1、Designation: C 1517 09Standard Test Method forDetermination of Metallic Impurities in Uranium Metal orCompounds by DC-Arc Emission Spectroscopy1This standard is issued under the fixed designation C 1517; 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 () indicates an editorial change since the last revision or reapproval.1. Scope1.1 This test method describes the steps necessary for thepreparation and determination o
3、f impurity metals in uraniummetal and uranium compounds by DC arc emission spectros-copy.1.2 The method is valid for those materials that can bedissolved in acid and/or converted to an oxide in a mufflefurnace (see Practice C 1347).1.3 This method uses the carrier distillation technique toselectivel
4、y carry the impurities into the arc, leaving theuranium oxide in the electrode. If it is necessary to determinethe carrier metal(usually a silver or strontium, or galliumcompound) as an impurity, another technique must be chosenfor that element.1.4 UnitsThe values stated in SI units are to be regard
5、edas standard. The values given in parentheses are for informa-tion only.1.5 This standard may involve hazardous materials, opera-tions and equipment. This standard does not purport to addressall of the safety concerns, if any, associated with its use. It isthe responsibility of the user of this sta
6、ndard to establishappropriate safety and health practices and determine theapplicability of regulatory limitations prior to use.2. Referenced Documents2.1 ASTM Standards:2C 753 Specification for Nuclear-Grade, Sinterable UraniumDioxide PowderC 761 Test Methods for Chemical, Mass Spectrometric,Spectr
7、ochemical, Nuclear, and Radiochemical Analysis ofUranium HexafluorideC 776 Specification for Sintered Uranium Dioxide PelletsC 788 Specification for Nuclear-Grade Uranyl Nitrate So-lution or CrystalsC 859 Terminology Relating to Nuclear MaterialsC 967 Specification for Uranium Ore ConcentrateC 1347
8、Practice for Preparation and Dissolution of UraniumMaterials for AnalysisE 130 Practice for Designation of Shapes and Sizes ofGraphite ElectrodesE 135 Terminology Relating to Analytical Chemistry forMetals, Ores, and Related Materials3. Terminology3.1 See definitions and terms in Terminologies C 859
9、 andE 135.4. Summary of Test Method4.1 Uranium metal, solutions and compounds are convertedto uranium oxide (U3O8) in a muffle furnace. A weighedamount of the oxide is mixed with an appropriate spectro-graphic carrier and loaded into a graphite electrode. Theelectrode is excited in a DC arc and the
10、light is dispersed by aspectrograph or spectrometer. The resulting spectrum is mea-sured electronically using a CCD, CID or CMOS camera orphotographed on photographic plates or film sensitive to theproper regions. The line intensities are compared directly tostandard plates or to calibration curves
11、derived from the arcedstandards.5. Significance and Use5.1 This test method is applicable to uranium metal, ura-nium oxides and compounds soluble in nitric or sulfuric acid,and uranium solutions which can be converted to uraniumoxide (U3O8) in a muffle furnace. It may be used to determinethe impurit
12、ies in uranium compounds as listed in SpecificationsC 753, C 776, C 788, and C 967.6. Apparatus6.1 Spectrograph or SpectrometerA spectrograph withsufficient resolving power and linear dispersion to separate theanalytical lines from other lines in the spectrum of the samplein the spectral region of 2
13、30.0 to 855.0 nm is required.1This test method is under the jurisdiction ofASTM Committee C26 on NuclearFuel Cycle and is the direct responsibility of Subcommittee C26.05 on Methods ofTest.Current edition approved June 1, 2009. Published July 2009. Originally approvedin 2002. Last previous edition a
14、pproved in 2002 as C 1517 02.2For 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.1Copyright ASTM International, 1
15、00 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959, United States.Instruments with a reciprocal linear dispersion in the first orderof 0.5 nm/mm or less are satisfactory. A direct-reading spec-trometer of comparable quality may be substituted for equip-ment listed, in which case the
16、 directions given by the manu-facturer should be substituted for those in this procedure.6.2 Excitation SourceUse an arc power source capable ofproviding a dc arc of up to 14-A dc, depending on the carrierused and electrode design.6.3 Excitation StandConventional type with adjustablewater-cooled ele
17、ctrode holders (may be fitted with automaticsample changers if desired).6.4 Photographic Processing EquipmentUse developing,fixing, washing and drying equipment.6.5 Microphotometer, having a precision of at least 6 1%for transmittances.6.6 Mixer, for dry materials.6.7 Platinum Crucible.6.8 Venting T
18、ool, (see Fig. 8, Test Methods C 761).6.9 Muffle Furnace, 1000C capability.7. Reagents and Materials7.1 Purity of MaterialsReagent grade chemicals shall beused in all tests. Unless otherwise indicated, it is intended thatall reagents conform to the specifications of the Committee ofAnalytical Reagen
19、ts of the American Chemical Society wheresuch specifications are available. Other grades may be usedprovided it is first ascertained that the reagent is of sufficientlyhigh purity to permit its use without lessening the accuracy ofthe determination.7.2 ElectrodesThe anode and counter electrodes shou
20、ldbe of the S-2, S 16 and C-1 types as given in Practice E 130 (orequivalent).NOTE 1Exact shapes and dimensions of the electrodes are not ascritical as given in Practice E 130; however, dimensions of the electrodesused should be consistent and it is essential that the same dimensionelectrodes be use
21、d for standards and samples.7.3 Photographic Processing SolutionsPrepare solutionsas noted in available literature (1,2).7.4 Photographic Film/PlatesUse photo emulsion SA-1and 1-N or equivalent.7.5 Powder Paper.7.6 Nitric Acid (HNO3)concentrated (70 %), electronicgrade, or equivalent.7.7 Sulfuric Ac
22、id (H2SO4)concentrated, electronic grade,or equivalent.7.8 Spectrographic CarrierThe following spectrographiccarriers have been used successfully for DC Arc analysis:7.8.1 Silver Chloride-Lithium Fluoride, 11:1 w/w ratio.7.8.2 Silver Chloride-Silver Fluoride, 4:1 w/w ratio.7.8.3 Gallium Oxide, 99.99
23、 % or better.7.8.4 Silver Chloride-Strontium Fluoride, 16.4 mol % SrF2in AgCl.7.8.5 Gallium Oxide-Lithium Fluoride, 11:1 w/w ratio.7.9 Mixing Vial, plastic, 12.7 mm (1/2 in.) by 25.4 mm (1in.) with cap and 10 mm (3/8 in.) plastic mixing bead.7.10 Standard Uranium Oxide (U3O8) DiluentUse NBLCRM 1294(
24、or its replacement or equivalent) of known impu-rity level as a diluent.8. Precautions8.1 Consult manufacturers Material Safety Data Sheets(MSDS) for chemical incompatibilities, specific hazards, orspill cleanup for any hazardous materials used in this method.8.2 All mixing and weighing operations i
25、nvolving uraniumoxides should be carried out in properly functioning hoods orexhaust boxes.9. Standardization and Calibration9.1 Standards:9.1.1 Standards may be synthesized by adding the impurityelements to purified U3O8(NBLCRM 1293, or equivalent) andhomogenizing. Impurities in powder form, prefer
26、ably as ox-ides, may be blended in U3O8; impurities in solution may beadded to U3O8and the mixture dried, blended and reignited, orthe impurities and uranium may be combined in solution andreconverted to U3O8. The individual elements should grade insuch a ratio as to facilitate visual comparisons co
27、vering thedesired analytical range for each.9.1.2 The compounds used to make U3O8impurity stan-dards should be of the highest purity available.9.1.3 Alternatively, commercially available uranium impu-rity standards, such as NBL CRM 1233and 1243seriesstandards, may be used. (Other standards may be av
28、ailable; theuser should determine quality and/or applicability prior to use.)These may be supplemented by synthetic standards to extendcalibration ranges, if necessary.9.1.4 For each standard used, prepare in the same ratio ofuranium oxide to carrier as for samples (see Table 1 for furtherdetails).9
29、.1.5 Charge the electrode and arc at the same conditions asdetermined to be optimum for the instrument in use.9.2 Calibration Curves:9.2.1 If a microphotometer is used, determine emulsioncalibration curves and analytical curves as described in avail-able literature (1,2).3Available from the US Depar
30、tment of Energy, New Brunswick Laboratory, D350, 9800 South CassAvenue,Argonne, IL60439,ATTN: Reference Material Sales.http:/www.nbl.doe.gov/TABLE 1 CarrierSample CombinationsCarrierMaterialCarrier Wt,(mg)Oxide Wt,(mg)ElectrodeCharge, (mg)Mixing Time,(s)AgCl/AgF(4:1)50 250 50 180AgCl/LiF(11:1)30 270
31、 100 60AgCl/SrF2(6:1)50 450 100 30Ga2O3/LiF(11:1)20 380 100 25Ga2O3A7 343 100 60AFor the determination of Ag and Li only.NOTEThe above listed combinations of carrier, uranium oxide andelectrode charge have been successfully used for the determination ofimpurities in uranium oxide. Other combinations
32、 may be available orsuitable. However, the user must demonstrate comparable precision andbias.C15170929.2.2 If a direct reading spectrometer is used, calibrateaccording to manufacturers instruction.9.2.3 For visual comparison, the darkness/width of eachstandard and impurity element line will establi
33、sh the individualanalyte concentrations.10. Procedure10.1 Sample Preparation10.1.1 Liquid Samples:10.1.1.1 Transfer into a platinum crucible a sufficientamount of liquid to yield not more than 2 g uranium oxide.10.1.1.2 Place the crucible on a hot plate and evaporate todryness. Do not allow to boil.
34、NOTE 2The addition of H2SO4may be necessary for solutions ofuranyl chloride to effect complete conversion to oxide.10.1.1.3 Continue the preparation at 10.1.2.2.10.1.2 Miscellaneous Uranium Oxides, Solids or Com-pounds:10.1.2.1 Transfer not more than2goftheuranium com-pound to a platinum crucible.10
35、.1.2.2 Place in a cool muffle and set the muffle to 900 650C.NOTE 3Some impurities (for example, Mo, W, Cr) may be lost at hightemperatures. Do NOT place samples directly in hot muffle. Lowertemperatures may be used if it is determined that complete oxideconversion is achieved.10.1.2.3 Leave the cru
36、cibles and samples in the muffle untilconversion to U3O8is complete.NOTE 4Times will vary depending on amount and type of sample; theuser must determine optimum time experimentally for his sample types.10.2 Addition of Carrier:10.2.1 Weigh an appropriate amount of uranium oxide intoa mixing vial and
37、 add the amount of carrier chosen (see Table1).10.2.2 Mix on a mixer for at least 1 min.NOTE 5Exact time will depend on efficiency of mixing action of themixer chosen, the amount of sample and carrier used. The user mustdetermine this experimentally for his sample type (see Table 1).10.3 Charge each
38、 electrode with the amount of uraniumoxide and carrier determined to be optimum. For each samplecharge duplicate electrodes.10.4 Grip each electrode with forceps and pack the chargeby tapping on a solid surface.10.5 Further compress and vent the charge with the ventingtool shortly before arcing the
39、samples. Wipe the venting toolwith tissue between different samples.NOTE 6Venting is dependent on the carrier used and may not berequired. A combination tamping/venting tool is permissible.10.6 Arc the electrodes at the conditions determined opti-mum for the instrument in use.10.7 If photographic fi
40、lm or plates are used, process asdirected in available literature (1,2). If a direct reading spec-trograph is used, the impurity values will be reported as eachelectrode is arced.10.8 Determine each impurity by comparing the lines foreach element using the calibration curves established in 9.2.11. P
41、recision and Bias11.1 There are not certified materials for the determinationof all elements that may be analyzed by this method. Norwould all the elements be expected in these materials. How-ever, there are standards available from the New BrunswickLaboratory certified for many of the elements of i
42、nterest. Datausing these standards and other available standards are listed inTables 3 and 4. Each user must determine the proper qualityTABLE 2 Typical Wavelengths and Limits of DetectionElement Wavelength(nm)LOD usingAgCl/AgF(ppm)LOD usingAgCl/LiF(ppm)LOD usingGa2O3/LiF(ppm)Al 308.21236.70151As 23
43、4.98 10 . . .Au 267.59 1 . . .B 249.77 0.1 0.4 0.5Ba 455.40493.4121Be 234.86249.450.111Bi 306.77 1 . . .Ca 396.84422.641025Cd 228.80 0.1 0.3 0.5Co 240.72340.5115Cr 284.33425.44427.482103Cs 852.11 10 . . .Cu 324.75327.40121Fe 248.33252.28302.0610202Ga 294.36 1 . . .Ge 265.12 1 . . .K 769.89 10 . . .L
44、i 670.78 0.2Mg 279.55280.272101Mn 279.48279.831101Mo 313.21 10Na 588.99589.59110Nb 316.34 10 . . .Ni 300.25341.48152P 255.33213.6210025Pb 283.31 4 3 1Pd 340.46 1 . . .Rb 780.02 20 . . .Sb 259.81 2 10Si 250.69251.61288.1610101Sn 283.99317.501021Sr 407.77 20 . . .Ta 265.33 35Ti 334.90337.2845V 292.403
45、18.3415W 294.70 100 . . .Zn 330.25213.86101030C1517093control and assurance measures for his application and thecarrier/sample combination used. Relative standard deviationsare calculated relative to average value. For different elementsthe relative standard deviation was found to be between 9 %and
46、23 %. These sigma are an indication of precision. Therelative difference from the certified values vary from 0 % to20 %. These numbers are an indication of the potential bias.This data was collected over a 12-month period in two differentlaboratories by several different technicians and is typical o
47、fdata for these techniques. For other elements not in thesestandards, the precision is normally 50 % to +100 % of thedetermined value. The user can expect precision and biasvalues for some elements (those with weak emission lines orhighly refractory elements) to be greater than the values listedinTa
48、bles 3 and 4.Those values must be determined by the user.12. Keywords12.1 carrier distillation; dc-arc; emission spectroscopy; im-purities in uraniumREFERENCES(1) Anderson, J. W. and Lincoln, A. J., “General Mathematical Approachto Emulsion Calibration in Optical Emission Spectroscopy,” AppliedSpect
49、roscopy, Vol 22, 1968, p. 753.(2) Woodyard, J. R., Piper, B. C., and Stever, K. R., “The Functional Formof the Emulsion Calibration Curve,” Applied Spectroscopy, Vol. 33,1979, p. 25.ASTM International takes no position respecting the validity of any patent rights asserted in connection with any item mentionedin this standard. Users of this standard are expressly advised that determination of the validity of any such patent rights, and the riskof infringement of such rights, are entirely their own responsibility.This standard is subject to revision at any
