1、Designation: C697 16Standard 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 29Total Chlorine and Fluorine by Pyrohydrolysis 30 to 37Sulfur by
5、 Distillation Spectrophotometry 38 to 46Plutonium Isotopic Analysis by Mass Spectrometry4Rare Earth Elements by Spectroscopy 47 to 54Trace Elements by CarrierDistillation Spectroscopy 55 to 62(Alternative: Impurities by ICP-AES or ICP-MS)Impurity Elements by Spark-Source Mass Spectrography 63 to 69M
6、oisture by the Coulometric Electrolytic Moisture Analyzer 70 to 77Total Gas in Reactor-Grade Plutonium Dioxide Pellets5Plutonium-238 Isotopic Abundance by Alpha Spectrometry3Americium-241 in Plutonium by Gamma-Ray Spectrometry2Rare Earths By Copper Spark-Spectroscopy 78 to 87Plutonium Isotopic Analy
7、sis by Mass Spectrometry 88 to 96Oxygen-To-Metal Atom Ratio by Gravimetry 97 to 1041.3 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
8、 its use. It is 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, 16.2.5, 44.7, 51.9 and92.5.1.2. Referenced Documents2.1
9、ASTM Standards:6C757 Specification for Nuclear-Grade Plutonium DioxidePowder for Light Water ReactorsC852 Guide for Design Criteria for Plutonium GloveboxesC859 Terminology Relating to Nuclear MaterialsC1068 Guide for Qualification of Measurement Methods bya Laboratory Within the Nuclear IndustryC11
10、08 Test Method for Plutonium by Controlled-PotentialCoulometryC1165 Test Method for Determining Plutonium byControlled-Potential Coulometry in H2SO4at a PlatinumWorking ElectrodeC1168 Practice for Preparation and Dissolution of PlutoniumMaterials for AnalysisC1206 Test Method for Plutonium by Iron (
11、II)/Chromium(VI) Amperometric Titration (Withdrawn 2015)7C1233 Practice for Determining Equivalent Boron Contentsof Nuclear MaterialsC1235 Test Method for Plutonium by Titanium(III)/Cerium(IV) Titration (Withdrawn 2005)7C1268 Test Method for Quantitative Determination of241Am in Plutonium by Gamma-R
12、ay SpectrometryC1307 Test Method for Plutonium Assay by Plutonium (III)Diode Array SpectrophotometryC1415 Test Method for238Pu Isotopic Abundance By AlphaSpectrometryC1432 Test Method for Determination of Impurities inPlutonium: Acid Dissolution, Ion Exchange MatrixSeparation, and Inductively Couple
13、d Plasma-AtomicEmission Spectroscopic (ICP/AES) Analysis1These test methods are under the jurisdiction of ASTM Committee C26 onNuclear Fuel Cycle and are the direct responsibility of Subcommittee C26.05 onMethods of Test.Current edition approved June 1, 2016. Published July 2016. Originally approved
14、in 1972. Last previous edition approved in 2010 as C697 10. DOI: 10.1520/C0697-16.2Discontinued as of November 15, 1992.3Discontinued as of January 1, 2004.4Discontinued as of May 30, 1980.5Discontinued as of June 2016.6For referenced ASTM standards, visit the ASTM website, www.astm.org, orcontact A
15、STM Customer Service at serviceastm.org. For Annual Book of ASTMStandards volume information, refer to the standards Document Summary page onthe ASTM website.7The last approved version of this historical standard is referenced onwww.astm.org.Copyright ASTM International, 100 Barr Harbor Drive, PO Bo
16、x C700, West Conshohocken, PA 19428-2959. United States1C1625 Test Method for Uranium and Plutonium Concentra-tions and Isotopic Abundances by Thermal IonizationMass SpectrometryC1637 Test Method for the Determination of Impurities inPlutonium Metal:Acid Digestion and Inductively CoupledPlasma-Mass
17、Spectroscopy (ICP-MS) AnalysisC1672 Test Method for Determination of Uranium or Pluto-nium Isotopic Composition or Concentration by the TotalEvaporation Method Using a Thermal Ionization MassSpectrometerD1193 Specification for Reagent WaterD4327 Test Method for Anions in Water by Suppressed IonChrom
18、atographyE60 Practice for Analysis of Metals, Ores, and RelatedMaterials by SpectrophotometryE115 Practice for Photographic Processing in Optical Emis-sion Spectrographic Analysis (Withdrawn 2002)7E116 Practice for Photographic Photometry in Spectro-chemical Analysis (Withdrawn 2002)7E130 Practice f
19、or Designation of Shapes and Sizes ofGraphite Electrodes (Withdrawn 2013)73. Terminology3.1 Except as otherwise defined herein, definitions of termsare as given in Terminology C859.4. Significance and Use4.1 Plutonium dioxide is used in mixtures with uraniumdioxide as a nuclear-reactor fuel. In orde
20、r to be suitable for thispurpose, the 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 C757.4.1.1 An assa
21、y is performed to determine whether thematerial has the minimum plutonium content specified on a dryweight basis.4.1.2 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
22、 specifications.4.1.3 Impurity content 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) as describedin Practice C1233.4.2 Fitness for Purpose of S
23、afeguards and Nuclear SafetyApplicationsMethods intended for use in safeguards andnuclear safety applications shall meet the requirements speci-fied by Guide C1068 for use in such applications.5. Reagents5.1 Purity of ReagentsReagent grade chemicals shall beused in all tests. Unless otherwise indica
24、ted, it is intended thatall reagents shall conform to the specifications 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 perm
25、it its use without lessening theaccuracy of the determination.5.2 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 lab
26、oratory facilities, glove boxes, fume hoods,and so forth, along with safe techniques, must be used inhandling samples containing these materials. Glove boxesshould be fitted with off-gas filters capable of sustainedoperation with dust-laden atmospheres. A detailed discussionof all the precautions ne
27、cessary is beyond the scope of thesetest methods; however, personnel who handle these materialsshould be familiar with such safe handling practices as aregiven in Guide C852 and in Refs (1-3).96.2 Adequate laboratory facilities, such as fume hoods andcontrolled ventilation, along with safe technique
28、s, must be usedin all procedures in this test method. Extreme care should beexercised in using hydrofluoric acid and other hot, concen-trated acids. Use of proper gloves is recommended. Refer to thelaboratorys chemical hygiene plan and other applicable guid-ance for handling chemical and radioactive
29、 materials and forthe management of radioactive, mixed, and hazardous waste.6.3 Hydrofluoric acid is a highly corrosive acid that canseverely burn skin, eyes, and mucous membranes. Hydroflu-oric acid differs from other acids because the fluoride ionreadily penetrates the skin, causing destruction of
30、 deep tissuelayers. Unlike other acids that are rapidly neutralized, hydro-fluoric acid reactions with tissue may continue for days if leftuntreated. Familiarization and compliance with the Safety DataSheet is essential.6.4 Perchloric acid (HClO4) forms explosive compoundswith organics and many meta
31、l salts.Avoid exposure by contactwith the skin or eyes, or by inhalation of fumes. Familiarizationand compliance with the Safety Data Sheet is essential. Carryout sample dissolution with perchloric acid in a fume hoodwith a scrubber unit that is specially designed for use withHClO4.7. Sampling and D
32、issolution7.1 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 C1168.8Reagent Chemicals, American Chemical Society Specifications, AmericanChemical Society, Washington, DC. For suggest
33、ions on the testing of reagents notlisted by the American Chemical Society, see Analar Standards for LaboraotryChemicals, 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
34、eses refer to the list of references at the end ofthese test methods.C697 162PLUTONIUM SAMPLE HANDLING8. 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 a
35、re just as applicable to any group handling thematerial.9. Summary of Test Method9.1 Plutonium dioxide 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
36、 has been foundadequate to prevent sorption of water, but care must beexercised to use equipment and sample containers known to bedry.10. Sample Handling Conditions10.1 All sampling and critical weighings are to be per-formed with consideration of the hygroscopic nature of pluto-nium and the applica
37、ble data quality objectives (DQOs). Insome instances an atmosphere with a dew point no greaterthan 23C may be needed to meet DQOs.10.2 All sampling equipment, including bottles, is to bedried before use. Plastic bottles are not to be used since theycannot be adequately dried. Glass bottles and alumi
38、num 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 water fromapparently dry aluminum foil. The foil should be dried at 110C beforeuse.10.3 Quantitative methods to correct for moistureabsorption, such as drying,
39、 must be avoided. The sample willnot be representative under these conditions. It is virtuallyimpossible to get equal amounts of moisture in the sample andbulk of the material at the same time.PLUTONIUM BY CONTROLLED-POTENTIAL COULOMETRY(This test method was discontinued in 1992 and replaced byTest
40、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 TITRATION(This test method was discontinued in 2003 and repl
41、aced byTest Method C1235, which was withdrawn in 2005.)PLUTONIUM BY AMPEROMETRIC TITRATIONWITH IRON (II)(This test method was discontinued in 1992 and replaced byTest Method C1206, which was withdrawn in 2015.)PLUTONIUM ASSAY BY PLUTONIUM(III) DIODEARRAY SPECTROPHOTOMETRY(With appropriate sample pre
42、paration, 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-gradeplutonium dioxide.12
43、. 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 reagent is added to the d
44、istillate 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 for 2 h at 110to 120C.14.2 Boric Aci
45、d 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 prepare, dissolve 5
46、0 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 to 1 L with wat
47、er, 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 with ammonia-fr
48、ee water.14.7 Sodium Hydroxide (9 N)Dissolve 360 g of sodiumhydroxide (NaOH) in ammonia-free water and dilute to 1 L.14.8 Sodium Hydroxide (50 %)Dissolve sodium hydrox-ide (NaOH) in an equal weight of water.C697 16314.9 Water (Ammonia-free)To prepare, pass distilled wa-ter through a mixed-bed resin
49、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 taken: (1) Cleanall glassware and rinse with ammonia-free water immediatelyprior to use, and (2) avoid contamination of the atmosphere inthe vicinity of the test by ammonia or other volatile nitrog-enous compounds.16. Procedure16.1 Dissolution of Sample:16.1.1 Transfer a weighed sample in the range from 1.0 to1.5 g
