1、Z5XISOInternationalStandardISO19396-1Secondedition2025-06Paintsandvarnishes一DeterminationofpHvalue一Part1:pHsensorswithglassmembranePeinturesetvernisDeterminationdeIavaleurdepHPartie1:SondesdepHamembraneenVerreReferencenumberISO19396-l:2025(en)COPYRIGHTPROTECTEDDOCUMENTISO2025Allrightsreserved.Unless
2、otherwisespecified,orrequiredinthecontextofitsimplementation,nopartofthispublicationmaybereproducedorutilizedotherwiseinanyformorbyanymeans,electronicormechanical,includingphotocopying,orpostingontheinternetoranintranet,withoutpriorwrittenpermission.PermissioncanberequestedfromeitherISOattheaddressb
3、eloworISO,smemberbodyinthecountryoftherequester.ISOcopyrightofficeCP401Ch.deBlandonnet8CH-1214Vernier,GenevaPhone:+41227490111Email:copyrightiso.orgWebsite:www.iso.orgPublishedinSwitzerlandContentsPageForewordivIntroductionv1 Scope12 Normativereferences13 Termsanddefinitions14 Principle45 Apparatusa
4、ndmaterials45.1 pHmeasuringapparatus45.2 pHmeter55.3 pHsensor55.4 Buffersolutions75.5 StoragesolutionforthepHsensors.76 Sampling77 PrOCedUre77.1 Testconditions77.2 Calibration77.3 Numberofdeterminations87.4 MeasuringthepHvalue88 Evaluation89 Precision89.1 General89.2 Repeatabilitylimit,r89.3 Reprodu
5、cibilitylimit,R910 Testreport9Annex A (informative)RecommendedpHsensorsfordifferentgroupsofcoatingmaterials,basedontheresultsofinterlaboratorytests10Annex B (informative)Determinationofprecision12Bibliography14ForewordISO(theInternationalOrganizationforStandardization)isaworldwidefederationofnationa
6、lstandardsbodies(ISOmemberbodies).TheworkofpreparingInternationalStandardsisnormallycarriedoutthroughISOtechnicalcommittees.Eachmemberbodyinterestedinasubjectforwhichatechnicalcommitteehasbeenestablishedhastherighttoberepresentedonthatcommittee.Internationalorganizations,governmentalandnon-governmen
7、tal,inliaisonwithISO,alsotakepartinthework.ISOcollaboratescloselywiththeInternationalElectrotechnicalCommission(IEC)onallmattersofelectrotechnicalstandardization.TheproceduresusedtodevelopthisdocumentandthoseintendedforitsfurthermaintenancearedescribedintheISO/IECDirectives,Part1.Inparticular,thedif
8、ferentapprovalcriterianeededforthedifferenttypesofISOdocumentshouldbenoted.ThisdocumentwasdraftedinaccordancewiththeeditorialrulesoftheISO/IECDirectives,Part2(seeWWW.iso.org/directives).ISOdrawsattentiontothepossibilitythattheimplementationofthisdocumentmayinvolvetheuseof（八）patent(三).ISOtakesnoposit
9、ionconcerningtheevidence,validityorapplicabilityofanyclaimedpatentrightsinrespectthereof.Asofthedateofpublicationofthisdocument,ISOhadnotreceivednoticeof（八）patent(三)whichmayberequiredtoimplementthisdocument.HoweverlImplementersarecautionedthatthismaynotrepresentthelatestinformation,whichmaybeobtaine
10、dfromthepatentdatabaseavailableatWWW.iso.org/patents.ISOshallnotbeheldresponsibleforidentifyinganyorallsuchpatentrights.Anytradenameusedinthisdocumentisinformationgivenfortheconvenienceofusersanddoesnotconstituteanendorsement.Foranexplanationofthevoluntarynatureofstandards,themeaningofISOspecificter
11、msandexpressionsrelatedtoconformityassessment,aswellasinformationaboutISOsadherencetotheWorldTradeOrganization(WTO)principlesintheTechnicalBarrierstoTrade(TBT),seeWWW.iso.org/iso/foreword.htmLThisdocumentwaspreparedbyTechnicalCommitteeISO/TC35,Paintsandvarnishes,SubcommitteeSC9,Generaltestmethodsfor
12、paintsandvarnishes,incollaborationwiththeEuropeanCommitteeforStandardization(CEN)TechnicalCommitteeCEN/TC139,Paintsandvarnishes,inaccordancewiththeAgreementontechnicalcooperationbetweenISOandCEN(ViennaAgreement).Thissecondeditioncancelsandreplacesthefirstedition(ISO19396-1:2017),whichhasbeentechnica
13、llyrevised.Themainchangesareasfollows: definitionsfortheoreticalslope,stabilityofmeasuredValUe,potentiometricmeasurementchain”and(referenceelement1havebeendeleted; thetermpHelectrode11hasbeenchangedto“pHSenSOrintheentiretextincludingthetitleofthedocument; thecalibration(7.2)hasbeenclarified; thenorm
14、ativereferenceshavebeenupdated.AlistofallpartsintheISO19396seriescanbefoundontheISOwebsite.Anyfeedbackorquestionsonthisdocumentshouldbedirectedtotheusersnationalstandardsbody.Acompletelistingofthesebodiescanbefoundatwww.iso.orR/members.htmLIntroductionThepHvalueofaqueousproductsisofdecisiveimportanc
15、efortheproductpropertiesanddurability.ThisdocumentcoversamethodforlaboratorymeasurementofthepHvalueofpolymerdispersionsandcoatingmaterialsusingpHsensorswithaglassmembrane.ISO19396-2specifiesamethodformeasuringthepHvalueusingpHsensorswithion-sensitivefield-effecttransistor(ISFET)technology.Paintsandv
16、arnishesDeterminationofpHvalue一Part1:pHsensorswithglassmembrane1 ScopeThisdocumentspecifiesamethodforlaboratorymeasurementofthepHvalueofpolymerdispersionsandcoatingmaterialsusingpHsensorswithaglassmembrane.2 NormativereferencesThefollowingdocumentsarereferredtointhetextinsuchawaythatsomeoralloftheir
17、contentconstitutesrequirementsofthisdocument.Fordatedreferences,onlytheeditioncitedapplies.Forundatedreferences,thelatesteditionofthereferenceddocument(includinganyamendments)applies.ISO1513,PaintsandvarnishesExaminationandpreparationOftestsampIesISO4618,PaintsandvarnishesVocabularyISO15528,Paints,v
18、arnishesandrawmaterialsforpaintsandvarnishesSamplingISO80000-9,QuantitiesandunitsPart9:Physicalchemistryandmolecularphysics3 TermsanddefinitionsForthepurposesofthisdocument,thetermsanddefinitionsgiveninISO4618,ISO80000-9andthefollowingapply.ISOandIECmaintainterminologydatabasesforuseinstandardizatio
19、natthefollowingaddresses: ISOOnlinebrowsingplatform:availableathttps:/www.iso.org/ObP IECElectropedia:availableathttps:WWW.electropedia.org/3.1pHmeasurefortheacidicorbasicreactionofanaqueoussolutionorpolymerdispersionNote1toentry:ForthenotationOfPH,thePandtheHareverticallyononeline.Thesameisvalidfor
20、pOH.Note2toentry:Theacidicreactionisdeterminedbytheactivityoftheexisting11hydrogenions”.Thebasicreactionisdeterminedbytheactivityoftheexistinghydroxideions.Thedirectrelationshipbetweentheactivitiesofthe“hydrogenionsandthehydroxideionsisdescribedbytheionicproductofthewater.3.2pHvaluedecadallogarithmo
21、fthehydrogenionactivitymultipliedwith(-1)with%+=%+h+whereQfistheactivityofthehydrogenionlinmol/kg;m0isthestandardmolality(1molkg);h+istheactivitycoefficientofthehydrogenion;%+isthemolalityofthehydrogenion,inmolkg.Note1toentry:ForfurtherdetailsseeDIN19261.3.3pHsensorpHelectrodepHcombinationelectrodep
22、HmeasuringchainpHsingle-rodmeasuringchainpotentiometricmeasuringchainprovidingavoltagewhichdependsonthepHvalue(3.2)ofthemeasuringmediumNote1toentry:ThetwoelectrochemicalhalfcellsarethepHmeasuringelectrodeandthereferenceelectrode(3.4)(seeFigure1).Bothelectrodescanbecombinedasasingle-rodmeasuringchain
23、inoneunit.Note2toentry:Anintegratedtemperaturesensorisrecommended(seeFigure1).Note3toentry:ThisdocumentreferstopHsensorswithglassmembrane.Thesensorshaftshouldbemadeofmaterialresistanttochemicalsandsolvents.Key6 innerreference7 glassmembrane8 internalbuffer9 temperaturesensorUpHproportionalvoltage1 r
24、eferenceelectrode,consistingof2,3and42 referenceelement3 referenceelectrolyte4 diaphragm5 pHmeasuringelectrode,consistingof6,7and8Figure1DesignofapHsensorwithglassmembraneandtemperaturesensor1.4referenceelectrodeelectrodeprovidingaconstantpotentialWhichisindependentfromXhepHvalue(3.2)ofthemeasuringm
25、ediumNote1toentry:Atthetimeofpublicationofthisdocument,themostcommonlyusedtypeisthesilver/silverchloridereferenceelectrode,whosepotentialisstabilizedbyaconstantconcentrationofpotassiumchloride(KCl)inthereferenceelectrolyte(3.5).1.5referenceelectrolyteaqueoussaltsolution(generallypotassiumchloridesol
26、ution),whosechlorideionactivitydeterminesthepotentialofthereferenceelectrode(3.4)Note1toentry:Atthediaphragm(3.6),thereferenceelectrolytehascontactwiththemeasuringmedium.Potassiumchloridesolutionisusedasreferenceelectrolyte,becauseK+ionsandCl-ionshavealmostthesameionmobilityand,therefore,onlyslightd
27、iffusionpotentialsresult.Note2toentry:Thereferenceelectrolyteshouldflowoutofthediaphragminordertoensureaconstantreferencepotential.Therefore,itisrefilledoccasionally.Forreferenceelectrodes(3.4)orpHsensors(3.3)withthickened/gelorsolidifiedelectrolyte,refillingoftheelectrolytecanbeomitted.Suchreferenc
28、eelectrodesorpHsensorsarecalledlow-maintenance.1.6diaphragmpermeablematerialinthesidesofthecasingofreferenceelectrodes(3.4),whichenablestheelectrolyticcontactbetweenreferenceelectrolytes(3.5)andmeasuringmediumandsimultaneouslyimpedestheexchangeofelectrolyteNote1toentry:FortypesOfdiaphragms,see5.3.1.
29、7measuringelectrodewithglassmembraneelectrodeprovidingapotentialwhichisafunctionofthepHvalue(3.2)1.8glassmembranemembranemadeofspecialglass,whoseinterfacetothemediumgivesrisetoanelectricalpotential(electrodefunction),whichisproportionaltothepH(3.1)ofthemedium1.9temperaturecompensationmathematicalcor
30、rectionofthetemperatureinfluenceonthemeasuringsignalNote1toentry:Bythis,thetemperaturedependencyofthepHvaluef3.2)ofthemeasuringmediumcannotbecompensated.Therefore,thetemperatureisalwaysrecordedtogetherwiththepHvalue.3.10practicalslopek,slopeofapHsensor(3.3),whichisobtainedbymeasuringthepHproportiona
31、lvoltagesofthepHsensorinatleasttworeferencebuffersolutions(3.12)(7k=pHNote1toentry:TheslopeobtainedduringcalibrationisacharacteristicforthequalityofthepHsensor.Note2toentry:Forfurtherdefinitionson“slopeandzeropoint“seeDIN19261.3.11zeropointPhopHvalue(3.2)ofapHsensor(3.3),forwhichthepHproportionalvol
32、tageofthepHsensorisU=0mVatagiventemperatureNote1toentry:Thezeropointcanalsobeindicatedintermsofavoltage(offsetvoltage,usuallyatpH=7.Note2toentry:ThezeropointobtainedduringcalibrationisacharacteristicforthequalityofthepHsensor.3.12buffersolutionsolutionwithapHvalue(3.2)ofknownmeasurementuncertaintyNo
33、te1toentry:ThebuffersolutionisusedforcalibrationandadjustmentofpHmeters.BuffersolutionshaveapHvaluethatislargelynon-sensitivetodilutionandacidorbasicaddition.4 PrincipleThisdocumentcomprisesthedescriptionofsuitablepHsensorsandtheircalibrationandcleaning,aswellastheprocedureofpHmeasurement.Thespecifi
34、edmethodsandmeasuringconditionsarebasedontheresultsofseveralinterlaboratorytests(seeAnnexBl.5 Apparatusandmaterials5.1 pHmeasuringapparatusUseapHmeasuringapparatus(SeeFigure2)forpHmeasurementofpolymerdispersionsandcoatingmaterialsconsistsofapHmeter,apHsensor,atleasttwobuffersolutions,containersforth
35、ebuffersolutionsandthematerialtobemeasured.Tocleanthesensor,aspraybottlewithdeionizedwaterorasuitablecleaningsolutionisrecommended.Inaddition,itcanbehelpfultouseastand,astirringtool,thermostats,aswellasdatarecordingandanalysissystems.Key1 pHmeter2 pHsensorwithtemperaturesensor3 stand4 buffersolution
36、s5 storagesolution(e.g.KClsolution)6 deionizedwater7 cleaningsolution(dependingontheproduct)8 measuringcontainersFigure 2 ExampleofapHmeasuringapparatus2.2 pHmeterThepHmetershallatleasthavethefollowingfunctions: pHvalue,withreadingaccuracyof0,01; pHproportionalvoltageofthepHsensor,withaccuracyofatle
37、ast1mV; adjustmentoftheoffsetandindicationofzeropointoroffset; adjustmentofthepracticalslope; indicationofthemeasuringtemperature; temperaturecompensation:manuallyorautomaticallywithconnectedtemperaturesensor(externalorintegratedinthepHsensor).2.3 pHsensorThetwoelectrochemicalhalfcells,i.e.thepHmeas
38、uringelectrodewithglassmembraneandthereferenceelectrode,arecombinedinoneunit(seeFigure3).Anintegratedtemperaturesensorisrecommended(seeFigure11.Key1 connectingcable(alternativelyplughead)2 bendprotection3 sensorhead4 sensorshaft5 diaphragm6 glassmembrane7 refillopening(closablee.g.byslide)Figure 3 E
39、xampleofapHsensorwithglassmembraneFormeasuringthepHvalueofpolymerdispersionsandcoatingmaterials,thefollowingpHsensorswithglassmembranearesuitablefseeFigure4.Thefollowingtypesaretypicallyusedasreferenceelectrodes,includingreferenceelectrolyte:TypeASolidelectrolyteelectrodewithperforatedorannular-gapd
40、iaphragm;thetypeofcalotteandsphericalglassmembraneisillustratedinFigUre4.TypeBLiquidelectrolyteelectrode,refillable,withanannular-gapdiaphragm(e.g.glasscutting).TypeCLiquidelectrolyteelectrode,refillable,withcapillarydiaphragm(e.g.ceramic,platinumwire,andfibre),attachedatthesideinthesensorshaft;thet
41、ypeofcalotteandsphericalglassmembraneisillustratedinFigUre4.TypeDLiquidelectrolyteelectrode,refillable,withprotrudingceramicdiaphragm,whichcanbeprotectedbyimposingadialysismembrane.Thedialysismembraneisdisposedofaftermeasuring.Thiswaythediaphragmdoesnothavecontactwiththepaint.Withoutthedialysismembr
42、ane,thesensorbehavesliketypeC.TypeDisrecommendedforcoatingmaterialswithhighionicstrength,suchaselectro-depositionpaints.RecommendedpHsensorsfordifferentgroupsofcoatingmaterialsarebasedontheresultsoftheinterlaboratorytestsCseeAnnexA).TypeATypeBTypeCTypeDFigure 4 pHsensors1.4 BuffersolutionsBuffersolu
43、tionswithspecificationsonprecision,durability,andtemperaturedependencyshallbeused.NOTEBuffersolutionscanchangeduringstorageinclosedandespeciallyinopencontainers.1.5 StoragesolutionforthepHsensorspHsensorsshallbestoredinasolutionwhichinhibitstheleachingofthereferenceelectrodesystem,e.g.KClsolution,c=
44、3mol/LNOTEDeionizedwaterisinappropriateforstorage(zerooffsetcausedbyleachingofthereferenceelectrode).6 SamplingTakearepresentativesampleoftheproducttobetestedasspecifiedinISO15528.ExamineandpreparethesamplesofcoatingmaterialsasspecifiedinISO1513.Sampling,transportofsamplesandsamplepreparationhaveinf
45、luenceonthepHvalue.7 Procedure7.1 TestconditionsInordertoreducethermalandelectricalhysteresiseffects,ensurethatthetemperaturesofthetestsamples,sensor,demineralizedordistilledrinsingwaterandbuffersolutionsareasclosetooneanotheraspossible.Thetemperaturesofthetestsamplesandbuffersolutionsshallnotdiffer
46、bymorethan1.Thetemperatureforthedeterminationshallbe(232)(272incountrieswithtropicalorhotclimates.ThepHvariationovertherangeof20to30isnegligiblecomparedtothesystemmeasurementuncertainty.Inaddition,thetemperaturecompensatorintheinstrumentshouldbesetattheactualtemperature.Thesampletobemeasuredshallbeh
47、omogenous.7.2 CalibrationCarryoutatleastatwo-pointcalibration.ThepHvaluesofthebuffersolutionsshouldcloselybracketthemeasuringrangeofthesamples.ThedifferencebetweenthevaluesofthetwobuffersolutionsshallbepH2.NOTEThepHvalueofbasicbuffersolutionschangesrelativelyfast,byabsorbingCO介Omtheairandtherebythemeasurementuncertaintyincreases.AdjustthepHmeterwiththedata(slopeandzeropointoroffset)obtainedduringcalibration.Discardtheusedbuffersolutionsafteruse.7.3 NumberofdeterminationsCarryoutthedeterminationinduplicate.Ifthesecondmeasurementdoes
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