ICS77.080.01CCSH11

T/CSTM00011E-2021

Generalrulesfororiginalpositionstatisticdistributionanalysisbylaserinduced

breakdownspectroscopy

激光誘導(dǎo)擊穿光譜原位統(tǒng)計分布分析方法通則

(EnglishTranslation)

Issueddate:2021-04-16Implementationdate:2021-07-16

IssuedbyChineseSocietyforTesting&Materials，Zhongguancun

T/CSTM00011E-2021

Foreword

ThisdocumentisdraftedrefertotherulesgivenintheGB/T1.1-2020(Directivesforstandardization-Part1:Rulesforthestructureanddraftingofstandardizingdocuments)Attentionisdrawntothepossibilitythatsomeoftheelementsofthisstandardmaybethesubjectofpatentrights.Theissuingbodyofthisdocumentshallnotbeheldresponsibleforidentifyinganyorallsuchpatentrights.

ThisdocumentwasproposedbyCSTM/FC99(TheintegratedfieldtechnicalcommitteeofChineseSocietyforTesting&Materials).

ThisdocumentispreparedbyCSTM/FC99.

ThisEnglishdocumentwastranslatedbyCSTM/FC99.IncaseofanydoubtaboutthecontentsofEnglishtranslation,theChineseoriginalshallbeconsideredauthoritative.

T/CSTM00011E-2021

Generalrulesfororiginalpositionstatisticdistributionanalysisbylaserinducedbreakdownspectroscopy

Warning—Peopleusingthisdocumentshouldhavepracticalworkexperienceinformallaboratory.Inthis

document,notallpossiblesafetyissuesarepointedout.Theuserisresponsiblefortakingappropriatesafetyandhealthmeasures,andensuringcompliancewiththeconditionsstipulatedbyrelevantnationallawsand

regulations.

1Scope

Thisdocumentspecifiesamethodoforiginalpositionstatisticdistributionanalysismethodbylaserinducedbreakdownspectroscopy.Thisdocumentincludestheterminology,basicprinciples,generalrequirementsforequipment,samples,analysisprocedures,etc.

Thisdocumentisapplicabletothestandardsfororiginalpositionstatisticaldistributionanalysisbylaser-inducedbreakdownspectroscopytobepreparedorrevised.

2Normativereferences

Thefollowingdocumentsarereferredtointhetextinsuchawaythatsomeoralloftheircontentconstitutesrequirementsofthisdocument.Fordatedreferences,onlytheeditioncitedapplies.Forundatedreferences,thelatesteditionofthereferenceddocument(includinganyamendments)applies.

GB/T14666-2003Termsforanalyticalchemistry

GB/T24213-2009Generalrulesfororiginalpositionstatisticdistributionanalysismethod

3Termsanddefinitions

Forthepurposesofthisdocument,thetermsanddefinitionsgiveninGB/T14666-2003,GB/T24213-2009andthefollowingapply.

3.1

originalpositionstatisticdistributionanalysis

Assampleisscannedandexcitedwithintheidentifiedanalysisarea,thespectralsignalscorrespondingtotheanalysispositionarecollectedsynchronously,andanalysedbymathematicalstatisticsmethods.Thedistributionstatisticalanalysisofthechemicalcompositionsandinclusionswithintheareaarerealized;

3.2

laserinducedbreakdownspectroscopy(LIBS)

Byfocusingthepulsedlaseronthesamplesurface,theplasmaisformedandtheemissionspectrumsareanalyzedtoachievetheinformationofthecompositionsandcontent;

3.3

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pulsefrequency

Numberoflaserpulsesemittedinonesecond;

3.4

laserburnspot

Spotsformedbylaserexcitationonthesamplesurface;

3.5

linescanningspeed

Linearvelocityofthelaserbeamwhichisrelativetothesamplemovement;

3.6

stepspace

Alongthescanningdirection,thedistancebetweenthecentersoftwoadjacentshots;

3.7

rowspace

Thedistancebetweenthecentersoftwoadjacentlinesofshotsunderlinescanmode;

3.8

scanningarea

Pre-setanalysisareaonsample‘ssurface;

3.9

burnarea

Ablationareaformedbythelaserwhilescanningandexcitingthesample;

3.10

specificpositioncontent

Theelementcontentwhichareobtainedonthespecificpositionofthesamplebylaserspectroscopyanalysis；

3.11

confidenceintervalofthecontents

Acontentintervalwhichiscenteredbythemediancontentvalueunderacertaindegreeofconfidence;[Source:GB/T24213-2009,3.9]

3.12

two-dimensioncontourmapofcontents

Themapthatshowsthecontentdistributionofspecificelementcorrespondingtocoordinates(X,Y)withinthescanningarea.Differentcolorsorgreylevelsindicatethecorrespondingcontent(asshowninFigure1);

[Source:GB/T24213-2009,3.10]

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Fig.1two-dimensioncontourcontentchartFig.2three-dimensioncontentview

3.13

three-dimensionimageofthecontents

Basedonthetwo-dimensionmapofthecontents，thevaluesofZaxisareusedadditionallytorepresentthe

contentsofelements(asshowninfigure2);

[Source:GB/T24213-2009,3.11]

3.14

linedistributiongraphofthecontents

Thegraphthatshowsthecontentchangesalongx(ory)directionofthespecificelement,wheny(orx)isfixed,(asshowninfigure3);

[Source:GB/T24213-2009,3.12]

Fig.3LinedistributiongraphofthecontentsFig.4Content-frequencyratiodistribution

3.15

content-frequencyratiodistribution

Withinthescanningarea，thecontentofacertainelementisusedasX-axis,theratioofthefrequencyofa

specificcontentvaluetothefrequencyofallmeasurementsisusedasY-axis（asseeninfigure4）.

3.16

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statisticresultsindifferentcontentrange

Withinthescanningarea,theratioofthefrequencyofthespecifiedcontentsegmenttothetotalmeasurement(asshowninfigure5).

[Source:GB/T24213-2009,3.14]

Fig.5Statisticresultsindifferentcontentrange

3.17

regionalcontent-frequencydistribution

Inanygivenareawithinthescanningarea,content-frequencydistributioncanbeperformed.Inthe

content-frequencydistributiongraph，thepositioncontentistakenasX-axis,andtheratioofthecontentofa

specificpositiontothecontentofallpositionsintheareaistakenasY-axis(asshowninfigure6);[Source:GB/T24213-2009,3.15]

Fig.6Regionalcontent-frequencydistribution

T/CSTM00011E-2021

3.18

maximumsegregationdegree

Withinthescanningarea,therearetwowaystocalculatethemaximumsegregationdegreeofanelement,themaximumdegreeofpoint-segregationM(x,y)andmaximumdegreeofmicro-segregationM(s).

Themaximumdegreeofpoint-segregationisexpressedbytheratioofthecontentcmatthehighestcontent

positionofaspecificelementtotheaveragecontentc,asshowninformula(1):

M(x,y)=cm/c （

1

）

Themaximumsegregationdegreeofthemicro-zoneM(s)isexpressedbytheratioofthemaximumaverage

contentcsofaspecificelementinanareaof1mm2totheaveragecontentc,asshowninformula(2):

M(s)=cs/c （

2

）

3.19

statisticsegregationdegree（S）

Withinthescanningarea,thecontentdistributionofaspecificelementisanalyzedbymathematical

statistics.ThestatisticalsegregationdegreeSatthe95%confidencelevelisobtained，whichiscenteredon

themedianvalueandwithintheconfidenceinterval［c1,c2］.Siscalculatedas:

S=(c2-c1)/2c0……（3）

where:

c0--medianvalue;

c1,c2--theupperandlowerlimitoftheconfidenceinterval;

Thelargerthevalueofthestatisticalsegregationdegree,themoreseriousthesegregationis.Thestatisticalsegregationdegreeis0whilethereisnosegregation.

[Source:GB/T24213-2009,3.17]

3.20

statisticfittingdegree

Withinthescanningarea,theratioofthecontentfittingsofanelementatallpositionstothe

contentspecified(orcontentsegments).

[Source:GB/T24213-2009,3.18]

3.21

inclusionstateanalysis

Whenthereareinclusionsinthesample,anabnormalspectralsignalwithhigherintensitythan

usualwillbegenerated.Theintensityandfrequencyofthesignalcancharacterizetheparticle

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sizeandcontentoftheinclusions.Throughthesynthesisandanalysisofabnormalsignalsof

differentelements,differenttypesofinclusionscanbequantitativelyanalyzed.

3.22

apparentdensity（DJ）

Withinthescanningarea,thesumofthecontentciofeachelementatthelaserexcitationposition.

DJ=Σci

3.23

averageapparentdensity（D）

Withinthescanningarea,theaverageapparentdensityofNpositions;

D=ΣDJ/N

[Source:GB/T24213-2009,3.21]

4Theory

Ahigh-energylaserbeamfromtheexcitationlightsourceisfocusedonthesample,thesurfaceofthesampleisinstantlyvaporizedandthefreeelectronstransitfromalow-energystatetoahigh-energystate.Thehigh-energystateisunstable,thefreeelectronsreturntogroundstateintheformofreleasedphotons.Qualitativeanalysisisrealizedaccordingtothewavelengthofthespectralline,meanwhilequantitativeanalysisisrealizedaccordingtotheintensityofthespectralsignal.Byscanningthespecifiedareabythelaser,thecompositiondistribution,theinclusioncontentdistributionandtheinclusionsizedistributionandotherinformationofthematerialcanbeobtained.

Performedtheoriginalpositionstatisticdistributionanalysisbylaser-inducedbreakdownspectroscopy(LIBS)ontherelativemotionsample.Theexcitedemissionspectraaredispersedintocharacteristicspectralline,theemissionlineintensitiesoftheselectedreferencelineandtheanalysislinearemeasured.Thecalibrationcurveissetupbythestandardsamples.Accordingtotheintensitiesandthecalibrationcurve,theelementscontentofthescanningareaisobtained.Theexcitationlocationinformationissynchronouslyobtained.Bystatisticaldistributionanalysis,variousinformationusedtoevaluatethedistributionofelementswithinthescanningareaisobtained,suchastwo-dimensioncontourmapofcontents,three-dimensionimageofthecontents,linedistributiongraphofthecontents,content-frequencydistribution,regionalcontent-frequencydistribution,maximumsegregationdegree,statisticsegregationdegree,statisticfittingdegree,apparentdensity,andthedistributionofthetypes,contentandparticlesizeofinclusions,etc.

5Apparatus

T/CSTM00011E-2021

5.1Analyzer

Thelaser-inducedbreakdownspectroscopyoriginalpositionstatisticanalyzerismainlycomposedofthefollowingunits:laserlightsource,laserfocusingopticalpath,three-dimensionalmobilesamplestage,lightsplittingsystem,signalacquisitionsystem,dataprocessingsystem.

TherearemanyfactorstoinfluenttheresultsofLIBS-OPA,suchasthedistancebetweenthelensandthesamplesurface,thebeamenergyofLIBS,theambientgasandpressure,delayedtime,theheightofsamplestageallhaveeffectsontheintensityofspectralline.Whilepre-excitationandintegralpulsewilleffecttheaccuracyoftheresults.

5.2Lasersource

Asystemthatcanprovideacontinuousandstablelaserwhichcanrealizetheenergycontrollableandthefrequencyadjustable.

5.3Laserfocusingopticalpath

Focussingthelaseremittedonthesamplesurface,whichismainlycomposedofacollimatorlens(group),adiaphragm,andafocusinglens(group).

5.4Three-dimensionalmobilesamplestage

Amechanicalmobilestagethatcansupportthesamplewhileexcitedandprovidecontinuousmovementofthesample.Ifneeded,low-pressurehigh-purityargoncanbeusedforatmosphereprotection.

5.5Lightsplittingsystem

Consistsofcollimatinglens,incidentslit,grating,etc.Thelightenterstheincidentslitthroughthecollimatinglens,slittedbythegrating.Andthecharacteristicspectrallightofeachelemententersthephotomultipliertube(PMT),chargecoupleddevice(CCD)orotherspectradetector.

Thereciprocaloftheprimaryspectraldispersionofthespectroscopicsystemshouldbelessthan0.6nm/mm,andthewavelengthrangeshouldbebetween170.0nm~420.0nm.IfC,P,Sandothershort-waveelementsneedtobeanalyzed,aninertgassystemoravacuumsystemshouldbeused.Andthevacuumlevelofthespectrometershouldbelessthan3Pa.

5.6Signalacquisitionsystem

Tocollectandstoreallspectralsignalswithintheexcitationareawithhighprecision.

5.7Scanningsystem

Accordingtothepre-setroutetoscanthesampletorealizethelineorsurfacescanninganalysisinthesamplearea.

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5.8Dataprocessingsystem

Everylaserpulsesignalisrelatedtothestateofitsexcitationposition.Considerablequantitiesofspectrumsignalsarecollectedbythehigh-precisionacquisitionsystemandtheintensitiesarestored.Bymathematicalstatisticalanalysis,theinformationofthepositioncontentdistributionoftheelementsandtherelateddefectstatedistributionrelatingtotheoriginalpositioncanbeobtained.

Inthissystem,thedistributionlawpatternoftheelementsmeasuredaredirectlycharacterizedbytwo-dimensioncontourmapofcontents,three-dimensionimageofthecontents,linedistributiongraphofthecontents,content-frequencydistribution,apparentdensitydistributionmap,inclusiondistributionmap.Andaveragecontent,maximumsegregationdegree,statisticsegregationdegree,statisticfittingdegree,averageapparentdensity,andthetype,contentandparticlesizeofinclusionsareappliedtoexpressthedistributiontoo.

6Samples

6.1Typesofthesample

Thesamplescanbedividedintotwotypes,whicharedirect-analysissamplesandsamplesneedtobeprepared.

6.2Sampling

Thesampleshouldbecutandpreparedwithregularshapeandeasy-to-hold.Thesampleanalysissurfaceusuallycoverscertaincharacteristicareassuchasthecentralareaoftheslaborthebillet.

6.3Preparation

Normallycuttingandsurfacetreatmentareneeded.Wirecuttingorsawingisusedforcuttingtothesuitablesize.Thesurfaceofthesampleshouldbeassmoothaspossible.

Agrinderormillingmachineisusedtotreatthesurface.Thesamplesurfaceshouldbesmoothandclean.ThesurfaceroughnessRaofthesampleshouldbelessthan0.3μm.Whenthegrinderormillingmachineis

unavailable,thegrindingequipmentisneededontheanalysisrequirements.Itisrecommendedthattheparticlesizeofthegrindingmaterialshouldbelessthan48μm.Thegrindingmaterialisusuallyalumina,zirconiaor

siliconcarbide.Toavoidthesamplecontaminationbythegrindingmaterialaspossible.

7Standardsamples,standardizationsamplesandcontrolsamples

7.1Standardsamples

Standardsamplesareusedtomakecalibrationcurvesintheoriginalpositionstatistical

distributionanalysisoflaser-inducedbreakdownspectroscopy.Thestandardsampleshouldbea

certifiedreferencematerials/samples,andthecontentofeachelementshouldhaveagradient

andcovertherangeofthemeasurement.Theselectedstandardsampleshouldmatchthesample

analyzed.Thenumberofshotspotsforthestandardsample'ssurfacescanningisshouldnotbe

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lessthan9.

7.2Standardizationsamples

Standardizationsamplesareusedtocorrectthedriftoftheinstrument,whichshouldbeuniform.

Whentwosamplesareusedforstandardization,thecontentsofeachelementshouldbetaken

closetotheupperandlowerlimitsofthecalibrationcurve.Theanalysisconditionsaresamewith

thestandardsamples.

7.3Controlsamples

Thecontrolsampleshaveasimilarmetallurgicalprocessandchemicalcompositionwiththe

analysissample,andthecompositionisevenlydistributed.Whennecessary,itcanbeusedto

calibratetheresultstocontroltheaccuracyofthemeasurement.Theanalysisconditionsare

samewiththestandardsamples.

8Analysis

8.1Environmentalrequirements

ThelaboratoryoftheLIBSoriginalpositionstatisticaldistributionanalyzershouldbeshockproof

andclean.Generally,theindoortemperatureshouldbekeptat25℃±2℃,andtherelative

humidityshouldbe40%~70%.

8.2Inspectionofopticalsystem

Thecollimatinglensshouldbecleanedregularly.Theopticalpathshouldbecalibrated

periodically.

8.3Stabilizationoftheinstrumentstate

Tomaketheinstrumentworkstable,thelasershouldbepre-poweredforanappropriatetime.The

opticalsystemshouldbepre-heatedtoaconstanttemperature.Whenavacuumopticalsystemis

used,thevacuumdegreelevelshouldbelessthan3Pa.

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Whenrestartinginstrumentafteralongshutdown,generallythepower-ontimeisnotlessthan4

hoursbeforeanalyzing.

Atestsampleshouldbepre-excitedbeforetheanalysistoensurethattheinstrumentisstableand

theanalysiscanbedone.

8.4Selectionofstandardsamplesandconfigurationtheworkingcondition

Accordingtothetypeandchemicalcompositionofthesample,standardsamplesand

standardizationsamplesareselected.

Accordingtotheanalysiselementandtheircontentrangeofthesamples,thereferenceline,

analysisline,excitati