1、Designation: C809 94 (Reapproved 2007) C809 13Standard Test Methods forChemical, Mass Spectrometric, and SpectrochemicalAnalysis of Nuclear-Grade Aluminum Oxide and AluminumOxide-Boron Carbide Composite Pellets1This standard is issued under the fixed designation C809; the number immediately followin
2、g the designation indicates the year 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 c
3、over procedures for the chemical, mass spectrometric, and spectrochemical analysis of nuclear-gradealuminum oxide and aluminum oxide-boron carbide composite pellets to determine compliance with specifications.1.2 The analytical procedures appear in the following order:SectionsBoron by Titrimetry 7 t
4、o 13Boron by Titrimetry and ICP OES 7 to 16Separation of Boron for Mass Spectrometry 14 to 19Separation of Boron for Mass Spectrometry 17 to 22Isotopic Composition by Mass Spectrometry 20 to 23Isotopic Composition by Mass Spectrometry 23 to 26Separation of Halides by Pyrohydrolysis 24 to 27Separatio
5、n of Halides by Pyrohydrolysis 27 to 30Fluoride by Ion-Selective Electrode 28 to 30Chloride and Fluoride by Ion-Selective Electrode 31 to 33Chloride, Bromide, and Iodide by Amperometric Microtitrimetry 31 to 33Chloride, Bromide, and Iodide by Amperometric Microtitrimetry 34 to 36Trace Elements by Em
6、ission Spectroscopy 34 to 46Trace Elements by Emission Spectroscopy 37 to 49Keywords 501.3 The values stated in SI units are to be regarded as the standard.1.4 This standard does not purport to address all of the safety concerns, if any, associated with its use. It is the responsibilityof the user o
7、f this standard to establish appropriate safety and health practices and determine the applicability of regulatorylimitations prior to use. (For specific precautionary statements, see Section 5.)2. Referenced Documents2.1 ASTM Standards:2C784 Specification for Nuclear-Grade Aluminum Oxide-Boron Carb
8、ide Composite PelletsC785 Specification for Nuclear-Grade Aluminum Oxide PelletsC791 Test Methods for Chemical, Mass Spectrometric, and Spectrochemical Analysis of Nuclear-Grade Boron CarbideC799 Test Methods for Chemical, Mass Spectrometric, Spectrochemical, Nuclear, and Radiochemical Analysis of N
9、uclear-Grade Uranyl Nitrate SolutionsD1193 Specification for Reagent WaterE115 Practice for Photographic Processing in Optical Emission Spectrographic Analysis (Withdrawn 2002)3E116 Practice for Photographic Photometry in Spectrochemical Analysis (Withdrawn 2002)31 These test methods are under the j
10、urisdiction of ASTM Committee C26 on Nuclear Fuel Cycle and are the direct responsibility of Subcommittee C26.03 on NeutronAbsorber Materials Specifications.Current edition approved July 1, 2007Jan. 1, 2013. Published August 2007January 2013. Originally approved in 1980. Last previous edition approv
11、ed in 20002007 asC809 94 (2000).(2007). DOI: 10.1520/C0809-94R07.10.1520/C0809-13.2 For referenced ASTM standards, visit the ASTM website, www.astm.org, or contact ASTM Customer Service at serviceastm.org. For Annual Book of ASTM Standardsvolume information, refer to the standards Document Summary p
12、age on the ASTM website.3 The last approved version of this historical standard is referenced on www.astm.org.This document is not an ASTM standard and is intended only to provide the user of an ASTM standard an indication of what changes have been made to the previous version. Becauseit may not be
13、technically possible to adequately depict all changes accurately, ASTM recommends that users consult prior editions as appropriate. In all cases only the current versionof the standard as published by ASTM is to be considered the official document.Copyright ASTM International, 100 Barr Harbor Drive,
14、 PO Box C700, West Conshohocken, PA 19428-2959. United States13. Significance and Use3.1 Aluminum oxide pellets are used in a reactor core as filler or spacers within fuel, burnable poison, or control rods. In orderto be suitable for this purpose, the material must meet certain criteria for impurity
15、 content. These test methods are designed to showwhether or not a given material meets the specifications for these items as described in Specification C785.3.1.1 Impurity content is determined to ensure that the maximum concentration limit of certain impurity elements is notexceeded.3.2 Aluminum ox
16、ide-boron carbide composite pellets are used in a reactor core as a component in neutron absorber rods. Inorder to be suitable for this purpose, the material must meet certain criteria for boron content, isotopic composition, and impuritycontent as described in Specification C784.3.2.1 The material
17、is assayed for boron to determine whether the boron content is as specified by the purchaser.3.2.2 Determination of the isotopic content of the boron is made to establish whether the 10B concentration is in compliancewith the purchasers specifications.3.2.3 Impurity content is determined to ensure t
18、hat the maximum concentration limit of certain impurity elements is notexceeded.4. Reagents4.1 Purity of ReagentsReagent grade chemicals shall be used in all tests. Unless otherwise indicated, it is intended that allreagents shall conform to the specifications of the Committee on Analytical Reagents
19、 of the American Chemical Society, wheresuch specifications are available.4 Other grades may be used, provided it is first ascertained that the reagent is of sufficiently highpurity to permit its use without lessening the accuracy of the determination.4.2 Purity of WaterUnless otherwise indicated, r
20、eference to water shall be understood to mean reagent water conforming toSpecification D1193, Type III.5. Safety Precautions5.1 Many laboratories have established safety regulations governing the use of hazardous chemicals and equipment. The usersof these test methods should be familiar with such sa
21、fety practices.6. Sampling6.1 Criteria for sampling aluminum oxide pellets are given in Specification C785.6.2 Criteria for sampling aluminum oxide-boron carbide composite pellets are given in Specification C784.BORON BY TITRIMETRY AND ICP OES7. Scope7.1 For the determination of boron in aluminum ox
22、ide-boron carbide composites by titrimetry and ICP OES the proceduresdetailed in Test Method C791, Sections 1726 shall be used.8. Summary of Test Method8.1 Powdered aluminum oxide-boron carbide composite is mixed with alkaline reagents and this mixture is fused to decomposethe aluminum oxide-boron c
23、arbide. The melt is dissolved in diluted hydrochloric acid and heated or purged with nitrogen to removecarbon dioxide. The boron as boric acid is titrated with standardized sodium hydroxide solution, using the mannitoboric acidprocedure. Alternatively, the boron in the samples solution is measured u
24、sing ICP OES.NOTE 1Sodium carbonate or a mixture of sodium carbonate and potassium carbonate (1:1) is normally used as alkaline reagent to decompose thealuminum oxide-boron carbide composite.9. Interferences9.1 TitrimetryBecause metallic impurities in high concentrations may distort the inflection p
25、oints of the titration aluminumshould be precipitated from the sample solution using barium carbonate. No distortion was found for concentrations of Fe 2 %,Ti 1 %. Interferences by dissolved CO2 shall be removed by heating the sample solution or by purging the sample solution withnitrogen.9.2 ICP OE
26、SInterference effects depend primarily upon the resolving power of the spectrometer and the selection of theanalytical lines. In practice, line interferences (spectral interferences) and non spectral interferences are critical. Non spectralinterferences are caused primarily by different chemical com
27、position of calibration solution and sample solution, resulting in an4 Reagent Chemicals, American Chemical Society Specifications, American Chemical Society, Washington, DC. For suggestions on the testing of reagents not listed bythe American Chemical Society, see Analar Standards for Laboratory Ch
28、emicals, BDH Ltd., Poole, Dorset, U.K., and the United States Pharmacopeia and NationalFormulary, U.S. Pharmacopeial Convention, Inc. (USPC), Rockville, MD.C809 132alteration of nebulization and excitation properties. Also memory-effects can play a role. The best way to minimize non spectralinterfer
29、ences is the use of calibration samples with the same composition of matrix, ideally certified reference materials.10. Apparatus10.1 See Test Methods C791, Section 20.11. Reagents11.1 See Test Methods C791, Section 21.12. Precautions12.1 See Test Methods C791, Section 22.13. Sampling and Sample Prep
30、aration13.1 See Test Methods C791, Section 23.14. Procedure14.1 See Test Methods C791, Section 24.15. Titrimetric Determination of Boron15.1 See Test Methods C791, Section 25.16. ICP OES16.1 See Test Methods C791, Section 26.SEPARATION OF BORON FOR MASS SPECTROMETRY17. Scope17.1 This test method cov
31、ers the determinationseparation of boron in aluminum oxide-boron carbide composites. As analternative, the procedure for total boron by titrimetry detailed in Test Methodsfrom aluminum and other impurities. The isotopiccomposition of the separated boron is measured using mass spectrometry. The C791
32、may be used.test method for isotopiccomposition is found in this standard.NOTE 2Alternatively, the separation of boron can be performed by pyrohydrolysis. A stream of moist oxygen is passed over the powdered sampleat 1100 C. The pyrohydrolytic reaction releases boric acid and boron oxide from the sa
33、mple, which volatilize and collect in the condensate (see TestMethods C791, Section 40). The condensate is used for measurement of isotopic composition by ICP-MS (see Test Methods C791, Section 32).18. Summary of Test Method18.1 The sample is crushed, passed through a 100-mesh screen, weighed in a g
34、lass boat, and introduced into a heavy-wall glasstube. Nitric acid is added to the tube and the contents mixed using a vortex mixer. The tube is sealed, placed into a safety container,heated for 6 h, cooled to room temperature, opened, and the contents washed into a beaker.Boron is put into solution
35、 using asealed-tube dissolution method. It is separated from aluminum and other impurities by solvent extraction The solution is adjustedto pH 9.0 and filtered, then adjusted to pH 3.5 and boiled to remove COand ion exchange.2. Substantially, a pure boric acid isobtained which can be titrated in the
36、 presence of mannitol with a standard solution of sodium hydroxide.,19. Interferences19.1 There are no known interferences not eliminated by this separation test method.20. Apparatus20.1 Analytical Balance, capable of weighing to 60.1 6 0.1 mg.20.2 Mortar, diamond (Plattner) (or equivalent).20.3 Sie
37、ve, No. 100 (150-m) U.S. Standard Sieve Series, 76-mm diameter, brass or stainless steel.20.4 Glass Boats, borosilicate, 4-mm wide, 3-mm deep, 40-mm long.20.5 Glass Tubing, heavy-wall borosilicate, 5-mm inside diameter by 250-mm long, sealed at one end.9.6 Mixer, vortex type.20.6 Glass Blowers Torch
38、.20.7 Iron Pipe, 12.7 by 254-mm long with threaded end caps.C809 13320.8 Muffle Furnace, capable of operation at 300C. The heated area must be of sufficient size to hold the capped iron pipe.20.9 pH Meter,Separatory Funnel, with pH electrodes and magnetic stirrer.60-mL with TFE-fluorocarbon stopcock
39、.20.10 Steam Bath. Mixer, vortex type.9.12 Hot Plate.20.11 Filter Paper, 11 cm, ashless ashless, slow filtering for fine precipitates.20.12 Buret, Ion Exchange Column, Class A, 25-mL.borosilicate glass, 5-mm inside diameter, 100-mm long with aTFE-fluorocarbon stopcock.20.13 Beaker, 50-mL, quartz or
40、TFE-fluorocarbon.21. Reagents10.1 Boric Acid, NIST SRM 951 or its replacement.10.2 Hydrochloric Acid (HCl), 1 N.10.3 Hydrochloric Acid (HCl), 0.1 N.10.4 Mannitol.21.1 Nitric Acid (sp gr 1.42)1.42)ConcentratedConcentrated Nitric Acid (HNO3).21.2 Cation Exchange Resin,580 to 100 mesh. Prepare the resi
41、n by treatment with 3 N HCl followed by water wash until theeffluent is neutral to pH paper.21.3 Chloroform (CHCl3).21.4 2-Ethyl-1,3Hexanediol Solution, 5 volume % in chloroform.21.5 Sodium Hydroxide (NaOH) Solution, Nitric Acid 1 (HNO3), 2 N,M. carbonate-free.21.6 Sodium Hydroxide (NaOH) Solution,
42、carbonate 0.1 N,(Na2CO3 carbonate-free.), powder.21.7 Sodium Hydroxide (NaOH) Solution, 0.025 (NaOH) Solution, 0.1 N, carbonate-free, standardized against NIST SRM951.carbonate-free. Store in a plastic bottle.22. Procedure22.1 Crush the aluminum oxide/boron carbide composite pellet using a diamond m
43、ortar until all the sample is passed througha No. 100 (150-m) screen.22.2 Weigh a 250-mg sample into a glass boat.22.3 Introduce the boat and sample into a heavy-wall glass tube, being very careful to prevent any of the sample from adheringto the wall of the tube near the open end.22.4 Introduce 0.5
44、 mL of concentrated HNO3 into the glass tube.22.5 Mix the sample and acid using the vortex mixer.22.6 Flame the glass tube to remove the moisture from the walls.22.7 Seal the glass tube. There are two methods available:22.7.1 Sealing the glass tube may be accomplished by constriction, then drawing o
45、ff a short piece of the tube, then workingdown the sealed end.22.7.2 A seal can be made by allowing the open end of the tube to flow together by heating and revolving the tube slowly. Whilethe tube is red with heat, the tube is warmed enough to blow out the seal to a rounded shape.shape22.8 Place th
46、e glass tube into a safety container which consists of a 12.7-mm inside diameter black iron pipe with screw capson each end. The caps can be tightened with finger tip control.22.9 Insert the assembly into a 300C muffle furnace with the top end of the assembly elevated and heat for 6 h.22.10 Remove t
47、he assembly from the muffle furnace and place into a tray, keeping the same end of the assembly elevated.22.11 Allow the assembly to cool to room temperature.22.12 Withdraw the glass tube from the safety container and file a notch about 13 mm from one end of the tube.NOTE 3ContentsContents of the tu
48、be may be under pressure.5 Dowex 50 8 (or equivalent).C809 13422.13 Heat a glass rod to red heat, then place the rod on the notch. This action should crack the glass tube; however, a lighttap may be needed to complete the break.22.14 Pipet 4 mL of water into the glass tube and mix using a vortex mix
49、er.22.15 Filter the solution through filter paper (15.3). Catch the filtrate in a 60-mL separatory funnel.22.16 Wash the contents from the glass tube intopaper with 15-mL of 2 aM 250-mLHNO3 beaker; however, if the aluminumoxide is stuck to the walls of the tube, shake on a vortex mixer Catch the wash in the separatory funnel.NOTE 2The matrix Al2O3 does not completely dissolve, but all of the boron is in solution.22.17 Add 10 mL of 5 % 2-ethyl-1,3 hexanediol solution to the separatory funnel and shake for 2 min.22.18 Drain the organic (lower) layer into a cl
