1、| | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | BRITISH STANDARD BS 6043-1.10:2000 ISO 129
2、77:1999 ICS 71.100.10 NO COPYING WITHOUT BSI PERMISSION EXCEPT AS PERMITTED BY COPYRIGHT LAW Methods of sampling and test for carbonaceous materials used in aluminium manufacture Part 1: Electrode pitch Section 1.10: Determination of volatile matter contentThis British Standard, having been prepared
3、 under the direction of the Sector Committee for Materials and Chemicals, was published under the authority of the Standards Committee and comes into effect on 15 January 2000 BSI 01-2000 ISBN 0 580 35776 7 BS 6043-1.10:2000 Amendments issued since publication Amd. No. Date Comments National forewor
4、d This British Standard reproduces verbatim ISO 12977:1999 and implements it as the UK national standard. It supersedes BS 6043-1.10:1994 which is withdrawn. The UK participation in its preparation was entrusted to Technical Committee CII/24, Raw materials for the aluminium industry, which has the r
5、esponsibility to: aid enquirers to understand the text; present to the responsible international/European committee any enquiries on the interpretation, or proposals for change, and keep the UK interests informed; monitor related international and European developments and promulgate them in the UK.
6、 A list of organizations represented on this committee can be obtained 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 “Inter
7、national Standards Correspondence Index”, or by using the “Find” facility of the BSI Standards Electronic Catalogue. A British Standard does not purport to include all the necessary provisions of a contract. Users of British Standards are responsible for their correct application. Compliance with a
8、British Standard does not of itself confer immunity from legal obligations. Summary of pages This document comprises a front cover, an inside front cover, the ISO title page, pages ii to iv, pages 1 to 10, an inside back cover and a back cover. The BSI copyright notice displayed in this document ind
9、icates when the document was last issued.Reference number ISO 12977:1999(E) ISO 1999 INTERNATIONAL STANDARD ISO 12977 First edition 1999-12-01 Carbonaceous materials used in the production of aluminium Pitch for electrodes Determination of volatile matter content Produits carbons utiliss pour la pro
10、duction de laluminium Brais pour lectrodes Dtermination de la teneur en matire volatileii blankISO12977:1999(E)iii Contents Page Foreword.iv 1 Scope1 2 Normativereferences1 3 Term,definitionandsymbols.1 4 Principle2 5 Reagents.3 6 Apparatus.3 7 Samplingandpreparationofthetestsample.4 8 Preparationof
11、thetestsolutions4 9 PreparationofthecalibrantsolutionsolutionC5 10 Selectionofchromatographicconditions.5 11 Calibration5 12 Determination.6 13 Calculationandexpressionofresults.6 14 Precision.8 15 Testreport9 AnnexA(informative)Boilingpointsofthecalibrantcompounds10ISO12977:1999(E) iv Foreword ISO(
12、theInternationalOrganizationforStandardization)isaworldwidefederationofnationalstandardsbodies(ISO memberbodies).TheworkofpreparingInternationalStandardsisnormallycarriedoutthroughISOtechnical committees.Eachmemberbodyinterestedinasubjectforwhichatechnicalcommitteehasbeenestablishedhas therighttober
13、epresentedonthatcommittee.Internationalorganizations,governmentalandnon-governmental,in liaisonwithISO,alsotakepartinthework.ISOcollaboratescloselywiththeInternationalElectrotechnical Commission(IEC)onallmattersofelectrotechnicalstandardization. InternationalStandardsaredraftedinaccordancewiththerul
14、esgivenintheISO/IECDirectives,Part3. DraftInternationalStandardsadoptedbythetechnicalcommitteesarecirculatedtothememberbodiesforvoting. PublicationasanInternationalStandardrequiresapprovalbyatleast75%ofthememberbodiescastingavote. AttentionisdrawntothepossibilitythatsomeoftheelementsofthisInternatio
15、nalStandardmaybethesubjectof patentrights.ISOshallnotbeheldresponsibleforidentifyinganyorallsuchpatentrights. InternationalStandardISO12977waspreparedbyTechnicalCommitteeISO/TC47, Chemistry, Subcommittee SC7, Aluminium oxide, cryolite, aluminium fluoride, sodium fluoride, carbonaceous materials for
16、the aluminium industry. AnnexAofthisInternationalStandardisforinformationonly.INTERNATIONALSTANDARD ISO12977:1999(E)1 Carbonaceousmaterialsusedintheproductionofaluminium PitchforelectrodesDeterminationofvolatilemattercontent 1 Scope ThisInternationalStandarddescribesanempiricalmethodforthedeterminat
17、ionofthevolatilemattercontentof pitchbygaschromatographicanalysisofitssolutionintoluene.Strictadherencetotheprocedureisessential becauseoftheempiricalnatureofthemethod. 2 Normativereferences Thefollowingnormativedocumentscontainprovisionswhich,throughreferenceinthistext,constituteprovisionsof thisIn
18、ternationalStandard.Fordatedreferences,subsequentamendmentsto,orrevisionsof,anyofthese publicationsdonotapply.However,partiestoagreementsbasedonthisInternationalStandardareencouragedto investigatethepossibilityofapplyingthemostrecenteditionsofthenormativedocumentsindicatedbelow.For undatedreferences
19、,thelatesteditionofthenormativedocumentreferredtoapplies.MembersofISOandIEC maintainregistersofcurrentlyvalidInternationalStandards. ISO565, Test sieves Metal wire cloth, perforated metal plate and electroformed sheet Nominal sizes of openings. ISO1042, Laboratory glassware One-mark volumetric flask
20、s. ISO6257, Carbonaceous materials used in the production of aluminium Pitch for electrodes Sampling. 3 Term,definitionandsymbols 3.1 Termanddefinition ForthepurposesofthisInternationalStandard,thefollowingtermanddefinitionapplies. 3.1.1 volatilemattercontent totalpercentagebymassofthosecomponentspr
21、esentinthepitchwhichhavegas-chromatographicretention timescorrespondingtoatmosphericpressureboilingpointsupto360Cundertheconditionsused 3.2 Symbols,subscriptsandsuperscripts 3.2.1 Symbols A surfaceareaofthechromatographicpeak a slopeoftheregressionline B equivalentboilingpointatatmosphericpressure b
22、 interceptoftheregressionlineISO12977:1999(E) 2 F factortoconverttabulatedpeakareastothecorrespondingpercentagesbymassintheoriginalpitch sample K A ratioofareasofdibenzothiophenetophenanthrene K T ratioofretentiontimes m massofcalibrantcompound R reproducibility R f responsefactorforcalibrantcompoun
23、ds(5.2) r repeatability T retentiontimeofthechromatographicpeak w d percentagebymassofdibenzothiophenepresentinsample 3.2.2 Subscriptsandsuperscripts A,B,CsolutionsA,B,CcorrespondingrespectivelytochromatogramsA,B,C d dibenzothiophene ii-thpeak p phenanthrene pitch pitch T retentiontime tot totalsurf
24、aceareaofcalibrantcompoundsinthechromatogram 0 presenceintheoriginalpitchsample contributionresultingfromtheadditionofthedibenzothiopheneinternalstandard 4Principle Acalibrationanalysisofamulticomponenttestmixtureofpurecompoundscomprisingselectedmajorcomponents ofcoaltartogetherwithaninternalstandar
25、dcomponentisperformedbygaschromatographyunderdefined conditionsonachromatographiccolumnhavinganon-polarstationaryphase. Theresultsofthisanalysisestablishasubstantiallyrectilinearrelationshipbetweenthechromatographicretention timesoftheindividualcomponentsofthemixtureandtheiratmosphericpressureboilin
26、gpoints.Inaddition,the analysisprovidesameanrelativeresponsefactorwhichrelatestheratioofthetotalmasstototalchromatographic peakareafortheselectedcalibrantstotheequivalentratiofortheinternalstandard. Becausetheselectedinternalstandardcompound,dibenzothiophene,isalsoanormalcomponentofcoaltaritis neces
27、sarytoperformtheensuingchromatographicanalysisofthepitchontwosolutions,onewithandonewithout additionoftheinternalstandard,thusenablingtheareatomassresponseofthechromatographtotheinternal standardtobecalculated. Fromthelatterfigureandfromthemeanrelativeresponsefactorforthecomponentsinthecalibrationte
28、stmixture theamountsofmaterialrepresentedbythepeaksofthetestsampleanalysischromatogramarecalculated.These data,togetherwiththepreviouslyestablishedrelationshipbetweenthechromatographicretentiontimeandtheISO12977:1999(E)3 atmosphericpressureboilingpointsofthecomponents,allowtheconstructionofasimulate
29、ddistillationcurveor tableofvaluesforthetestsample. Fromthesevalues,thesumofthepercentagesofcomponentswithatmosphericpressureboilingpointsuptoand including360Cmaybecalculatedbyinterpolation. 5 Reagents WARNINGRefertothereagentsuppliersHealthandSafetydatasheetsfortheprecautionswhichareto betakenforth
30、esafeuseofthereagentslistedunder5.1,5.2and5.3. 5.1 Dibenzothiophene,ofatleast98%puritybymass. 5.2 Calibrantcompounds 1) comprisingnaphthalene,2-methylnaphthalene,acenaphthene,dibenzofuran, fluorene,phenanthrene,fluorantheneandpyrene,allofwhichshallbeofatleast98%purityandnoneofwhich shallcontainameas
31、urableamountofanyimpuritywhichco-eluteswiththedibenzothiophene(5.1)underthe chromatographicconditionsused. NOTE BoilingpointsofthecalibrantcompoundsaregiveninannexA. 5.3 Toluene,ofanalyticalreagentquality. 6 Apparatus Ordinarylaboratoryapparatusandthefollowing. 6.1 Gaschromatograph,havingaheatedinje
32、ctorcapableofoperatingat300C,aflame-ionizationdetector anditsassociatedamplifier,andequippedforusewithcapillarycolumnsunderprogrammed-temperature conditionsfromapproximately50Cto300C,withheatingratesof1C/minto10C/min. Itispreferablethatsplitlessinjectionisused.Ifanyotherarrangementisused,itshallbere
33、cordedinthetestreport (seeclause15). 6.2 Electronicintegrator,designedforprocessingthesignalfromthegaschromatograph(6.1)togivethe retentiontimesandareasofthechromatographicpeaks. Theintegratormaybecombinedwiththegaschromatograph(6.1)ormaybeaseparateunit. 6.3 Capillarycolumn,havinganon-polarstationar
34、yphasewithlow-bleedcharacteristicsunderthe chromatographicconditionsusedinthetest. Whenthecolumnisoperatedundertheselectedanalysisconditionswithoutinjectionofasample,thebaselineof thechromatogramshallremainrectilinearwithoutsignificantvariationovertherangeofretentiontimeswhich includestheretentionti
35、mesofnaphthaleneandpyrene. NOTE1 Typicallythecolumnwillbeof12mto25mlength,constructedoffusedsilicacapillarytubinghavinganinternal diameterof0,53mmminimum,takingintoaccountsplitlessinjectionandtheinjectionvolumeselected(seeclause10). Thecolumnshallhaveachemically-bondedstationaryphaseofthepoly(dimeth
36、ylsiloxane)type. NOTE2 Otherstationaryphaseswhichhavetherequiredlow-bleedcharacteristicsandgivesymmetricalpeaksshowinga similarlyrectilinearrelationshipbetweentheretentiontimesandtheboilingpointsofthecalibrantslistedin5.2areacceptable. 1)“Calibrant“compoundsareusedasthereferencematerialsforcalibrati
37、on.ISO12977:1999(E) 4 6.4 Chromatographicsyringes,ofatypeandcapacityappropriatetothecharacteristicsoftheinjectionsystem ofthegaschromatograph(6.1). NOTE Typicallytherequiredcapacitywillbeintherange1 lto25 l. 6.5 Volumetricflasks,conformingtotherequirementsofISO1042,ofcapacity10mland100ml. 6.6 Ultras
38、onicbath,ofatypedesignedforgenerallaboratoryuse. NOTE Typicallythiswillhaveapowerratingof100Wto200Wandanoperatingfrequencyof40kHz. 6.7 Pestleandmortar,constructedof,orfacedwith,hardmaterialwhichwillnotbeabradedandthereby contaminatethesample. NOTE Typicalsuitablematerialsincludeagate,tungstencarbide
39、andsiliconcarbide. 6.8 Testsieve,of212 mnominalaperture,conformingtotherequirementsofISO565andhavingalidand receiver. 7 Samplingandpreparationofthetestsample Preparearepresentativesampleofapproximately5gto10gofthepitchbythemethoddescribedinISO6257. Grindthesamplewiththepestleandmortar(6.7)untilallth
40、epitchpassesthroughthetestsieve(6.8). 8 Preparationofthetestsolutions 8.1 TestsolutionAwithoutaddedinternalstandard Weighapproximately1gofthegroundtestsample(seeclause7)tothenearest0,1mgdirectlyintoa10ml volumetricflask(6.5). Recordthemassthenaddsufficienttoluene(5.3)tofillthebulboftheflaskwithoutre
41、achingthecalibrationmark, andlooselyinsertthestopper. Iftheultrasonicbath(6.6)hasaheatingfacilitycapableofmaintainingthecontentsatatemperatureof60Cto 70C,placetheflaskinthebathandsubjectittoultrasonictreatmentatatemperatureinthisrangefor20min. Iftheultrasonicbathisnotcapableofmaintainingitscontentsa
42、t60Cto70C,heattheflaskanditscontentsto 60Cto70Cinawaterbathfor5min,thensubjectittoultrasonictreatmentfor5min.Repeattheheatingand ultrasonictreatmentoperationsthreemoretimes,togiveatotalof20minultrasonictreatment. Removetheflaskandallowittocooltoambienttemperature.Filltheflaskwithtolueneuptothecalibr
43、ationmark, insertthestopperthenshaketheflaskvigorouslybyhandforapproximately20s.Allowtheflaskanditscontentsto remainundisturbedforaminimumof1handpreferablyovernighttoallowthesuspendedsolidmattertosettle beforeanalysis. Keepthesolutionoutofdirectsunlightorstrongdaylight,andatatemperaturebetween15Cand
44、30Cuntil required.Performtheanalysiswithin48hofpreparingthesolution. NOTE Thesettlingperiodisintendedtoreducetheamountofinsolublematerialwhichissubsequentlydrawnwiththe solutionintothesyringe(6.4)andinjectedintothegaschromatograph(6.1),andthustolimitfoulingoftheinjectionportor columnwithinvolatilede
45、positswhichwouldotherwisedegradetheperformanceofthesystem.Providedthatcareistakento preventanylossofthesolutionoritsvolatilecomponents,thesettlingprocessmaybeshortenedbycentrifugingasuitably- sizedaliquotportion,orbyfilteringthroughasuitablefilterwhichdoesnotinteractwiththesolution.ISO12977:1999(E)5
46、 8.2 TestsolutionBwithaddedinternalstandard Weighapproximately0,01gofthedibenzothiophene(5.1)tothenearest0,1mgdirectlyintoa10mlvolumetric flask(6.5)thenpreparethesolutionasdescribedin8.1.Recordthemassesofdibenzothiopheneandpitchtaken. 9 PreparationofthecalibrantsolutionsolutionC Weigh0,1g 0,001gdibe
47、nzothiophene(5.1)and0,001gofeachofthecalibrantcompounds(5.2)tothenearest 0,1mgdirectlyintoa100mlvolumetricflask(6.5);recordthemasses,thenaddsufficienttoluene(5.3)tofillthe bulboftheflaskbutremainbelowthecalibrationmark. Placetheflaskintheultrasonicbath(6.6)andsubjectittoultrasonictreatmentuntilallth
48、esolidshavedissolved. Allowtheflasktocooltoambienttemperaturethenaddtoluenetobringthesolutionuptothecalibrationmark. Shaketheflasktomixthesolution. Keepthesolutionoutofdirectsunlightorstrongdaylightandstoreitinthedarkandatatemperaturebetween 15Cand30C,untilrequired.Discardthesolutionafteronemonthand
49、prepareafreshsolution. 10Selectionofchromatographicconditions Settheoperatingparametersforthegaschromatograph(6.1),thecapillarycolumn(6.3)andtheelectronic integrator(6.2)foroptimumperformanceinthefollowinganalysis,accordingtothemanufacturersinstructions. Takecareiftheelectronicintegratorhasaminimumareafacilitywhichenablesittoignoresmallpeaks,and ensurethatthisissettothelowestvalueconsistentwithsatisfactoryoperation. Settheelectronicintegratortoignorethetoluenesolventpeakandcollectdataonlyforthesubsequentpeaks. Settheinitia
