSonwithref—
Applicationsto
the
EvaluationofInclusions[J].Joumal
erence
materialsadhocprepared,thesecondstep
0fCrystal
Gro叭h,1999,413—419.
ofthisstudy,couldbe
a
semi—quantitative
or
quan—
[7]MeillandR,et
a1.Rapid
CharacterisationofHetero—
titativeanalysisoftheinclusions.
geneities(Inclusionsand
Segregation)bySpectralTech—
References
niques[J].JournalofCrystalGfowth,1999,420一427.
[8]Jo谢tt
R.Rapid
Detemination
ofsteelCleanliness[C].
[1]MullerE,ZuberC,B?hlenJM.on—Linespark—DAT
ECSC
Project72lO—GD/806FinalReport,1994.
fbrultimateeIementalanalvsisandadditionalmetalschar—
[9]MathyH,TusSetV,LamberigtsM.AnEvaluationof
acterization
with
0pticalEmissionSpectroscopy[Z].
SulphideIndusionContentAssessmentMethodsIn、,ac—ThermoARLAppliedResearchLaboratories,2006.
uum—ProcessedSteels,2006.
[2]MullerG,StahnkeF,Bleiner
D,Faststeel—cleanness[10]10。sta
A,silva.Th咖10dynamjc
aspectS
ofinduSilm∞画一
characterization
bymeansofIaser—assistedplasmaspec—ne刮119insteels[J].RareMetais,2006,25(5):412—
trametricmeth()ds[J].Talanta,2006,70(5):991—
419.
钢中夹杂物的常规定性分析
TORTORETOGiampietro,SCIABoLETTADomenico,RoTICIANISilvio
(ThyssenKrupp
Acciai
SpecialiTerni,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
万方数据
6
第27卷第4期
2007年4月
冶金分析MetallurgicalAnalysis
V01.27.No.4April,2007
{II
文章编号:1000—7571(2007)04—0001—06
RoutinequalitatiVeanalysisof
inclusionsinsteel
研究与试验报告
蒂TORTOREToGiampietro‘,SCIABOLETTADomenico,
ROTICIANISilvio
(ThyssenKrupp
Acciai
SpecialiTemi,Temi,Italy)
Abstr舵t:MoSt
microscopy
on
investigationsofinclusionsandprecipitateswere,andstillare,donebyoptical
polishedsteelsurfaces.Improvementoftheresolutionofpulsediscriminationanal—
ysis-opticalemiSsionspectrometry(PDA—OES)isexpectedinthe∞mingyearS.Size,numberandspatialdistribution
can
berecorded.Duringautomaticrnonitoring,combinedwitheitherelectron
is
probemicro—analysis(EPMA)orPDA-OES,ap01ishedsteelsurface
shapeanditssurfacecharacteristicsteUthehistoryof
to
scanned.Althou曲area
not
and
perimeteroftheinclusionsisrecorded,derivationoftheirshapesis
a
evident.Theinclusion’s
particularinclusion.Thereforebeingableaboutinclusion
readthehistorymayresultinadditional
to
infomation
a
fo瑚ation,growth
and
evolution.Theaimofthisworkwasfind
correlationbetweenSEM/EDSanalysisandOES/
to
PDAtechniques.ThePDA—oEStechniqueswereusedstaillleSssteel,aSwell
aS
analyzequalitativelytheinclusionsin
or
incarbonsteel.Onthebaseofthisstudy,Semi—quantitative
quantita—
tiveanalysisoftheinclusionswillbeexpectedtorealizebyconsideringtheheightandtheintensity
ofthepeakswithpropercompa“SOnKeywords:
to
referencematerials.
opticalemissionspectroscopy;non—
stainlesssteel;pulSediscriminationanalysis;
meta¨icinclusions
CLCnumber:0657.63
D0cumentcode:A
ThesteelindustryisfacedwiththechaUengeofproducinghigherqualityandcleanersteel,while
increasing
也eirdeannessindex.
Mostim怪缸gatiOnsofineIusionsa11d
were,aJldstiUare,dDnebyoptical
productivity.
onthisbase
significant
micI唧y
can
precipitates
on
pol—
progresshasbeenmadeintheanalySisofironand
iShedsteels1】rfaoes.
FH瑚1960on啪rds
elec臼Dnmi—
steel:sampleanalysistime,sensitivity,
andaccuracy
precision
clDscopybecamewid爱pread.Thisnotodye陇出lesin一
haveallbeensubstantiaUyimpt.oved
inthelastyears.
嘣i野monlaIgerm碰;mfications,butiteasilybeO(m=1:bined、^,ith删yticaltec:h11iques,calledelec旬Dn
at
Adl旧noedsClftwareapplicatjoninopticalerlliSsliCln
spectrometry,、ⅣitlltheaoquiSitionoft11e1ightintensity
p出rni静砌灿(EP凇)[1-2].In
small
EPMAthe
6ktmn
b哪,which
iSinScarulingrIⅪDdeuSed
鲥tted
byeachsin西esparkoft11ediScharge,opensforimaging,西v签riSe
t0“sSiIm
call
ofX-myS谢th
pr爱蛇nt.
H】ost
newgoalsintheapplicationofthiStEdlmque.Optical
wavelen戥hScharacteristicfbrt11eeleInentSTheapplic撕onofof出e
p;lrmneters
an
蹦SSion
Sple(=t1_cIⅡ1eterscoddnotodydisplay,within
a
EM厄PMA
chamctedSe
fewSeamds,the
d戚cal
O(mlp商tion
of
metal蛐一
printout,
and
describingt11eSteddediness.USing
ples,butaLts0,inreal6meandonthe
valllableinfbtTnation
saIlle
back_scatteredelectronsfbrimagingtheinduSionSshaw
ab珈lt小ejrindl】sion
o()ntent
Si鲥ficallt
00ntrast
to乱pohsheds渊“缸.The
Reoeiveddate:2006一09—16
Bio呻phy:GianlpietroTortoreto(1947一)。male。Ph.D。Laboratories
万方数据
mail:gi锄tof@1ibem.it.
Manager,ThyssenKrupp
Acciai
Speciali
Terni。E—
一1一
第27卷第4期2007年4月
冶金分析
V0l・27・No・4
MetauurgicalAnalysiS
April,2007
large
c0咖aSt
betweens乜eel
m缸x
a11dinclusions
en—
ablesautomaticmom幻ringif
a
sanlpkm0、唧mentsys—
t锄is
attached.Number,diameterandpedm酏erd
indusionscc疽TIbined、耐thrnicrpanalyses咖bereoDrd—
ed.Despiteiheauto姐ticmom砸ngthemetllodiSrd—
ativdvSlowdue
to
the
ti雠nec联;s奶7
f6f
accLlrate删一
ysis.
Spark—S0urce
optical
“ssion
Spec心mleny
((娅S),wmch
iS
s协dardforbulkstedanal姆s,∞m—
binedwithpulse
dbcri耐nationanalysis(PDA)haS
re—
cendybeendevelopedandismuchfaSterthanE ̄P—
MA[3—4|.In()ESPlDA,the
plaSnlacreates
ernissiC憷
of
li{出t、^,ith
wavden础scharactedsticfortheeIanents
pn葛ent.The
plaslm
is
producedduringelectricdis—
char_ge.Sincet11e
area
affectedbythe
pl猢is1arger
than吐眦of
an
dectmn
b咖for
EPⅣ睑,雠resolu—
tionofOESPDA
iS舢ch
less妇forEPMA,e.g.
30一50脚and
1—5
pm,re{;pectivd,5q].Inlp聊e—
m∞tdd旋Te9011】tion
d(黔PDAis镪【pe魄edh
the
∞mingyears.Size,mmiberandSpa6aldis试butioncan
be
re咖dod【9—10j.
AnalySis
are
performed
on
a
singleinstrument
at
clearlylower
costs,
in
comparison
to
existing
techniauesforsteelcleannesswhichare
time
con—
sumingand
expensive(SEM/EDSMicrograph).
AnOESmethodtoanalyseindusionsinstain—
lesssteelispresentedinthis
paper,acr.oss
a
study
ofthelightemittedbyeachsinglespark.Graphsofthe
overlappingof
the
lightsofelements,
con—
stituentoftheinclusions,areshowed.
Theaimof
our、∞rk
waStoanalySeexpected
differentphasesofoxides,carbidesandnitritesin
steelin
a
faStway,togivemore
infomation
tothe
productionandqualitycontr01.Atthe
momentitis
not
possible
a
quantitativeanalySis,wedonothave
referencematerialswitha
certifiedvalueofinctu—
sions,
nevertheleSs
a
qualitative
detemination
of
them
can
bealsouseful.
Theanalyticalprogramscan
beconfigured
aS
well
as
claSSicalpro罾rams,eachelement
canbecal—ibratedanddriftcorrected,theirresults
can
bedis-
played,stored,printedanddistributed,datahan—dlingakorithms
can
beeasilyselected
or
plugged
intothesoftware.
万方数据
一2—1
Experimental
IncIusiondetectionandanalysisweredone
un—
der
a
scanning
electron
microscope
SEM/EDS
CambridgeMod.with
tungsten
wiretodetectand
analyseallsecondphaseparticlesthatwereVisible
at
a
magnificationof1,000×.S涵ark—inducedopticalemission
spectroscopy
is
∞mmonlv
usedtodeterminethenominalchemistry
ofconductivesolidspecimens.
Inthiswork,
an
opticalEmissionSpectrometerARL4460ofThe卜
rno(乃rp.wasused.
Cbrrespondingopticalemissionintensityspec—
tra
can
berepresented
as
densityfunctionsobtained
byaccumulatingthenumberofpulSeSineachclass
ofintenSityallowedbythephotomultiplierSand
aS・
sociatedelectronicchain.
Thesespectra
are
usually
very
noisybecauseofsvstem
resolutionandanalysed
pulse
number
(1,500)limitations.
As
a
consequence,they
ex。
hibitimportantfillingdefects
atSomeintenSityleV。
els,alongwith
exceSS
fillings
at
otherleVels.
2
Inclusionsprecipitation
The{irst
st印doⅢre辩archwas幻ve《y,by
op—
ticalandscandng
inclusions
instajnIess
Steel
SaI]啊es.‰of伽dd删
dect姒1ical
midⅨ∞py,theoOilS,afbera
sellsitizing
them】al
tri舭nt
e)c成utedm
la_bOfat。fy
t0
predpi协tethephases,areshowed.
ADhotoofchromiumcarbides,obtainedafter
SenSitisingat675℃for1handat
a
magnification
of200X,isreportedinF谵.1:
Fig.1
se瞄iti髓dmicr憾tr眦ture(at675℃for
1
h)
Of
a
typic蚰austeniticstainlesss“埒l
(withtheevidence0fchmmiumc盯bid髂
M23c6
p陀cipitat酋)
Thefollowingfigure(Fig.2)referS
toto
ansee
EDS,
are
printed.From
theresults
we
can
say
austeniticstainlesssteelwhereitispossibleinclusions
whose
analysis,
thatthemaincompositionoftheinclusions
isbased
on
present
performedby
SEM/oxidesofA1,(、aandSi.
Fig.2
oxid鹤inclusionsina吣teniticstainIesssteeIarIdEI'sanaIysis
Fig.3
Thesameconclusions
can
oxid鹤incIusionsinausteniticstainIe蟠st∞landEDS蛆alysisbedroppeddownfromthefollowingsample.
InF培.4,anausteniticstainlesssteelstabilizedwithTiisreported,inthissamplewefoundinclu—sionsofTiNaccordingto
SEM/EDSanalySis。
Inconclusionthedistributionoftheindusionsindifferent
sampleswereanalysedby
SEM厄DS
can
micrOgraph.
Fromtheanalysisobtained,we
understandthatthe
are
followingoxidesandnitrideS
the
maincomponentsoftheinclusions:Cao,
Si02,A1203,TiN.
Wedid
not
considerthe
are
presence
ofFeandCr
oxidesbecausethey
l耗.4
themainconstituentsofthe
on
nt蛐i哪疵ridei眦I璐io璐in卸姚litic咖IIle略
titaniumandEDSanalysis
steelanalvsedandcouldinterfereanalysis.
SEM/EDS
steeIstabilizedby
万方数据
一3
第27卷第4期2007年4月
冶金分析v文27,No.4
April,2007
MetallurgicalAnalysis
3
IncIusionsanalysisbyoES
onceidentifiedthephases,by
highintensitypulsescouldcorrespondtoelements
containedininclusionswhenthev
and
anyto
arenot
due
to
SEM/EDS
kindofLABpollution.
Thechosenparameter
optical
Microscopy,we
startedthedetermination
indicatehighintensitypulsesistheaveragevalue
ofthembyOpticalEmissionSpectrometry.
Fmmthefollowinggraphs,whereeachsingle
sparkis
reported,wein
the
can
addedbythreetimesofstandarddeviationofthe
ones
||一^ihindicationofansparks.||Anof1argersizeof
oⅣer
assumethattheinclu.
theinclusionsisgiven
derofsixFig.5
a
or
thisreference
value(or—
In
an
sionsread
sampl毛sby
SEM厄DS
are
alSoninetimesofstandarddeviation).
readbyOES.
Thelowintensitypulsescorrespondtothe
sponse
re.
graph
indicating业03
inclusionsin
austeniticstainlesssteelisreported.Theoverlaps
ofelementsinsolutioninthemetalandthe
60∞
55∞50∞4S∞●—∞0
of02and趾pulseSindicatethepresence
of砧203.
3册
3∞D
2枷
1
2∞O
1脚
5∞
L
5∞
.{f.IJ|lJL』血I队,。u}J~一,“。…...。。LL血lu止.L止.-l~
…-”。’r
1’
湖枷
’’…rT…。n“…■…1-’r1Tr’r_P。r’-…'■’叮l‘■’…”’1●’'。’1—111I
嘲8∞’肋1抽’椭1枷1枷2彻
灿山
洲
”r_…。‘1j’胛T"
“I山II111山』柚idlI山。-.ILk|I|-川.1.山
l’I”,’『r’1’I"’_
■nH7Ir
r。1-。-1啊'T-r’1I『-
'_’’’’叩1”1■
伽
Fig.6
晰8∞
of
Typical粕alysis
steel
tit粕ium
nitrideincI晒io璐in
f电州ticstainI嘟
stabili跹dbytit粕iumbyoES(TiupNdown)
4
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s
In
a
tnstee-
V01.27.No.4ADril,2007
sampleof
ferriticstainless
to
see
steel,
aS
InF遮.7,、Ve
call
see,twodjfferemoverhpping
showedinFig.6,itisalsopossible
ence
thepres—ofthepea:I【sofsdiO。nandoxygenat也elowersideof
ofTiN.
sparkmmiberst11at朗叩hasizeSthe
presenoe
of
siQ.
12脚
11咖10咖9J啪
8埘
7∞06.O∞5.0∞
3脚2脚’脚
●.∞O
J
r池L从1.IJl|…lI-ILI
枷
枷
咖
鲫
.。lJj¨ll也“…I虬.L。h。l。。.:。|【J
'脚
1瑚
1枷
1枷
1枷
2咖
再电.7
PDA蛐alysis
spark
0f
Ca锄旧们碘}啪si弘蚰pIotted
upo
vs.
number(Ca
ox—
down)
We
didn’texactlyknowifaggregatesof
present
overlappingofthe
suggest
peaksofAlandSithatcould
an
idescouldbe
reaS0n
inthe
theinclusions.Fbrthis
of
our
thepresenceof
aggregate
or
clusterof
weexamined
reSponse
samples
an
sihcates(withstoichoiometryA12()3一Si()2).
andinsomeofthem,itwaspossibletofound
日6‘2De
6●2
枷蜘e∞嘲
Fig.8c盯bon
TypicaI粕alysis
in
of
chr帅ium
c盯bide
obtained
bythesignaIof
oES蛐aIysis(evidenceofIargerinte璐itypeab)andpu№in-
te砸itydistribution(hisbogram)ofc盯bonsignalsofehromiumcarbidesindusiO璐
FinanyinF谵.8,fI.omthesignalofcarbonof
an
PDA帆st∞1
with
quency
ofpeaksofCdeviation
over
the
average
plusthree
of
austeniticstainlesssteel18/8sensitised,thefre—standardcould
justify
the
presence
万方数据
5——
第27卷第4期冶金分析V。1.27.No.42007年4月
MetaUurgicalAnalySis
APril,2007
chromiumcarbide(Cr23C6).
Aboutthehigher
995.
sparknumberpeaks,theycouldrepresent
a
poSsi—
[3]PissenbergerA,Pissenberger
E.AutomaticCleanness
bleevidenceof
an
aggregatesofcarbide.
Instain—
Detemination
of
Pmduction
Sampleswith0ES/’PDA,
lesssteelscarbonitrides
as
well
7th
as
carbidescouldbe
J.Angeli(ed.):ProceedingsInternat[c].work—
and
present,we
are
stillinvestigatingon
theiridentifi—
shopPmgresSinAnal”icalChemistryintheSteelMetalIndustries,2006.
cationbothby
SEM/EDS
andbyOES.
[4]H哪merlin
M,MeillandaR,Falkb
H,et
a1.Applica—
4ConclusiOns
tionof
vacuumultmvioletlaSer—inducedbreaklown
spec—
trometryforsteelanalysiscompariSon谢thspark—optical
onthebaseoftheresultsobtaineditispossi—
锄iSSiollspectr㈨etry[J].SpectrochimicaActa:Part
B,
ble
tosay
thattheoES
can
beusedtoanalyse,in
a
2001,56(6):661—669.firststep,theinclusionspresentinstainlesssteel,
[5]RocaboisP,LehmannJ,Gaye
H,et
a1.Kineticsofpre—
as
wen
as
incarbonsteel[1].
cipitation
ofnon—metallicinclusionsduringSolidificationof
Of
courSe
themethod,abSOlutelyfast,isonly
steeI[J]。JoumaIofCryStaI
Growth,1999,198/199:
838—843.
qualitative.Cbnsideringtheheightandtheintedsi—
[6]FalkH,Wintjens
P.Evaluationof
Single.Sparksand
its
ty
ofthepeaks,after
a
proper
compariSonwithref—
Applicationsto
the
EvaluationofInclusions[J].Joumal
erence
materialsadhocprepared,thesecondstep
0fCrystal
Gro叭h,1999,413—419.
ofthisstudy,couldbe
a
semi—quantitative
or
quan—
[7]MeillandR,et
a1.Rapid
CharacterisationofHetero—
titativeanalysisoftheinclusions.
geneities(Inclusionsand
Segregation)bySpectralTech—
References
niques[J].JournalofCrystalGfowth,1999,420一427.
[8]Jo谢tt
R.Rapid
Detemination
ofsteelCleanliness[C].
[1]MullerE,ZuberC,B?hlenJM.on—Linespark—DAT
ECSC
Project72lO—GD/806FinalReport,1994.
fbrultimateeIementalanalvsisandadditionalmetalschar—
[9]MathyH,TusSetV,LamberigtsM.AnEvaluationof
acterization
with
0pticalEmissionSpectroscopy[Z].
SulphideIndusionContentAssessmentMethodsIn、,ac—ThermoARLAppliedResearchLaboratories,2006.
uum—ProcessedSteels,2006.
[2]MullerG,StahnkeF,Bleiner
D,Faststeel—cleanness[10]10。sta
A,silva.Th咖10dynamjc
aspectS
ofinduSilm∞画一
characterization
bymeansofIaser—assistedplasmaspec—ne刮119insteels[J].RareMetais,2006,25(5):412—
trametricmeth()ds[J].Talanta,2006,70(5):991—
419.
钢中夹杂物的常规定性分析
TORTORETOGiampietro,SCIABoLETTADomenico,RoTICIANISilvio
(ThyssenKrupp
Acciai
SpecialiTerni,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
万方数据
6