1、Designation: C698 10Standard Test Methods forChemical, Mass Spectrometric, and SpectrochemicalAnalysis of Nuclear-Grade Mixed Oxides (U, Pu)O2)1This standard is issued under the fixed designation C698; the number immediately following the designation indicates the year oforiginal adoption or, in the
2、 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, and spectroche
3、mical analysis of nuclear-grade mixed oxides, (U, Pu)O2, powders and pellets to deter-mine compliance with specifications.1.2 The analytical procedures appear in the following order:SectionsUranium in the Presence of Pu by Potentiometric Titration2Plutonium by Controlled-Potential Coulometry2Plutoni
4、um by Amperometric Titration with Iron (II)2Nitrogen by Distillation Spectrophotometry Using Nessler Re-agent7 to 14Carbon (Total) by Direct Combustion-Thermal Conductivity 15 to 26Total Chlorine and Fluorine by Pyrohydrolysis 27 to 34Sulfur by Distillation-Spectrophotometry 35 to 43Moisture by the
5、Coulometric, Electrolytic Moisture Analyzer 44 to 51Isotopic Composition by Mass Spectrometry3Rare Earths by Copper Spark Spectroscopy 52 to 59Trace Impurities by Carrier Distillation Spectroscopy 60 to 69Impurities by Spark-Source Mass Spectrography 70 to 76Total Gas in Reactor-Grade Mixed Dioxide
6、Pellets 77 to 84Tungsten by Dithiol-Spectrophotometry 85 to 93Rare Earth Elements by Spectroscopy 94 to 97Plutonium-238 Isotopic Abundance by Alpha Spectrometry4Americium-241 in Plutonium by Gamma-Ray SpectrometryUranium and Plutonium Isotopic Analysis by Mass Spectrom-etry98 to 106Oxygen-to-Metal A
7、tom Ratio by Gravimetry 107 to 1151.3 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 theresponsibility of the user of
8、this standard to establish appro-priate safety and health practices and determine the applica-bility of regulatory limitations prior to use. (For specificsafeguard and safety precaution statements, see Sections 11,20, 64, and 112 and 102.6.1.)2. Referenced Documents2.1 ASTM Standards:5C697 Test Meth
9、ods for Chemical, Mass Spectrometric, andSpectrochemical Analysis of Nuclear-Grade PlutoniumDioxide Powders and PelletsC833 Specification for Sintered (Uranium-Plutonium) Di-oxide PelletsC852 Guide for Design Criteria for Plutonium GloveboxesC1008 Specification for Sintered (Uranium-Plutonium) Di-ox
10、ide PelletsFast Reactor FuelC1009 Guide for Establishing a QualityAssurance Programfor Analytical Chemistry Laboratories Within the NuclearIndustryC1068 Guide for Qualification of Measurement Methods bya Laboratory Within the Nuclear IndustryC1108 Test Method for Plutonium by Controlled-PotentialCou
11、lometryC1128 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 Analyze Nuclear Fuel Cycle Mate-rialsC1165 Test Method for Determining Plutonium byControlled-Potential Cou
12、lometry in H2SO4at a PlatinumWorking ElectrodeC1168 Practice for Preparation and Dissolution of Pluto-nium Materials for AnalysisC1204 Test Method for Uranium in Presence of Plutoniumby Iron(II) Reduction in Phosphoric Acid Followed byChromium(VI) TitrationC1206 Test Method for Plutonium by Iron (II
13、)/Chromium(VI) Amperometric TitrationC1210 Guide for Establishing a Measurement System Qual-ity Control Program forAnalytical Chemistry LaboratoriesWithin the Nuclear IndustryC1268 Test Method for Quantitative Determination of Am-ericium 241 in Plutonium by Gamma-Ray Spectrometry1These test methods
14、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, 2010. Published July 2010. Originally approvedin 1972. Last previous edition approved in 2004 as C698 04. DOI: 10.1520/C06
15、98-10.2Discontinued as of November 15, 1992.3Discontinued as of May 30, 1980.4Discontinued as of January 1, 2004.5For 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
16、 standards Document Summary page onthe ASTM website.1Copyright ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959, United States.C1297 Guide for Qualification of Laboratory Analysts forthe Analysis of Nuclear Fuel Cycle MaterialsC1415 Test Method for238Pu Isotop
17、icAbundance ByAlphaSpectrometryC1432 Test Method for Determination of Impurities 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, Ore
18、s, and RelatedMaterials by Molecular Absorption SpectrometryE115 Practice for Photographic Processing in Optical Emis-sion Spectrographic Analysis6E116 Practice for Photographic Photometry in Spectro-chemical Analysis63. Significance and Use3.1 Mixed oxide, a mixture of uranium and plutoniumoxides,
19、is used as a nuclear-reactor fuel in the form of pellets.The plutonium content may be up to 10 weight %, and thediluent uranium may be of any235U enrichment. In order to besuitable for use as a nuclear fuel, the material must meet certaincriteria for combined uranium and plutonium content, effective
20、fissile content, and impurity content as described in Specifica-tion C833.3.1.1 The material is assayed for uranium and plutonium todetermine whether the plutonium content is as specified by thepurchaser, and whether the material contains the minimumcombined uranium and plutonium contents specified
21、on a dryweight basis.3.1.2 Determination of the isotopic content of the plutoniumand uranium in the mixed oxide is made to establish whetherthe effective fissile content is in compliance with the purchas-ers specifications.3.1.3 Impurity content is determined to ensure that themaximum concentration
22、limit of certain impurity elements isnot exceeded. Determination of impurities is also required forcalculation of the equivalent boron content (EBC).4. Reagents4.1 Purity of ReagentsReagent grade chemicals shall beused in all tests. Unless otherwise indicated, it is intended thatall reagents shall c
23、onform to the specifications of the Commit-tee on Analytical Reagents of the American Chemical Society,where such specifications are available.7Other grades may beused, provided it is first ascertained that the reagent is ofsufficiently high purity to permit its use without lessening theaccuracy of
24、the determination.4.2 Purity of WaterUnless otherwise indicated, referencesto water shall be understood to mean reagent water conformingto Specification D1193.5. Safety Precautions5.1 Since plutonium- and uranium-bearing materials areradioactive and toxic, adequate laboratory facilities, glovedboxes
25、, fume hoods, etc., along with safe techniques must beused in handling samples containing these materials.Adetaileddiscussion of all the precautions necessary is beyond the scopeof these test methods; however, personnel who handle thesematerials should be familiar with such safe handling practicesas
26、 are given in Guide C852 and in Refs (1) through (3).85.2 Committee C26 Safeguards Statement:95.2.1 The materials nuclear grade mixed oxides (U, Pu)O2powders and pellets to which these test methods apply aresubject to nuclear safeguards regulations governing their pos-session and use. The following
27、analytical procedures in thesetest methods have been designated as technically acceptable forgenerating safeguards accountability measurement data: Ura-nium by Controlled Potential Coulometry; Plutonium byControlled-Potential Coulometry; Plutonium byAmperometricTitration with Iron(II); Plutonium-238
28、 Isotopic Abundance byAlpha Spectrometry; and Uranium and Plutonium IsotopicAnalysis by Mass Spectrometry.5.2.2 When used in conjunction with appropriate certifiedreference materials (CRMs), these procedures can demonstratetraceability to the national measurements base. However,adherence to these pr
29、ocedures does not automatically guaran-tee regulatory acceptance of the resulting safeguards measure-ments. It remains the sole responsibility of the user of these testmethods to assure that its application to safeguards has theapproval of the proper regulatory authorities.5.3 Adequate laboratory fa
30、cilities, 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 the laboratoryschemical hygiene plan and other
31、 applicable guidance forhandling chemical and radioactive materials and for the man-agement of radioactive, mixed, and hazardous waste.5.4 Hydrofluoric acid is a highly corrosive acid that canseverely burn skin, eyes and mucous membranes. Hydrofluoricacid is similar to other acids in that the initia
32、l extent of a burndepends on the concentration, the temperature, and the durationof contact with the acid. Hydrofluoric acid differs from otheracids because the fluoride ion readily penetrates the skin,causing destruction of deep tissue layers. Unlike other acidsthat are rapidly neutralized, hydrofl
33、uoric acid reactions withtissue may continue for days if left untreated. Due to theserious consequence of hydrofluoric acid burns, prevention ofexposure or injury of personnel is the primary goal. Utilizationof appropriate laboratory controls (hoods) and wearing ad-equate personal protective equipme
34、nt to protect from skin andeye contact is essential.6Withdrawn. The last approved version of this historical standard is referencedon www.astm.org.7Reagent Chemicals, American Chemical Society Specifications, AmericanChemical Society, Washington, DC. For suggestions on the testing of reagents notlis
35、ted 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.8The boldface numbers in parentheses refer to the list of references a
36、t the end ofthese test methods.9Based upon Committee C26 Safeguards Matrix (C1009, C1068, C1128, C1156,C1210, C1297).C698 1026. Sampling and Dissolution6.1 Criteria for sampling this material are given in Specifi-cation C833.6.2 Samples can be dissolved using the appropriate disso-lution techniques
37、described in Practice C1168.URANIUM IN THE PRESENCE OF PLUTONIUM BYPOTENTIOMETRIC TITRATION(This test method was discontinued in 1992 and replaced byTest Method C1204.)PLUTONIUM BY CONTROLLED POTENTIALCOULOMETRY(This test method was discontinued in 1992 and replaced byTest Method C1165.)PLUTONIUM BY
38、 CONTROLLED-POTENTIALCOULOMETRY(With appropriate sample preparation, controlled-potentialcoulometric measurement as described in Test Method C1108may be used for plutonium determination.)PLUTONIUM BY AMPEROMETRIC TITRATIONWITH IRON(II)(This test method was discontinued in 1992 and replaced byTest Me
39、thod C1206.)NITROGEN BY DISTILLATIONSPECTROPHOTOMETRY USING NESSLERREAGENT7. Scope7.1 This test method covers the determination of 5 to 100g/g of nitride nitrogen in mixtures of plutonium and uraniumoxides in either pellet or powder form.8. Summary of Test Method8.1 The sample is dissolved in hydroc
40、hloric acid by thesealed tube test method or by phosphoric acid-hydrofluoricacid solution, after which the solution is made basic withsodium hydroxide and nitrogen is separated as ammonia bysteam distillation. Nessler reagent is added to the distillate toform the yellow ammonium complex and the abso
41、rbance of thesolution is measured at approximately 430 nm (4, 5).9. Apparatus9.1 Distillation Apparatus (see Fig. 1).9.2 Spectrophotometer, visible-range.10. Reagents10.1 Ammonium Chloride (NH4Cl)Dry the salt for 2 h at110 to 120C.10.2 Boric Acid Solution (40 g/litre)Dissolve 40 g ofboric acid (H3BO
42、3) in 800 mL of hot water. Cool to approxi-mately 20C and dilute to 1 L.10.3 Hydrochloric Acid (sp gr 1.19)Concentrated hydro-chloric acid (HCl).10.4 Hydrofluoric Acid (sp gr 1.15)Concentrated hydrof-luoric acid (HF).10.5 Nessler ReagentTo prepare, dissolve 50 g of potas-sium iodide (KI) in a minimu
43、m 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 (NaOH) and dilute to 1 L with water. Mix,and allow the solution to stand ove
44、rnight. Decant the superna-tant liquid and store in a brown bottle.10.6 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-free water.10.7 Sodium Hydroxide (9N)D
45、issolve 360 g of sodiumhydroxide (NaOH) in ammonia-free water and dilute to 1 L.10.8 Sodium Hydroxide Solution(50 %)DissolveNaOH in an equal weight of ammonia-free water.10.9 Water, Ammonia-FreeTo prepare, pass distilled wa-ter through a mixed-bed resin demineralizer and store in atightly stoppered
46、chemical-resistant glass bottle.11. Precautions11.1 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) avoi
47、d contamination of the atmosphere inthe vicinity of the test by ammonia or other volatile nitrog-enous compounds.12. Procedure12.1 Dissolution of Sample:FIG. 1 Distillation ApparatusC698 10312.1.1 Transfer a weighed sample, in the range from 1.0 to1.5 g, to a 50-mL beaker.NOTE 1Pellet samples should
48、 be crushed to a particle size of 1 mm orless with a diamond mortar.12.1.2 To the sample add 5 mL of HCl (sp gr 1.19) and 3drops of HF (sp gr 1.15). Heat to put the sample into solution.NOTE 2Concentrated phosphoric acid or mixtures of phosphoric acidand hydrofluoric acids or of phosphoric and sulfu
49、ric acids may be used forthe dissolution of mixed oxide samples. Such acids may require apurification step in order to reduce the nitrogen blank before being used inthis procedure.12.2 Distillation:12.2.1 Quantitatively transfer the sample solution to thedistilling flask of the apparatus. Add 20 mL of ammonia-freewater and then clamp the flask into place on the distillationapparatus (see Fig. 2).12.2.2 Turn on the steam generator but do not close with thestopper.12.2.3 Add 5 mL of boric acid solution (4 %) to a 50-mLgraduated flask and position this trap so
