ASTM C758-2004(2010) Standard Test Methods for Chemical Mass Spectrometric Spectrochemical Nuclear and Radiochemical Analysis of Nuclear-Grade Plutonium Metal《核纯级金属钚的化学、质谱、光谱化学、核(放.pdf

1、Designation: C758 04 (Reapproved 2010)Standard Test Methods forChemical, Mass Spectrometric, Spectrochemical, Nuclear,and Radiochemical Analysis of Nuclear-Grade PlutoniumMetal1This standard is issued under the fixed designation C758; the number immediately following the designation indicates the ye

2、ar oforiginal adoption 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,m

3、ass spectrometric, spectrochemical, nuclear, and radiochemi-cal analysis of nuclear-grade plutonium metal to determinecompliance with specifications.1.2 The analytical procedures appear in the following order:Sec-tionsDissolution Procedure2Plutonium by Controlled-Potential Coulometry3Plutonium by Am

4、perometric Titration with Iron (II)2Plutonium by Ceric Sulfate Titration Test Method3Plutonium by Diode Array Spectrophotometry3Uranium by Arsenazo I Spectrophotometric Test Method 8-10Thorium by Thorin Spectrophotometric Test Method 11-13Iron by 1,10-Phenanthroline Spectrophotometric Test Method 14

5、-16Iron by 2,28-Bipyridyl Spectrophotometric Test Method 17-23Impurities by ICP-AESChloride by the Thiocyanate Spectrophotometric Test Method 24-26Fluoride by Distillation-Spectrophotometric Test Method 2728Nitrogen by Distillation-Nessler Reagent Spectrophotometric TestMethod2930Carbon by the Direc

6、t Combustion-Thermal Conductivity TestMethod31-33Sulfur by Distillation-Spectrophotometric Test Method 34-36Isotopic Composition by Mass Spectrometry 37 and38Plutonium-238 Isotopic Abundance by Alpha SpectrometryAmericium-241 by Extraction and Gamma Counting 39-41Americium-241 by Gamma Counting3Gamm

7、a-Emitting Fission Products, Uranium, and Thorium byGamma-Ray Spectroscopy42-49Rare Earths by Copper Spark Spectrochemical Test Method 50-52Tungsten, Niobium (Columbium), and Tantalum by Spectro-chemical Test Method53-55Sample Preparation for Spectrographic Analysis for Trace Impurities56-601.3 The

8、values stated in SI units are to be regarded asstandard. No other units of measurement are included in thisstandard.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 this standard to establish appro-priate

9、 safety and health practices and determine the applica-bility of regulatory limitations prior to use. For specificsafeguard and safety hazards statements, see Section 6.2. Referenced Documents2.1 ASTM Standards:4C697 Test Methods for Chemical, Mass Spectrometric, andSpectrochemical Analysis of Nucle

10、ar-Grade PlutoniumDioxide Powders and PelletsC698 Test Methods for Chemical, Mass Spectrometric, andSpectrochemicalAnalysis of Nuclear-Grade Mixed Oxides(U, Pu)O2)C759 Test Methods for Chemical, Mass Spectrometric,Spectrochemical, Nuclear, and Radiochemical Analysis ofNuclear-Grade Plutonium Nitrate

11、 SolutionsC852 Guide for Design Criteria for Plutonium GloveboxesC1009 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

12、 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 Analyze Nuclear Fuel Cycle Mate-rialsC1165 Test Method for Determining

13、 Plutonium byControlled-Potential Coulometry in H2SO4at a PlatinumWorking ElectrodeC1168 Practice for Preparation and Dissolution of Pluto-nium Materials for Analysis1These test methods are under the jurisdiction of ASTM Committee C26 onNuclear Fuel Cycle and are the direct responsibility of Subcomm

14、ittee C26.05 onMethods of Test.Current edition approved Jan. 1, 2010. Published February 2010. Originallyapproved in 1973. Last previous edition approved in 2004 as C758 04. DOI:10.1520/C0758-10.2Discontinued as of February 10, 1998.3Discontinued as of November 15, 19924For referenced ASTM Standards

15、, visit the ASTM website, www.astm.org, orcontact ASTM Customer Service at serviceastm.org. For Annual Book of ASTMStandardsvolume information, refer to the standards Document Summary page onthe ASTM website.1Copyright ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 194

16、28-2959, United States.C1206 Test Method for Plutonium by Iron (II)/Chromium(VI) Amperometric 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)

17、 Titration5C1268 Test Method for Quantitative Determination of Am-ericium 241 in Plutonium by Gamma-Ray SpectrometryC1297 Guide for Qualification of Laboratory Analysts forthe Analysis of Nuclear Fuel Cycle MaterialsC1307 Test Method for PlutoniumAssay by Plutonium (III)Diode Array Spectrophotometry

18、C1415 Test Method for238Pu IsotopicAbundance ByAlphaSpectrometryC1432 Test Method for Determination of Impurities inPlutonium: Acid Dissolution, Ion Exchange Matrix Sepa-ration, and Inductively Coupled Plasma-Atomic EmissionSpectroscopic (ICP/AES) Analysis3D1193 Specification for Reagent Water3. Sig

19、nificance and Use3.1 These test methods are designed to show whether agiven material meets the purchasers specifications.3.1.1 An assay is performed to determine whether thematerial has the specified plutonium content.3.1.2 Determination of the isotopic content of the plutoniumis made to establish w

20、hether the effective fissile content is incompliance with the purchasers specifications.3.1.3 Impurity content is verified by a variety of methods toensure that the maximum concentration limit of specifiedimpurities is not exceeded. Determination of impurities is alsorequired for calculation of the

21、equivalent boron content (EBC).4. Committee C-26 Safeguards Statement64.1 The material (plutonium metal) to which these testmethods apply is subject to nuclear safeguards regulationsgoverning its possession and use. The following analyticalprocedures in these test methods have been designed astechni

22、cally acceptable for generating safeguards accountabilitymeasurement data: Plutonium by Controlled-Potential Cou-lometry; Plutonium by Ceric Sulfate Titration; Plutonium byAmperometric Titration with Iron(II); Plutonium by DiodeArray Spectrophotometry and Isotopic Composition by MassSpectrometry.4.2

23、 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 the resulting safeguards measure-ments. It

24、 remains the sole responsibility of the user of these testmethods to assure that their application to safeguards has theapproval of the proper regulatory authorities.5. Reagents and Materials5.1 Purity of ReagentsReagent grade chemicals shall beused in all test methods. Unless otherwise indicated, i

25、t isintended that all reagents shall conform to the specifications ofthe Committee onAnalytical Reagents of theAmerican Chemi-cal Society, where such specifications are available.7Othergrades may be used, provided it is first ascertained that thereagent is of sufficient high purity to permit its use

26、 withoutlessening the accuracy of the determination.5.2 Purity of WaterUnless otherwise indicated, referenceto water shall be understood to mean reagent water conformingto Specification D1193.6. Safety Hazards6.1 Since plutonium bearing materials are radioactive andtoxic, adequate laboratory facilit

27、ies, gloved boxes, fume hoods,etc., along with safe 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 han

28、dling practices as aregiven in Guide C852 and in Refs. (1-3).87. Sampling7.1 In the absence of ASTM test methods for samplingplutonium metal, alternative techniques are recommended(3-6).7.2 Cognizance shall be taken of the fact that variousimpurities can be introduced into samples during the process

29、 ofsampling. The particular impurities introduced are a functionof the method of sampling (for example, iron and alloyingelements in drill turning, oxygen or components of cooling oil,or both, from lathe turnings, etc.). It is necessary for thepurchaser and the seller to recognize this possibility f

30、orcontamination during sampling and mutually agree on the mostsuitable method.7.3 Sample size shall be sufficient to perform the following:7.3.1 Quality verification tests at the sellers plant,7.3.2 Acceptance tests at the purchasers plant, and7.3.3 Referee tests in the event these become necessary.

31、7.4 All samples shall be identified clearly by the sellersbutton number and by the lot number, and all pieces of metalin that lot shall be identified clearly by the lot number and thepiece number.7.4.1 Alot is defined as a single button, fraction of a button,or multiple castings from a single melt o

32、f plutonium metal.Buttons, fractions of buttons, or multiple castings are usuallysupplied in pieces of not less than 50 g. All pieces shall beidentified positively as coming from a particular button,fraction of a button, or casting.5Withdrawn. The last approved version of this historical standard is

33、 referencedon www.astm.org.6Based upon Committee C-26 Safeguards Matrix (C1009, C1068, C1128,C1156, C1210, C1297).7“Reagent Chemicals,American Chemical Society Specifications,”Am. Chemi-cal Soc., Washington, DC. For suggestions on the testing of reagents not listed bytheAmerican Chemical Society, se

34、e “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.C758 04 (2010)27.4.2 A lot shall normally not be less than 1800 g ofp

35、lutonium, except as necessary to meet some special require-ment. The maximum size of a lot will depend on equipmentsize of the producer and criticality considerations.DISSOLUTION PROCEDURE(This practice is replaced by Standard Practice C1168).PLUTONIUM BY CONTROLLED-POTENTIALCOULOMETRY(This test met

36、hod 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 AMPEROMETRIC TITRATIONWITH

37、 IRON(II)(This test method was discontinued in 1992 and replaced byTest Method C1206)PLUTONIUM BY CERIC SULFATE TITRATION TESTMETHOD(This test method is replaced by Test Method C1235.)TEST METHOD FOR PLUTONIUM ASSAY BYPLUTONIUM(III) DIODE ARRAYSPECTROPHOTOMETRY(With appropriate sample preparation, t

38、he measurementdescribed in Test Method C1307 may be used for plutoniumdetermination.)URANIUM BY ARSENAZO ISPECTROPHOTOMETRIC TEST METHOD8. Scope8.1 This test method covers the determination of uranium inthe range from 300 to 3000 g/g of plutonium.9. Summary of Test Method9.1 Plutonium metal dissolve

39、d in 6 N HCl is reduced toPu(III) with hydroxylamine hydrochloride. The uranium andplutonium are separated by anion exchange; then the uraniumis determined by measuring the absorbance of the U(VI)-Arsenazo I complex in a 1-cm cell at a wavelength of 600 nmversus a reagent blank.10. Procedure10.1 Tra

40、nsfer an aliquot of sample solution, prepared inaccordance with Practice C1168, that contains approximately70 mg of plutonium, to a 50-mL beaker and add 1 mL of nitricacid (sp gr 1.42) and heat to boiling. Proceed with thedetermination of uranium in accordance with the appropriatesections of Test Me

41、thods C759.NOTE 1Since the sample starts as plutonium metal and is thendissolved in acid and diluted to volume and an aliquot of this solutiontaken for the uranium determination, the following equation for calculat-ing the uranium concentration must be substituted for the equation givenin 28.1 of Te

42、st Methods C759:R 5 Y 2 B!D/AW (1)where:R = micrograms U per gram Pu,A, B = constants in linear calibration equation,D = dilution factor = V/Ewhere:V = volume in which sample solution was diluted, mL, andE = volume of aliquot of V used for uranium determina-tion, mL,W = weight of test portion of Pu

43、metal sample, g, andY = a b = corrected absorbance of sample,where:a = absorbance of sample solution, andb = average absorbance of duplicate calibration blanks.THORIUM BY THORIN SPECTROPHOTOMETRICTEST METHOD11. Scope11.1 This test method covers the determination of thoriumin the range from 10 to 150

44、 g/g of plutonium in nuclear-gradeplutonium metal.12. Summary of Test Method12.1 To an acid solution of plutonium metal, lanthanum isadded as a carrier and is precipitated along with thorium asinsoluble fluoride, while the plutonium remains in solution andis decanted after centrifugation of the samp

45、le. The thorium andlanthanum fluoride precipitates are dissolved in perchloric acidand the absorbance of the thorium-Thorin complex is measuredat a wavelength of 545 nm versus a reference solution. Themolar absorptivity of the colored complex is of 15 600 forthorium concentration in the range from 5

46、 to 70 g Th/10 mLof solution.13. Procedure13.1 Transfer an aliquot of solution of plutonium metal,prepared in accordance with Sections 6 and 7 of these testmethods, that contains from 10 to 70 g of thorium and nogreater than 500 mg of plutonium, into a 20-mL beaker.13.2 Determine the thorium concent

47、ration in accordancewith the appropriate sections of Test Methods C759.NOTE 2Since the starting sample is plutonium metal the followingequation for calculating the thorium concentration must be substituted forthe equation given in 49.3 of Test Methods C759:Th, g/g of Pu 5 Y 2 B!D/AW (2)where:A, B =

48、constants in the linear calibration equation,W = sample weight, g,D = dilution factor = V/EC758 04 (2010)3where:V = volume to which dissolved plutonium metal is diluted,mL, andE = volume of aliquot of V taken for determination, mL,Y = a b = corrected absorbance of sample solutionwhere:a = absorbance

49、 of sample solution, andb = average absorbance from the duplicate reagent blanks(see section 47.2.1 of Test Methods C759).IRON BY 1,10-PHENANTHROLINESPECTROPHOTOMETRIC TEST METHOD14. Scope14.1 This test method covers the determination of micro-gram quantities of iron in nuclear-grade plutonium metal.15. Summary of Test Method15.1 Ferric iron is reduced to ferrous iron with hydroxy-lamine hydrochloride. Solutions of 1,10-phenanthroline andacetate buffer are added and the pH adjusted to 3.5 to 4.5. Theabsorbance of the red-orange complex (C12H8N2)3Fe+2isread