1、DRAFT FOR DEVELOPMENT DD ENV 14273:2002 Advanced technical ceramics Ceramic powders Determination of crystalline phases in zirconia ICS 81.060.30 NO COPYING WITHOUT BSI PERMISSION EXCEPT AS PERMITTED BY COPYRIGHT LAWDD ENV 14273:2002 This Draft for Development, having been prepared under the directi
2、on of the Materials and Chemicals Sector Policy and Strategy Committee, was published under the authority of the Standards Policy and Strategy Committee on 13 June 2002 BSI 13 June 2002 ISBN 0 580 39807 2 National foreword This Draft for Development is the official English language version of ENV 14
3、273:2002. This publication is not to be regarded as a British Standard. It is being issued in the Draft for Development series of publications and is of a provisional nature because it is considered that further experience is required in its application before it is converted into a European and hen
4、ce British Standard. It should be applied on this provisional basis, so that information and experience of its practical application may be obtained. Comments arising from the use of this Draft for Development are requested so that UK experience can be reported to the European organization responsib
5、le for its conversion into a European Standard. A review of this publication will be initiated 2 years after its publication by the European organization so that a decision can be taken on its status at the end of its three-year life. The commencement of the review period will be notified by an anno
6、uncement in Update Standards. According to the replies received by the end of the review period, the responsible BSI Committee will decide whether to support the conversion into a European Standard, to extend the life of the prestandard or to withdraw it. Comments should be sent in writing to the Se
7、cretary of BSI Technical Committee RPI/13, Advanced technical ceramics, at 389 Chiswick High Road, London W4 4AL, giving the document reference and clause number and proposing, where possible, an appropriate revision of the text. A list of organizations represented on this committee can be obtained
8、on request to its secretary. Cross-references The British Standards which implement international or European publications referred to in this document may be found in the BSI Standards Catalogue under the section entitled “International Standards Correspondence Index”, or by using the “Find” facili
9、ty of the BSI Standards Electronic Catalogue. Summary of pages This document comprises a front cover, an inside front cover, the ENV title page, pages 2 to 14, an inside back cover and a back cover. The BSI copyright date displayed in this document indicates when the document was last issued. Amendm
10、ents issued since publication Amd. No. Date CommentsEUROPEANPRESTANDARD PRNORMEEUROPENNE EUROPISCHEVORNORM ENV14273 May2002 ICS81.060.30 Englishversion AdvancedtechnicalceramicsCeramicpowders Determinationofcrystallinephasesinzirconia CramiquestechniquesavancesPoudrescramiques Dterminationdesphasesc
11、ristallinesdanslazircone HochleistungskeramikKeramischePulverBestimmung derkristallinenPhaseninZirconiumoxid ThisEuropeanPrestandard(ENV)wasapprovedbyCENon11April2002asaprospectivestandardforprovisionalapplication. TheperiodofvalidityofthisENVislimitedinitiallytothreeyears.AftertwoyearsthemembersofC
12、ENwillberequestedto submittheir comments,particularlyonthequestionwhethertheENVcanbeconvertedintoaEuropeanStandard. CENmembersarerequiredtoannouncetheexistenceofthisENVinthesamewayasforanENandtomaketheENVavailablepromp tly atnationallevelinanappropriateform.Itispermissibletokeepconflictingnationalst
13、andardsinforce(inparalleltothe ENV)untilthefinal decisionaboutthepossibleconversionoftheENVintoanENisreached. CENmembersarethenationalstandardsbodiesofAustria,Belgium,CzechRepublic,Denmark,Finland,France,Germany,Greece, Iceland,Ireland,Italy,Luxembourg,Malta,Netherlands,Norway,Portugal,Spain,Sweden,
14、SwitzerlandandUnitedKingdom. EUROPEANCOMMITTEEFORSTANDARDIZATION COMITEUROPENDENORMALISATION EUROPISCHESKOMITEEFRNORMUNG ManagementCentre:ruedeStassart,36B1050Brussels 2002CEN Allrightsofexploitationinanyformandbyanymeansreserved worldwideforCENnationalMembers. Ref.No.ENV14273:2002EENV14273:2002(E)
15、2 Contents page Foreword 3 1 Scope 3 2 Normativereferences 3 3 Principle 3 4A p p a r a t u s 4 5 Samplepreparation 4 6 Testprocedure 4 6.1 Qualitativeanalysis 5 6.2 QuantitativeanalysisMethodA:Polymorphmethod 5 6.3 QuantitativeanalysisMethodB:Fullpatternmethod 5 7 Qualitativeandquantitativeanalysis
16、oftherecordedXraydiffractionpattern 5 7.1 Qualitativeanalysis 5 7.2 QuantitativeanalysisMethodA:Polymorphmethod 6 7.2.1 Calculation 6 7.3 QuantitativeanalysisMethodB:Fullpatternmethod 9 7.3.1 Symbolsanddefinitions 9 7.3.2 Calculation 10 7.4 Limitationstothequantitativeanalysis 11 7.4.1 Generallimita
17、tions 11 7.4.2 MethodA:Polymorphmethod 11 7.4.3 MethodB:Fullpatternmethod 11 8 Testreport 11 8.1 Qualitativeanalysis 11 8.2 Quantitativeanalysis 12 AnnexA (normative) Determinationofstabiliseramountfromcellparameters 13 Bibliography 14ENV14273:2002(E) 3 Foreword Thisdocument(ENV14273:2002)hasbeenpre
18、paredbyTechnicalCommitteeCEN/TC184 “Advancedtechnicalceramics“,thesecretariatofwhichisheldbyBSI. AnnexAisnormative. ThisPrestandardincludesaBibliography. AccordingtotheCEN/CENELECInternalRegulations,thenationalstandardsorganizationsofthe followingcountriesareboundtoannouncethisEuropeanPrestandard:Au
19、stria,Belgium,Czech Republic,Denmark,Finland,France,Germany,Greece,Iceland,Ireland,Italy,Luxembourg,Malta, Netherlands,Norway,Portugal,Spain,Sweden,SwitzerlandandtheUnitedKingdom. 1Scope ThisEuropeanPrestandardspecifiesamethodfortheroutinequalitativeandquantitative determinationofthecrystallinephase
20、s(monoclinic,tetragonalandcubic)presentinzirconiapowders usingXraypowderdiffraction. 2 Normativereferences ThisEuropeanPrestandardincorporatesbydatedorundatedreferenceprovisionsfromother publications.Thesenormativereferencesarecitedattheappropriateplacesinthetextandthe publicationsarelistedhereafter
21、.Fordatedreferences,subsequentamendmentstoorrevisionsofanyof thesepublicationsapplytothisEuropeanPrestandardonlywhenincorporatedinitbyamendmentor revision.Forundatedreferencesthelatesteditionofthepublicationreferredtoapplies(including amendments). ENISO/IEC17025 Generalrequirementsforthecompetenceof
22、testingandcalibrationlaboratories (ISO/IEC17025:1999). 3Principle Thequalitativeandquantitativedeterminationofthecrystallinephasespresentinagivenzirconia powderisderivedfromtheXraydiffractionanalysisofarepresentativesampleofthispowder. Thequalitativeanalysisreliesonacomparisonoftherecordedspectrumwi
23、thavailablereferencedata (e.g.ICDDJCPDSdatabase). Forthequantitativeanalysis,twomethodsareused:thepolymorphmethodandthefullpattern method.Thelatterconsistsofdeterminingscalefactorsbyaleastsquaresprocedureinvolvingall recordeddiffractionpeaks1,2.Theformerisawellestablishedmethod,detailsofwhichcanbe f
24、oundinbasictextbooks3;itreliesonacomparisonofthemeasuredintensitiesofselected reflectionsfromthepreviouslyidentifiedphases. NOTE AthirdmethodavailableforquantitativeanalysisistheRietveldmethod.Thismethoddeterminesthe phaseconstitutionofthesamplebyfittingthewholeXraydiffractionspectrumthroughaniterat
25、iverefinement approach.Thisrefinementcanbelimitedtothescalefactorsofeachphasepresent(i.e.thevolumefractionof thephases)orcanaddressawholesetofparameters(e.g.cellparameters,atomicpositions).AlthoughitisENV14273:2002(E) 4 recognisedthatRietveldrefinementisprobablythemostreliablemethodandismoreandmorep
26、roposedin commercialXRDpackagesforquantitativeanalysis,thismethodisatpresentbeyondthescopeofthis Prestandard. 4Apparatus DataacquisitionisperformedusingaBraggBrentanodiffractometer.Thefollowingexperimental settingsarerecommended: CopperXraytube; Precisegoniometer(twothetaerror 0,5); Primarysollersli
27、twithadivergence 2,5; 5 Divergenceslit 1; Receiving slit 2mm; Scatterslit 1; Secondary monochromator; Narrowlinefocus. NOTE Inthosecaseswherethesamplepreparationleadsinevitablytoaninhomogeneousgrainstructure and/orcomposition(e.g.grainswithaninhomogeneousradialphasedistribution),theuseofanXraytubewi
28、th shorterwavelength,forinstance,amolybdenumXrayorsilverXraytube,isrecommended.TheshorterXray wavelengthprovidesagreaterdepthofpenetrationresultinginamorerepresentativeanalysisinthesecases. 5 Samplepreparation Inordertoavoidprimaryextinctionandassuregoodstatistics,thepowdertobeanalysedshallhavea hom
29、ogeneousgrainsizelessthan40m. Byanadequatesamplingprocedure,arepresentativetestsampleofthispowderistakenandpressed intothecavityofthesampleholder.Usethebackfillpressingtechniquetoobtainaflatandsmooth samplesurfaceandtoreducepreferredorientation.Thedimensionsofthesampleholderwillbesuch thatXraysirrad
30、iatingoutsideofthesamplevolumecanbeavoided. NOTE Ifthepowderisobtainedfromasolidmonolithicsamplebycomminution(e.g.usingacrushingjawin combinationwithavibratorymilloralike)itisnecessarytobeawarethatthesamplepreparationmayaffectthe typeandamountofthecrystallinephasespresentandthat,accordingly,thephase
31、compositiondeterminedmay beirrelevant. 6 Testprocedure Settheexcitationvoltagetoatleast40kVandthecurrentintensityattheanodeofthecopperXray tubetoatleast35mA. NOTE IfadifferentXraytubeisused,changetheexcitationparametersaccordingly. Dataacquisitionispreferablyperformedinthestepscanningmode,thestepsiz
32、ebeingsetbetween 0,01and0,05twotheta.Alternativelyrecordthespectrumundercontinuousmodewithan integrationwidthof0,01or0,02.ENV14273:2002(E) 5 6.1 Qualitativeanalysis Setthescanningrangefrom10to80twothetaandrecordthewholeXraydiffractionpattern.Select acountingtimesuchthatagoodpeaktobackgroundsignalrat
33、ioisobtained.Practically,itshouldbe sufficientlylongtoobtaina s rel 0,02forthemaximumpeakintherangescanned.Therelative standarddeviation, s rel ,isgivenby N N N N b t b t rel - + = (1) with N t thetotalcountsand N b thecountsofthebackground. 6.2 QuantitativeanalysisMethodA:Polymorphmethod Forthepoly
34、morphmethodcollectingthedataunderthefollowingspecificconditionsisrecommended. Definetwomeasurementsprograms: Thefirst,scanbetween26,5and33,5twotheta,withacountingtimesuitablefor achievinga s rel 0,01onthemaximumpeak; Thesecond,scanbetween70and77twotheta,withacountingtimesuitablefor achieving s rel 0
35、,02onthemaximumpeak; 6.3 QuantitativeanalysisMethodB:Fullpatternmethod ForthefullpatternmethodtheXrayspectrumrecordedforthepreliminaryqualitativeanalysisshallbe used. 7 QualitativeandquantitativeanalysisoftherecordedXraydiffraction pattern 7.1 Qualitativeanalysis Useanautomaticormanualsearchandident
36、ifythecrystallinephasespresentaccordingtotheICDD JCPDSPDFreferencedatabank. NOTE Thefollowingdatasetsarerecommended,basedonthepresentavailableinformation.However,asthe ICDDJCPDSPDFdatabankisregularlyupgraded,foranexactanalysis,updateddatasetsshouldbeused.ENV14273:2002(E) 6 Crystallinephase JCPDSPDFN
37、r. Monoclinic(Baddeleyite,syn) 371484 Tetragonal 421164or170923 Cubic(pure) 270997 Cubic(yttriadoped) 371307 Cubic(calciadoped) 260341 7.2 QuantitativeanalysisMethodA:Polymorphmethod 7.2.1Calculation CalculationoftheintegratedintensitiesI(hkl) phase Theintensities I(hkl) phase tobeusedinsubsequentca
38、lculationaretheintegratedintensitiescomputedfromfitted andseparatedpeaks. NOTE1 Duetooverlappingofthepeaksofdifferentphasesitisrecommendedforthedeterminationofpeakintensitiestouse aprofilefittingmethod.Theprogramusedshouldincorporateaprofileshapefunctionsufficientlyflexible(e.g.PseudoVoigt , Voigtor
39、PearsonVII;notonlyGaussianorCauchy).Profilefittingprogramsareavailableinmostoftheinstrumentalsoftware packagesonthemarket.Alternativelytheycanbeobtainedfromvarioussources4. NOTE2 Theuseofgraphicalmethodsisinallcasesdiscouraged. CalculationoftheintensityfactorsR(hkl) phase Areliabledeterminationofthe
40、crystallinephasecompositionofthepowdersamplebythepolymorphmethod requirestheuseofcorrectintensityfactorsvalues.Thisinturnimpliesapreciseknowledgeofthecrystallographic structureofthephasespresent. TherecommendedintensityfactorvaluesarereportedinTable1below.Foranyotherzirconia/stabilisersystem and/orr
41、eflection,derivationoftheintensityfactorsshouldbedoneaccordingtoequation(2)usingrelevant crystallographicdataavailablefromtheliterature. 2 2 hkl hkl phase . . ). 2 ( ) ( V F p LP hkl R = (2) with LP(2q )theLorentzPolarizationfactor,correctedifneededfortheinfluenceofthemonochromatorcrystal, p hkl the
42、multiplicityfactorofthespecificreflection, F hkl thestructurefactorand V,thevolumeoftheunitcell.Fora detailedexplanationofthesefactors,oneshouldrefertothe“InternationalTablesforXrayCrystallography“5.ENV14273:2002(E) 7 Table1Recommendedintensityfactorsforselectedreflections Stabiliser Phase R(hkl ) R
43、ef Monoclinic 3 , 60 ) 111 ( m = R 8 , 84 ) 11 1 ( m = - R Yttria Tetragonal % mol . 2523 , 1 71 , 194 ) 101 ( 5 . 1 t YO R - = 6 % mol . 091046 , 0 5248 , 4 ) 004 ( 5 . 1 t YO R - = 6 % mol . 2252 , 0 759 , 10 ) 220 ( 5 . 1 t YO R - = 6 Cubic % mol . 39054 , 1 222 , 183 ) 111 ( 5 . 1 c YO R + = 6 %
44、 mol . 0321621 , 0 6733 , 12 ) 400 ( 5 . 1 c YO R - = 6 Magnesia Cubic % mol . . 6796 , 2 65 , 195 ) 111 ( c MgO R - = 7 Calcia Cubic % mol . . 3726 , 2 65 , 195 ) 111 ( c CaO R - = 7 NOTE1 Theaboveequationsassumethestabilisercontentisknown,forexampleasaresultofapreliminarychemical analysisofthepowder(e.g.byXrayfluorescenceanalysis). NOTE2 Inthecaseinwhichthestabiliseramountisunknown,thestabilisercontent
