1、Designation: C 697 04Standard Test Methods forChemical, Mass Spectrometric, and SpectrochemicalAnalysis of Nuclear-Grade Plutonium Dioxide Powders andPellets1This standard is issued under the fixed designation C 697; the number immediately following the designation indicates the year oforiginal adop
2、tion or, in the case of revision, the year of last revision. A number in parentheses indicates the year of last reapproval. Asuperscript epsilon (e) indicates an editorial change since the last revision or reapproval.1. Scope1.1 These test methods cover procedures for the chemical,mass spectrometric
3、, and 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 Sulfat
4、e Titration3Plutonium 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
5、 by 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 Coulome
6、tric 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 Sp
7、ectrometry 97 to 105Oxygen-To-Metal Atom Ratio by Gravimetry 106 to 1141.3 This standard does not purport to address all of thesafety concerns, if any, associated with its use. It is theresponsibility of the user of this standard to establish appro-priate safety and health practices and determine th
8、e 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 Standards:5C 757 Specification for Nuclear-Grade Plutonium DioxidePowder, SinterableC 852 Guide for Design Criteria for Plu
9、tonium GloveboxesC 1009 Guide for Establishing a Quality Assurance Pro-gram for Analytical Chemistry Laboratories Within theNuclear IndustryC 1068 Guide for Qualification of Measurement Methodsby a Laboratory Within the Nuclear IndustryC 1108 Test Method for Plutonium by Controlled-PotentialCoulomet
10、ryC 1128 Guide for Preparation of Working Reference Mate-rials for Use in the Analysis of Nuclear Fuel CycleMaterialsC 1156 Guide for Establishing Calibration for a Measure-ment Method Used to Analyze Nuclear Fuel Cycle Mate-rialsC 1165 Test Method for Determining Plutonium byControlled-Potential Co
11、ulometry in H2SO4at a PlatinumWorking ElectrodeC 1168 Practice for Preparation and Dissolution of Pluto-nium Materials for AnalysisC 1206 Test Method for Plutonium by Iron (II)/Chromium(VI) Amperometric TitrationC 1210 Guide for Establishing a Measurement SystemQuality Control Program for Analytical
12、 Chemistry Labo-ratories Within the Nuclear IndustryC 1235 Test Method for Plutonium by Titanium(III)/Cerium(IV) TitrationC 1268 Test Method for Quantitative Determination ofAmericium 241 in Plutonium by Gamma-Ray Spectrom-etryC 1297 Guide for Qualification of Laboratory Analysts forthe Analysis of
13、Nuclear Fuel Cycle Materials1These methods are under the jurisdiction of ASTM Committee C26 on NuclearFuel Cycle and are the direct responsibility of Subcommittee C26.05 on Methods ofTest.Current edition approved Jan. 1, 2004. Published February 2004. Originallyapproved in 1972. Last previous editio
14、n approved in 1998 as C 697 98.2Discontinued as of November 15, 1992.3Discontinued as of xxxx, 2003.4Discontinued 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 infor
15、mation, refer to the standards Document Summary page onthe ASTM website.1Copyright ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959, United States.C 1307 Test Method for Plutonium Assay by Plutonium(III)Diode Array SpectrophotometryC 1415 Test Method for238Pu
16、Isotopic Abundance By Al-pha SpectrometryC 1432 Test Method for Determination of Impurities inPlutonium: Acid Dissolution, Ion Exchange Matrix Sepa-ration, and Inductively Coupled Plasma-Atomic EmissionSpectroscopic (ICP/AES) AnalysisD 1193 Specification for Reagent WaterE 60 Practice for Photometri
17、c and SpectrophotometricMethods for Chemical Analysis of MetalsE 115 Practices for Photographic Processing in OpticalEmission Spectrographic AnalysisE 116 Practice for Photographic Photometry in Spectro-chemical Analysis3. Significance and Use3.1 Plutonium dioxide is used in mixtures with uraniumdio
18、xide as a nuclear-reactor fuel. In order 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 describ
19、ed in Speci-fication C 757.3.1.1 An assay is performed to determine whether thematerial 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 conte
20、nt is in compliance with the purchas-ers specifications.3.1.3 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).4. Committee C-26
21、Safeguards Statement64.1 The materials (plutonium dioxide powders and pellets)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
22、generating safe-guards accountability measurement data: Plutonium byControlled-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 Is
23、o-topic Analysis by Mass Spectrometry.4.2 When used in conjunction with appropriate 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 t
24、he 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. Reagents5.1 Purity of ReagentsReagent grade chemicals shall beused in all tests. Unless othe
25、rwise indicated, 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.7Other grades may beused, provided it is first ascertained that the reagent is ofsufficiently high pu
26、rity to permit 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 D 1193.6. Safety Precautions6.1 Since plutonium bearing materials are radioactive andtoxic,
27、 adequate laboratory facilities, gloved boxes, fume hoods,etc., along with safe techniques, must be used in handlingsamples containing these materials. A detailed discussion of allthe precautions necessary is beyond the scope of these testmethods; however, personnel who handle these materialsshould
28、be familiar with such safe handling practices as aregiven in Guide 852 and in Refs (1) through (3).87. Sampling and Dissolution7.1 Criteria for sampling this material are given in Specifi-cation C 757.7.2 Samples can be dissolved using the appropriate disso-lution technique described in Practice C 1
29、168.PLUTONIUM 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 are just as applicable to any group handling thematerial.9. Summary of Tes
30、t 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 has been foundadequate to prevent sorption of water, but care must beexe
31、rcised to use equipment and sample containers known to bedry.6Based upon Committee C-26 Safeguards Matrix (C 1009, C 1068, C 1128,C 1156, C 1210, C 1297).7“Reagent Chemicals, American Chemical Society Specifications,” Am. Chemi-cal Soc., Washington, DC. For suggestions on the testing of reagents not
32、 listed bythe American Chemical Society, see “Reagent Chemicals and Standards,” by JosephRosin, D. Van Nostrand Co., Inc., New York, NY, and the “United StatesPharmacopeia.”8The boldface numbers in parentheses refer to the list of references at the end ofthese test methods.C69704210. Sample Handling
33、 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 theycannot be adequately dried. Glass bottles and aluminum
34、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 to correct for moisture absorp-tion, such as drying, m
35、ust 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 method was discontinued in 1992 and replaced byTest Me
36、thod C 1165.)PLUTONIUM BY CONTROLLED-POTENTIALCOULOMETRY(With appropriate sample preparation, controlled-potentialcoulometric measurement as described in Test Method C 1108may be used for plutonium determination.)PLUTONIUM BY CERIC SULFATE TITRATION(This test method was discontinued in 2003 and repl
37、aced byTest Method C 1235.)PLUTONIUM BY AMPEROMETRIC TITRATIONWITH IRON (II)(This test method was discontinued in 1992 and replaced byTest Method C 1206.)STANDARD TEST METHOD FOR PLUTONIUMASSAY BY PLUTONIUM(III) DIODE ARRAYSPECTROPHOTOMETRY(With appropriate sample preparation, the measurementdescrib
38、ed in Test Method C 1307 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. Summary of Test Method12.1 Th
39、e 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 distillate to form theyellow amm
40、onium 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.FIG. 1 Distillation ApparatusC69704314. Reagents14.1 Ammonium Chloride (NH4Cl)Dry salt for2hat110to 120C.14.2 Boric Aci
41、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
42、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
43、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
44、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.14.9 Water (Ammonia-free)To prepare, pass distilled wa-ter through a mixed-bed resin deminera
45、lizer 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
46、 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 to a 50-mL beaker.NOTE 2Crush the pellet sampl
47、es to a particle size of 1 mm or less ina diamond mortar.16.1.2 To the sample add 5 mL of HCl and 3 drops of HF.Heat to put sample into solution.NOTE 3Concentrated phosphoric acid or mixtures of phosphoric acidand hydrofluoric acids or of phosphoric and sulfuric acids may be used forthe dissolution
48、of plutonium dioxide. Such acids may require a purifica-tion step in order to reduce the nitrogen blank before being used in thisprocedure.16.2 Distillation:16.2.1 Quantitatively transfer the sample solution to thedistilling flask of the apparatus. Add 20 mL of ammonia-freewater; then clamp the flas
49、k into place on the distillationapparatus (see Fig. 1).16.2.2 Turn on the steam generator, but do not close withthe stopper.16.2.3 Add 5 mL of 4 % H3BO3solution to a 50-mLgraduated flask and position this trap so that the condenser tipis below the surface of the H3BO3solution.16.2.4 Transfer 20 mL of 50 % NaOH solution to the funnelin the distillation head.16.2.5 When the water begins to boil in the steam generator,replace the stopper and slowly open the stopcock on thedistilling flask to allow the NaOH solution to run into thesample solution.NOTE 4The NaOH
