1、Designation: C697 10Standard Test Methods forChemical, Mass Spectrometric, and SpectrochemicalAnalysis of Nuclear-Grade Plutonium Dioxide Powders andPellets1This standard is issued under the fixed designation C697; the number immediately following the designation indicates the year oforiginal adopti
2、on or, in the case of revision, the year of last revision. A number in parentheses indicates the year of last reapproval. Asuperscript epsilon () indicates an editorial change since the last revision or reapproval.1. Scope1.1 These test methods cover procedures for the chemical,mass spectrometric, a
3、nd spectrochemical analysis of nuclear-grade plutonium dioxide powders and pellets to determinecompliance with specifications.1.2 The analytical procedures appear in the following order:SectionsPlutonium Sample Handling 8 to 10Plutonium by Controlled-Potential Coulometry2Plutonium by Ceric Sulfate T
4、itration3Plutonium by Amperometric Titration with Iron(II)2Plutonium by Diode Array Spectrophotometry3Nitrogen by Distillation Spectrophotometry Using NesslerReagent11 to 18Carbon (Total) by Direct CombustionThermal Conductivity 19 to 30Total Chlorine and Fluorine by Pyrohydrolysis 31 to 38Sulfur by
5、 Distillation Spectrophotometry 39 to 47Plutonium Isotopic Analysis by Mass Spectrometry4Rare Earth Elements by Spectroscopy 48 to 55Trace Elements by CarrierDistillation Spectroscopy 56 to 63Impurities by ICP-AESImpurity Elements by Spark-Source Mass Spectrography 64 to 70Moisture by the Coulometri
6、c Electrolytic Moisture Analyzer 71 to 78Total Gas in Reactor-Grade Plutonium Dioxide Pellets 79 to 86Plutonium-238 Isotopic Abundance by Alpha Spectrometry3Americium-241 in Plutonium by Gamma-Ray Spectrometry2Rare Earths By Copper Spark-Spectroscopy 87 to 96Plutonium Isotopic Analysis by Mass Spect
7、rometry 97 to 105Oxygen-To-Metal Atom Ratio by Gravimetry 106 to 1141.3 The values stated in SI units are to be regarded asstandard. The values given in parentheses are for informationonly.1.4 This standard does not purport to address all of thesafety concerns, if any, associated with its use. It is
8、 theresponsibility of the user of this standard to establish appro-priate safety and health practices and determine the applica-bility of regulatory limitations prior to use. For specificprecautionary statements, see Sections 6, 15, 24, 111, and 52.9and 101.5.1 .2. Referenced Documents2.1 ASTM Stand
9、ards:5C757 Specification for Nuclear-Grade Plutonium DioxidePowder, SinterableC852 Guide for Design Criteria for Plutonium GloveboxesC1009 Guide for Establishing a QualityAssurance Programfor Analytical Chemistry Laboratories Within the NuclearIndustryC1068 Guide for Qualification of Measurement Met
10、hods bya Laboratory Within the Nuclear IndustryC1108 Test Method for Plutonium by Controlled-PotentialCoulometryC1128 Guide for Preparation of Working Reference Mate-rials for Use in Analysis of Nuclear Fuel Cycle MaterialsC1156 Guide for Establishing Calibration for a Measure-ment Method Used to An
11、alyze Nuclear Fuel Cycle Mate-rialsC1165 Test Method for Determining Plutonium byControlled-Potential Coulometry in H2SO4at a PlatinumWorking ElectrodeC1168 Practice for Preparation and Dissolution of Pluto-nium Materials for AnalysisC1206 Test Method for Plutonium by Iron (II)/Chromium(VI) Amperome
12、tric TitrationC1210 Guide for Establishing a Measurement System Qual-ity Control Program forAnalytical Chemistry LaboratoriesWithin the Nuclear IndustryC1235 Test Method for Plutonium by Titanium(III)/Cerium(IV) Titration61These test methods are under the jurisdiction of ASTM Committee C26 onNuclear
13、 Fuel Cycle and are the direct responsibility of Subcommittee C26.05 onMethods of Test.Current edition approved June 1, 2010. Published July 2010. Originally approvedin 1972. Last previous edition approved in 2004 as C697 04. DOI: 10.1520/C0697-10.2Discontinued as of November 15, 1992.3Discontinued
14、as of January 1, 2004.4Discontinued as of May 30, 1980.5For referenced ASTM standards, visit the ASTM website, www.astm.org, orcontact ASTM Customer Service at serviceastm.org. For Annual Book of ASTMStandards volume information, refer to the standards Document Summary page onthe ASTM website.6Withd
15、rawn. The last approved version of this historical standard is referencedon www.astm.org.1Copyright ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959, United States.C1268 Test Method for Quantitative Determination of Am-ericium 241 in Plutonium by Gamma-Ray Spe
16、ctrometryC1297 Guide for Qualification of Laboratory Analysts forthe Analysis of Nuclear Fuel Cycle MaterialsC1307 Test Method for PlutoniumAssay by Plutonium (III)Diode Array SpectrophotometryC1415 Test Method for238Pu IsotopicAbundance ByAlphaSpectrometryC1432 Test Method for Determination of Impu
17、rities inPlutonium: Acid Dissolution, Ion Exchange Matrix Sepa-ration, and Inductively Coupled Plasma-Atomic EmissionSpectroscopic (ICP/AES) AnalysisD1193 Specification for Reagent WaterE60 Practice for Analysis of Metals, Ores, and RelatedMaterials by Molecular Absorption SpectrometryE115 Practice
18、for Photographic Processing in Optical Emis-sion Spectrographic Analysis6E116 Practice for Photographic Photometry in Spectro-chemical Analysis63. Significance and Use3.1 Plutonium dioxide is used in mixtures with uraniumdioxide as a nuclear-reactor fuel. In order to be suitable for thispurpose, the
19、 material must meet certain criteria for plutoniumcontent, isotopic composition, and impurity content. These testmethods are designed to show whether or not a given materialmeets the specifications for these items as described in Speci-fication C757.3.1.1 An assay is performed to determine whether t
20、hematerial has the minimum plutonium content specified on a dryweight basis.3.1.2 Determination of the isotopic content of the plutoniumin the plutonium dioxide powder is made to establish whetherthe effective fissile content is in compliance with the purchas-ers specifications.3.1.3 Impurity conten
21、t is determined to ensure that themaximum concentration limit of certain impurity elements isnot exceeded. Determination of impurities is also required forcalculation of the equivalent boron content (EBC).4. Committee C26 Safeguards Statement74.1 The materials (plutonium dioxide powders and pellets)
22、to which these test methods apply are subject to nuclearsafeguards regulations governing their possession and use. Thefollowing analytical procedures in these test methods havebeen designated as technically acceptable for generating safe-guards accountability measurement data: Plutonium byControlled
23、-Potential Coulometry; Plutonium by Ceric SulfateTitration; Plutonium by Amperometric Titration with Iron (II);Plutonium by Diode Array Spectrometry Plutonium-238 Iso-topic Abundance by Alpha Spectrometry; and Plutonium Iso-topic Analysis by Mass Spectrometry.4.2 When used in conjunction with approp
24、riate CertifiedReference Materials (CRMs), these procedures can demon-strate traceability to the national measurement base. However,adherence to these procedures does not automatically guaran-tee regulatory acceptance of the resulting safeguards measure-ments. It remains the sole responsibility of t
25、he user of these testmethods to assure that its application to safeguards has theapproval of the proper regulatory authorities.5. Reagents5.1 Purity of ReagentsReagent grade chemicals shall beused in all tests. Unless otherwise indicated, it is intended thatall reagents shall conform to the specific
26、ations of the Commit-tee on Analytical Reagents of the American Chemical Society,where such specifications are available.8Other grades may beused, provided it is first ascertained that the reagent is ofsufficiently high purity to permit its use without lessening theaccuracy of the determination.5.2
27、Purity of WaterUnless otherwise indicated, referencesto water shall be understood to mean reagent water conformingto Specification D1193.6. Safety Precautions6.1 Since plutonium bearing materials are radioactive andtoxic, adequate laboratory facilities, gloved boxes, fume hoods,etc., along with safe
28、 techniques, must be used in handlingsamples containing these materials.Adetailed discussion of allthe precautions necessary is beyond the scope of these testmethods; however, personnel who handle these materialsshould be familiar with such safe handling practices as aregiven in Guide C852 and in Re
29、fs (1) through (3).96.2 Adequate laboratory facilities, such as fume hoods andcontrolled ventilation, along with safe techniques, must be usedin this procedure. Extreme care should be exercised in usinghydrofluoric acid and other hot, concentrated acids. Use ofproper gloves is recommended. Refer to
30、the laboratoryschemical hygiene plan and other applicable guidance forhandling chemical and radioactive materials and for the man-agement of radioactive, mixed, and hazardous waste.6.3 Hydrofluoric acid is a highly corrosive acid that canseverely burn skin, eyes, and mucous membranes. Hydrofluo-ric
31、acid is similar to other acids in that the initial extent of aburn depends on the concentration, the temperature, and theduration of contact with the acid. Hydrofluoric acid differsfrom other acids because the fluoride ion readily penetrates theskin, causing destruction of deep tissue layers. Unlike
32、 otheracids that are rapidly neutralized, hydrofluoric acid reactionswith tissue may continue for days if left untreated. Due toserious consequences of hydrofluoric acid burns, prevention ofexposure or injury of personnel is the primary goal. Utilizationof appropriate laboratory controls (hoods) and
33、 wearing ad-equate personal protective equipment to protect from skin andeye contact is essential.7Based upon Committee C26 Safeguards Matrix (C1009, C1068, C1128, C1156,C1210, C1297).8Reagent Chemicals, American Chemical Society Specifications, AmericanChemical Society, Washington, DC. For suggesti
34、ons on the testing of reagents notlisted by the American Chemical Society, see Analar Standards for LaboratoryChemicals, BDH Ltd., Poole, Dorset, U.K., and the United States Pharmacopeiaand National Formulary, U.S. Pharmacopeial Convention, Inc., (USPC), Rockville,MD.9The boldface numbers in parenth
35、eses refer to the list of references at the end ofthese test methods.C697 1027. Sampling and Dissolution7.1 Criteria for sampling this material are given in Specifi-cation C757.7.2 Samples can be dissolved using the appropriate disso-lution technique described in Practice C1168.PLUTONIUM SAMPLE HAND
36、LING8. Scope8.1 This test method covers the conditions necessary topreserve the integrity of plutonium dioxide samples. Condi-tions listed here are directed toward the analytical chemist.However, they are just as applicable to any group handling thematerial.9. Summary of Test Method9.1 Plutonium dio
37、xide is very hygroscopic. In a short time itcan sorb sufficient water from an uncontrolled atmosphere todestroy the validity of the most accurate analytical methods.An atmosphere with a dew point of 23C has been foundadequate to prevent sorption of water, but care must beexercised to use equipment a
38、nd sample containers known to bedry.10. Sample Handling Conditions10.1 All sampling and critical weighings are to be per-formed in an atmosphere with a dew point no greaterthan 23C.10.2 All sampling equipment, including bottles, is to bedried before use. Plastic bottles are not to be used since they
39、cannot be adequately dried. Glass bottles and aluminum foilare to be dried at 110C for at least 1 h and kept in a desiccatoruntil used.NOTE 1It has been shown that plutonium dioxide will sorb waterfrom apparently dry aluminum foil. The foil should be dried at 110Cbefore use.10.3 Quantitative methods
40、 to correct for moisture absorp-tion, such as drying, must be avoided. The sample will not berepresentative under these conditions. It is virtually impossibleto get equal amounts of moisture in the sample and bulk of thematerial at the same time.PLUTONIUM BY CONTROLLED-POTENTIAL COULOMETRY(This test
41、 method was discontinued in 1992 and replaced byTest Method C1165.)PLUTONIUM BY CONTROLLED-POTENTIALCOULOMETRY(With appropriate sample preparation, controlled-potentialcoulometric measurement as described in Test Method C1108may be used for plutonium determination.)PLUTONIUM BY CERIC SULFATE TITRATI
42、ON(This test method was discontinued in 2003 and replaced byTest Method C1235.)PLUTONIUM BY AMPEROMETRIC TITRATIONWITH IRON (II)(This test method was discontinued in 1992 and replaced byTest Method C1206.)STANDARD TEST METHOD FOR PLUTONIUMASSAY BY PLUTONIUM(III) DIODE ARRAYSPECTROPHOTOMETRY(With app
43、ropriate sample preparation, the measurementdescribed in Test Method C1307 may be used for plutoniumdetermination.)NITROGEN BY DISTILLATIONSPECTROPHOTOMETRYUSING NESSLER REAGENT11. Scope11.1 This test method covers the determination of 5 to 100g/g of nitride nitrogen in 1-g samples of nuclear-gradep
44、lutonium dioxide.12. Summary of Test Method12.1 The sample is dissolved in hydrochloric acid by thesealed tube method or by phosphoric acid hydrofluoric acidsolution, after which the solution is made basic with sodiumhydroxide and nitrogen is separated as ammonia by steamdistillation. Nessler reagen
45、t is added to the distillate to form theyellow ammonium complex and the absorbance of the solutionis measured at approximately 430 nm (4,5).13. Apparatus13.1 Distillation Apparatus, see Fig. 1.13.2 Spectrophotometer, visible range.14. Reagents14.1 Ammonium Chloride (NH4Cl)Dry salt for2hat110to 120C.
46、14.2 Boric Acid Solution (40 g/L)Dissolve 40 g of boricacid (H3BO3) in 800 mL of hot water. Cool to approximately20C and dilute to 1 L.14.3 Hydrochloric Acid (sp gr 1.19)Concentrated hydro-chloric acid (HCl).14.4 Hydrofluoric Acid (48 %)Concentrated hydrofluoricacid (HF).14.5 Nessler ReagentTo prepa
47、re, dissolve 50 g of potas-sium iodide (KI) in a minimum of cold ammonia-free water,approximately 35 mL. Add a saturated solution of mercuricchloride (HgCl2, 22 g/350 mL) slowly until the first slightprecipitate of red mercuric iodide persists. Add 400 mL of 9 Nsodium hydroxide solution and dilute t
48、o 1 L with water, mix,and allow the solution to stand overnight. Decant supernatantliquid and store in a brown bottle.14.6 Nitrogen Standard Solution (1 mL = 0.01 mg N)Dissolve 3.819 g of NH4Cl in water and dilute to 1 L. Transfer10 mL of this solution to a 1-L volumetric flask and dilute tovolume w
49、ith ammonia-free water.14.7 Sodium Hydroxide (9 N)Dissolve 360 g of sodiumhydroxide (NaOH) in ammonia-free water and dilute to 1 L.C697 10314.8 Sodium Hydroxide (50 %)Dissolve sodium hydrox-ide (NaOH) in an equal weight of water.14.9 Water (Ammonia-free)To prepare, pass distilled wa-ter through a mixed-bed resin demineralizer and store in atightly stoppered chemical-resistant glass bottle.15. Precautions15.1 The use of ammonia or other volatile nitrogenouscompounds in the vicinity can lead to serious error. Thefollowing precautionary measures should be tak
