1、Designation: C 698 04Standard Test Methods forChemical, Mass Spectrometric, and SpectrochemicalAnalysis of Nuclear-Grade Mixed Oxides (U, Pu)O2)1This standard is issued under the fixed designation C 698; the number immediately following the designation indicates the year oforiginal adoption or, in t
2、he 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, and spectro
3、chemical 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 Coulometry2Plut
4、onium by Amperometric Titration with Iron (II)2Nitrogen by Distillation Spectrophotometry Using Nessler Re-agent7to14Carbon (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
7、Atom Ratio by Gravimetry 107 to 1151.3 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 the applica-bility of regulatory limit
8、ations 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:5C 697 Test Methods for Chemical, Mass Spectrometric, andSpectrochemical Analysis of Nuclear-Grade PlutoniumDioxide Powders and Pellets
9、C 833 Specification for Sintered (Uranium-Plutonium) Di-oxide PelletsC 852 Guide for Design Criteria for Plutonium GloveboxesC 1008 Specification for Sintered (uranium-Plutonium) Di-oxide PelletsFast Reactor FuelC 1009 Guide for Establishing a Quality Assurance Pro-gram for Analytical Chemistry Labo
10、ratories Within theNuclear IndustryC 1068 Guide for Qualification of Measurement Methodsby a Laboratory Within the Nuclear IndustryC 1108 Test Method for Plutonium by Controlled-PotentialCoulometryC 1128 Guide for Preparation of Working Reference Mate-rials for Use in the Analysis of Nuclear Fuel Cy
11、cleMaterialsC 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 Coulometry in H2SO4at a PlatinumWorking ElectrodeC 1168 Practice for Preparation and Dissolution of Pluto-n
12、ium Materials for AnalysisC 1204 Test Method for Uranium in the Presence of Pluto-nium by Iron (II) Reduction in Phosphoric Acid Followedby Chromium (VI) TitrationC 1206 Test Method for Plutonium by Iron (II)/Chromium(VI) Amperometric Titration1These test methods are under the jurisdiction of ASTM C
13、ommittee C26 onNuclear Fuel Cycle and are the direct responsibility of Subcommittee C26.05 onMethods of Test.Current edition approved Jan. 1, 2004. Published February 2004. Originallyapproved in 1972. Last previous edition approved in 1998 as C698 98.2Discontinued as of November 15, 1992.3Discontinu
14、ed as of May 30, 1980.4Discontinued as of xxxx, 2003.5For 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.1Copyrig
15、ht ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959, United States.C 1210 Guide for Establishing a Measurement SystemQuality Control Program for Analytical Chemistry Labo-ratories Within the Nuclear IndustryC 1268 Test Method for Quantitative Determination ofA
16、mericium 241 in Plutonium by Gamma-Ray Spectrom-etryC 1297 Guide for Qualification of Laboratory Analysts forthe Analysis of Nuclear Fuel Cycle MaterialsC 1415 Test Method for238Pu Isotopic Abundance By Al-pha SpectrometryC 1432 Test Method for Determination of Impurities inPlutonium: Acid Dissoluti
17、on, Ion Exchange Matrix Sepa-ration, and Inductively Coupled Plasma-Atomic EmissionSpectroscopic (ICP/AES) AnalysisD 1193 Specification for Reagent WaterE 60 Practice for Photometric and SpectrophotometricMethods for Chemical Analysis of MetalsE 115 Practices for Photographic Processing in OpticalEm
18、ission Spectrographic AnalysisE 116 Practice for Photographic Photometry in Spectro-chemical Analysis3. Significance and Use3.1 Mixed oxide, a mixture of uranium and plutoniumoxides, is used as a nuclear-reactor fuel in the form of pellets.The plutonium content may be up to 10 weight %, and thedilue
19、nt 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, effectivefissile content, and impurity content as described in Specifica-tion C 833.3.1.1 The material is assayed for uranium
20、and plutonium todetermine whether the plutonium content is as specified by thepurchaser, and whether the material contains the minimumcombined uranium and plutonium contents specified on a dryweight basis.3.1.2 Determination of the isotopic content of the plutoniumand uranium in the mixed oxide is m
21、ade 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 limit of certain impurity elements isnot exceeded. Determination of impurities is also required forcalculation of th
22、e 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 conform to the specifications of the Commit-tee on Analytical Reagents of the American Chemical Society,where such sp
23、ecifications are available.6Other 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.4.2 Purity of Water Unless otherwise indicated, refer-ences to water shall be understood to mean r
24、eagent waterconforming to Specification D 1193.5. Safety Precautions5.1 Since plutonium- and uranium-bearing materials areradioactive and toxic, adequate laboratory facilities, glovedboxes, fume hoods, etc., along with safe techniques must beused in handling samples containing these materials. A det
25、aileddiscussion 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 are given in Guide C 852 and in Refs (1) through (3).75.2 Committee C-26 Safeguards Statement:85.2.1 The mate
26、rials 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 analytical procedures in thesetest methods have been designated as technically acceptable forgenerating safe
27、guards accountability measurement data: Ura-nium by Controlled Potential Coulometry; Plutonium byControlled-Potential Coulometry; Plutonium by AmperometricTitration with Iron(II); Plutonium-238 Isotopic Abundance byAlpha Spectrometry; and Uranium and Plutonium IsotopicAnalysis by Mass Spectrometry.5
28、.2.2 When used in conjunction with appropriate certifiedreference materials (CRMs), these procedures can demonstratetraceability to the national measurements base. However,adherence to these procedures does not automatically guaran-tee regulatory acceptance of the resulting safeguards measure-ments.
29、 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.6. Sampling and Dissolution6.1 Criteria for sampling this material are given in Specifi-cation C 833.6.2 Samples can be dissolved usi
30、ng the appropriate disso-lution techniques described in Practice C 1168.URANIUM IN THE PRESENCE OF PLUTONIUM BYPOTENTIOMETRIC TITRATION(This test method was discontinued in 1992 and replaced byTest Method C 1204.)PLUTONIUM BY CONTROLLED POTENTIALCOULOMETRY(This test method was discontinued in 1992 a
31、nd replaced byTest Method C 1165.)6“Reagent Chemicals, American Chemical Society Specifications,” Am. Chemi-cal Soc., Washington, DC. For suggestions on the testing of reagents not listed bythe American Chemical Society, see “Reagent Chemicals and Standards,” by JosephRosin, D. Van Nostrand Co., Inc
32、., New York, NY, and the “United StatesPharmacopeia.”7The boldface numbers in parentheses refer to the list of references at the end ofthese test methods.8Based upon Committee C-26 Safeguards Matrix (C 1009, C 1068, C 1128,C 1156, C 1210, C 1297).C698042PLUTONIUM BY CONTROLLED-POTENTIALCOULOMETRY(Wi
33、th appropriate sample preparation, controlled-potentialcoulometric measurement as described in Test Method C 1108may be used for plutonium determination.)PLUTONIUM BY AMPEROMETRIC TITRATIONWITH IRON(II)(This test method was discontinued in 1992 and replaced byTest Method C 1206.)NITROGEN BY DISTILLA
34、TIONSPECTROPHOTOMETRY 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 hydrochloric acid by thesealed tube te
35、st 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 absorbance of thesolution is measure
36、d 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 for2hat110 to 120C.10.2 Boric Acid Solution (40 g/litre)Dissolve 40 g ofboric acid (H3BO3) in 800 mL of hot water. Cool toa
37、pproximately 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 Reagent To prepare, dissolve 50 g of potas-sium iodide (KI) in a minimum of cold ammonia-free water,approxi
38、mately 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 overnight. Decant the superna-tant liqu
39、id 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)Dissolve 360 g of sodiumhydroxide (Na
40、OH) 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 chemical-resistant glass bottle.11.
41、 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) avoid contamination of the atmosphere
42、inthe vicinity of the test by ammonia or other volatile nitrog-enous compounds.12. Procedure12.1 Dissolution of Sample:12.1.1 Transfer a weighed sample, in the range from 1.0 to1.5 g, to a 50-mL beaker.NOTE 1Pellet samples should be crushed to a particle size of 1 mm orless with a diamond mortar.12.
43、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 sulfuric acids may be used forthe dissolution of mixed oxide samples. Such a
44、cids may require apurification step in order to reduce the nitrogen blank before being used inthis procedure.12.2 Distillation:FIG. 1 Distillation ApparatusC69804312.2.1 Quantitatively transfer the sample solution to thedistilling flask of the apparatus. Add 20 mL of ammonia-freewater and then clamp
45、 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 that the condenser tipis below the surface of the boric acid solution.1
46、2.2.4 Transfer 20 mL of NaOH solution (50 %) to thefunnel in the distillation head.12.2.5 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 3The NaOH solution mus
47、t be added slowly to avoid a violentreaction which may lead to loss of sample.12.2.6 Steam distill until 25 mL of distillate has collected inthe trap.12.2.7 Remove the trap containing the distillate from thedistillation apparatus, and remove the stopper from the steamgenerator.12.2.8 Transfer the co
48、oled distillate to a 50-mL volumetricflask.12.2.9 Prepare a reagent blank solution by following steps12.1.1 through 12.2.8.12.3 Measurement of Nitrogen:12.3.1 Add 1.0 mL of Nessler reagent to each of thedistillates collected in 12.2.8 and 12.2.9. Dilute to volume withammonia-free water, mix, and let
49、 stand for 10 min.12.3.2 Measure the absorbance of the solutions at 430 nm ina 1-cm cell. Use water as the reference.12.4 Calibration Curve:12.4.1 Add 0, 5, 10, 25, 100, and 150 g of nitrogen fromthe nitrogen standard solution to separate distilling flasks.Then, add 5 mL of HCl and 3 drops of HF plus 20 mL ofammonia-free water to each flask.12.4.2 Process each solution by the procedure in 12.2through 12.3 (omit step 12.2.9).12.4.3 Correct for the reagent blank reading and plot theabsorbance of each standard against micrograms of nitrogenper 50 mL of solution.1
