ASTM C809-19

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. Because
it may not be technically possible to adequately depict all changes accurately, ASTM recommends that users consult prior editions as appropriate. In all cases only the current version
of the standard as published by ASTM is to be considered the official document.
Designation: C809 − 13 C809 − 19
Standard Test Methods for
Chemical, Mass Spectrometric, and Spectrochemical
Analysis of Nuclear-Grade Aluminum Oxide and Aluminum
Oxide-Boron Carbide Composite Pellets
This standard is issued under the fixed designation C809; the number immediately following the designation indicates the year of
original adoption or, in the case of revision, the year of last revision. A number in parentheses indicates the year of last reapproval. A
superscript epsilon (´) indicates an editorial change since the last revision or reapproval.
1. Scope
1.1 These test methods cover procedures for the chemical, mass spectrometric, and spectrochemical analysis of nuclear-grade
aluminum oxide and aluminum oxide-boron carbide composite pellets to determine compliance with specifications.
1.2 The analytical procedures appear in the following order:
Sections
Boron by Titrimetry and ICP OES 7 to 16
Boron by Titrimetry and ICP OES 8 to 17
Separation of Boron for Mass Spectrometry 17 to 22
Separation of Boron for Mass Spectrometry 18 to 23
Isotopic Composition by Mass Spectrometry 23 to 26
Isotopic Composition by Mass Spectrometry 24 to 27
Separation of Halides by Pyrohydrolysis 27 to 30
Separation of Halides by Pyrohydrolysis 28 to 31
Chloride and Fluoride by Ion-Selective Electrode 31 to 33
Chloride and Fluoride by Ion-Selective Electrode 32 to 34
Chloride, Bromide, and Iodide by Amperometric Microtitrimetry 34 to 36
Chloride, Bromide, and Iodide by Amperometric Microtitrimetry 35 to 37
Trace Elements by Emission Spectroscopy 37 to 49
Trace Elements by Emission Spectroscopy 38 to 50
Keywords 50
Keywords 51
1.3 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 responsibility
of the user of this standard to establish appropriate safety safety, health, and healthenvironmental practices and determine the
applicability of regulatory limitations prior to use. (For specific precautionary statements, see Section 56.)
1.5 This international standard was developed in accordance with internationally recognized principles on standardization
established in the Decision on Principles for the Development of International Standards, Guides and Recommendations issued
by the World Trade Organization Technical Barriers to Trade (TBT) Committee.
2. Referenced Documents
2.1 ASTM Standards:
C784 Specification for Nuclear-Grade Aluminum Oxide-Boron Carbide Composite Pellets
C785 Specification for Nuclear-Grade Aluminum Oxide Pellets
C791 Test Methods for Chemical, Mass Spectrometric, and Spectrochemical Analysis of Nuclear-Grade Boron Carbide
C799 Test Methods for Chemical, Mass Spectrometric, Spectrochemical, Nuclear, and Radiochemical Analysis of Nuclear-
Grade Uranyl Nitrate Solutions
C859 Terminology Relating to Nuclear Materials
C1128 Guide for Preparation of Working Reference Materials for Use in Analysis of Nuclear Fuel Cycle Materials
These test methods are under the jurisdiction of ASTM Committee C26 on Nuclear Fuel Cycle and are the direct responsibility of Subcommittee C26.03 on Neutron
Absorber Materials Specifications.
Current edition approved Jan. 1, 2013Feb. 1, 2019. Published January 2013March 2019. Originally approved in 1980. Last previous edition approved in 20072013 as
C809 – 94 (2007).C809 – 13. DOI: 10.1520/C0809-13.10.1520/C0809-19.
For referenced ASTM standards, visit the ASTM website, www.astm.org, or contact ASTM Customer Service at service@astm.org. For Annual Book of ASTM Standards
volume information, refer to the standard’s Document Summary page on the ASTM website.
Copyright © ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959. United States
C809 − 19
D1193 Specification for Reagent Water
E115 Practice for Photographic Processing in Optical Emission Spectrographic Analysis (Withdrawn 2002)
E116 Practice for Photographic Photometry in Spectrochemical Analysis (Withdrawn 2002)
3. Terminology
3.1 Definitions—For definitions of terms relating to nuclear materials, see Terminology C859.
3.2 Definitions of Terms Specific to This Standard:
3.2.1 analytical or emission line—the particular wavelength of electromagnetic radiation used in determining the presence or
concentration of an element.
3.2.2 calibration—the act, process, or result of establishing the relationship between the response of an instrument and the
amount of analyte present.
3.2.3 calibration samples or solutions (standards)—samples or solutions with known analyte contents or analyte concentrations,
respectively, to establish the relationship between the response of an instrument and the amount of analyte.
3.2.4 certified reference material (CRM)—a reference material, accompanied by a certificate, one or more of whose property
values are certified by a procedure which establishes traceability to an accurate realization of the unit in which the property values
are expressed, and for which each certified value is accompanied by an uncertainty at a stated level of confidence.
3.2.5 DCArc OES—optical emission spectrometry (OES) with direct current arc (DCArc) as excitation source.
3.2.6 ICP MS—mass spectrometry (MS) with inductively coupled plasma (ICP) as ionization source.
3.2.7 ICP OES—optical emission spectrometry (OES) with inductively coupled plasma (ICP) as excitation source.
3.2.8 matrix—all components of a material except the analyte.
3.2.9 method—instructions used to produce a numerical result, which are detailed in a document referred to as “the method.”
3.2.10 optical emission spectrometry (OES)—pertaining to emission spectrometry in the ultraviolet, visible, or infrared
wavelength regions of the electromagnetic spectrum.
3.2.11 sample—a portion of a material selected and processed to render its composition representative of the composition of the
whole.
3.2.12 standardization—the experimental establishment of the concentration of a reagent solution.
3.2.13 TIMS—thermal ionization mass spectrometry.
3.2.14 titrimetry—a method of quantitatie chemical analysis that is used to determine the concentration of an identified analyte.
4. Significance and Use
4.1 Aluminum oxide pellets are used in a reactor core as filler or spacers within fuel, burnable poison, or control rods. In order
to be suitable for this purpose, the material must meet certain criteria for impurity content. These test methods are designed to show
whether or not a given material meets the specifications for these items as described in Specification C785.
4.1.1 Impurity content is determined to ensure that the maximum concentration limit of certain impurity elements is not
exceeded.
4.2 Aluminum oxide-boron carbide composite pellets are used in a reactor core as a component in neutron absorber rods. In
order to be suitable for this purpose, the material must meet certain criteria for boron content, isotopic composition, and impurity
content as described in Specification C784.
4.2.1 The material is assayed for boron to determine whether the boron content is as specified by the purchaser.
4.2.2 Determination of the isotopic content of the boron is made to establish whether the B concentration is in compliance
with the purchaser’s specifications.
4.2.3 Impurity content is determined to ensure that the maximum concentration limit of certain impurity elements is not
exceeded.
5. Reagents
5.1 Purity of Reagents—Reagent grade chemicals shall be used in all tests. Unless otherwise indicated, it is intended that all
reagents shall conform to the specifications of the Committee on Analytical Reagents of the American Chemical Society, where
such specifications are available. Other grades may be used, provided it is first ascertained that the reagent is of sufficiently high
purity to permit its use without lessening the accuracy of the determination.
The last approved version of this historical standard is referenced on www.astm.org.
Reagent Chemicals, American Chemical Society Specifications, American Chemical Society, Washington, DC. For suggestions on the testing of reagents not listed by
the American Chemical Society, see Analar Standards for Laboratory Chemicals, BDH Ltd., Poole, Dorset, U.K., and the United States Pharmacopeia and National
Formulary, U.S. Pharmacopeial Convention, Inc. (USPC), Rockville, MD.
C809 − 19
5.2 Purity of Water—Unless otherwise indicated, reference to water shall be understood to mean reagent water conforming to
Specification D1193, Type III.
6. Safety Precautions
6.1 Many laboratories have established safety regulations governing the use of hazardous chemicals and equipment. The users
of these test methods should be familiar with such safety practices.
7. Sampling
7.1 Criteria for sampling aluminum oxide pellets are given in Specification C785.
7.2 Criteria for sampling aluminum oxide-boron carbide composite pellets are given in Specification C784.
BORON BY TITRIMETRY AND ICP OES
7. Scope
7.1 For the determination of boron in aluminum oxide-boron carbide composites by titrimetry and ICP OES the procedures
detailed in Test Method C791, Sections 17–26 shall be used.
8. Scope
8.1 For the determination of boron in aluminum oxide-boron carbide composites by titrimetry and ICP OES the procedures
detailed in Test Method C791, Sections 18 – 27 shall be used.
9. Summary of Test Method
9.1 Powdered aluminum oxide-boron carbide composite is mixed with alkaline reagents and this mixture is fused to decompose
the aluminum oxide-boron carbide. The melt is dissolved in diluted hydrochloric acid and heated or purged with nitrogen to remove
carbon dioxide. The boron as boric acid is titrated with standardized sodium hydroxide solution, using the mannitoboric acid
procedure. Alternatively, the boron in the samples solution is measured using ICP OES.
NOTE 1—Sodium carbonate or a mixture of sodium carbonate and potassium carbonate (1:1) is normally used as alkaline reagent to decompose the
aluminum oxide-boron carbide composite.
10. Interferences
10.1 Titrimetry—Because metallic impurities in high concentrations may distort the inflection points of the titration aluminum
should be precipitated from the sample solution using barium carbonate. No distortion was found for concentrations of Fe < 2 %,
Ti < 1 %. Interferences by dissolved CO shall be removed by heating the sample solution or by purging the sample solution with
nitrogen.
10.2 ICP OES—Interference effects depend primarily upon the resolving power of the spectrometer and the selection of the
analytical lines. In practice, line interferences (spectral interferences) and non spectral interferences are critical. Non spectral
interferences are caused primarily by different chemical composition of calibration solution and sample solution, resulting in an
alteration of nebulization and excitation properties. Also memory-effects can play a role. The best way to minimize non spectral
interferences is the use of calibration samples with the same composition of matrix, ideally certified reference materials. When
certified reference materials are not available, consider Guide C1128 for preparation of working reference materials.
11. Apparatus
11.1 See Test Methods C791, Section 20.21.
12. Reagents
12.1 See Test Methods C791, Section 21.22.
13. Precautions
13.1 See Test Methods C791, Section 22.23.
14. Sampling and Sample Preparation
14.1 See Test Methods C791, Section 23.24.
15. Procedure
15.1 See Test Methods C791, Section 24.25.
C809 − 19
16. Titrimetric Determination of Boron
16.1 See Test Methods C791, Section 25.26.
17. ICP OES
17.1 See Test Methods C791, Section 26.27.
SEPARATION OF BORON FOR MASS SPECTROMETRY
17. Scope
17.1 This test method covers the separation of boron from aluminum and other impurities. The isotopic composition of the
separated boron is measured using mass spectrometry. The test method for isotopic composition is found in this standard.
NOTE 2—Alternatively, the separation of boron can be performed by pyrohydrolysis. A stream of moist oxygen is passed over the powdered sample
at 1100 °C. The pyrohydrolytic reaction releases boric acid and boron oxide from the sample, which volatilize and collect in the condensate (see Test
Methods C791, Section 40). The condensate is used for measurement of isotopic composition by ICP-MS (see Test Methods C791, Section 32).
18. Scope
18.1 This test method covers the separation of boron from aluminum and other impurities. The isotopic composition of the
separated boron is measured using mass spectrometry. The test method for isotopic composition is found in this standard.
18.2 Alternatively, the separation of boron can be performed by pyrohydrolysis. A stream of moist oxygen is passed over the
powdered sample at 1100°C. The pyrohydrolytic reaction releases boric acid and boron oxide from the sample, which volatilize
and collect in the condensate (see Test Methods C791, Section 41). The condensate is used for measurement of isotopic
composition by ICP-MS (see Test Methods C791, Section 33).
19. Summary of Test Method
19.1 Boron is put into solution using a sealed-tube dissolution method. It is separated from aluminum and other impurities by
solvent extraction and ion exchange.
20. Interferences
20.1 There are no known interferences not eliminated by this separation test method.
21. Apparatus
21.1 Analytical Balance, capable of weighing to 6 0.1 60.1 mg.
21.2 Mortar, diamond (Plattner) (or equivalent).
21.3 Sieve, No. 100 (150-μm) U.S. Standard Sieve Series, 76-mm diameter, brass or stainless steel.
21.4 Glass Boats, borosilicate, 4-mm wide, 3-mm deep, 40-mm long.
21.5 Glass Tubing, heavy-wall borosilicate, 5-mm inside diameter by 250-mm long, sealed at one end.
21.6 Glass Blower’s Torch.
21.7 Iron Pipe, 12.7 by 254-mm long with threaded end caps.
21.8 Muffle Furnace, capable of operation at 300°C. The heated area must be of sufficient size to hold the capped iron pipe.
21.9 Separatory Funnel, 60-mL with TFE-fluorocarbon stopcock.
21.10 Mixer, vortex type.
21.11 Filter Paper, ashless, slow filtering for fine precipitates.
21.12 Ion Exchange Column, borosilicate glass, 5-mm inside diameter, 100-mm long with a TFE-fluorocarbon stopcock.
21.13 Beaker, 50-mL, quartz or TFE-fluorocarbon.
22. Reagents
22.1 Nitric Acid (sp gr 1.42)—Concentrated Nitric Acid (HNO ).
22.2 Cation Exchange Resin, 80 to 100 mesh. Prepare the resin by treatment with 3 N HCl followed by water wash until the
effluent is neutral to pH paper.
22.3 Chloroform (CHCl ).
Dowex 50 × 8 (or equivalent).
C809 − 19
22.4 2-Ethyl-1,3Hexanediol Solution, 5 volume % in chloroform.
22.5 Nitric Acid (HNO ), 2 M.
22.6 Sodium carbonate (Na CO ), powder.
2 3
22.7 Sodium Hydroxide (NaOH) Solution, 0.1 N, carbonate-free. Store in a plastic bottle.
23. Procedure
23.1 Crush the aluminum oxide/boron carbide composite pellet using a diamond mortar until all the sample is passed through
a No. 100 (150-μm) screen.
23.2 Weigh a 250-mg sample into a glass boat.
23.3 Introduce the boat and sample into a heavy-wall glass tube, being very careful to prevent any of the sample from adhering
to the wall of the tube near the open end.
23.4 Introduce 0.5 mL of concentrated HNO into the glass tube.
23.5 Mix the sample and acid using the vortex mixer.
23.6 Flame the glass tube to remove the moisture from the walls.
23.7 Seal the glass tube. There are two methods available:
23.7.1 Sealing the glass tube may be accomplished by constriction, then drawing off a short piece of the tube, then working
down the sealed end.
23.7.2 A seal can be made by allowing the open end of the tube to flow together by heating and revolving the tube slowly. While
the tube is red with heat, the tube is warmed enough to blow out the seal to a rounded shapeshape.
23.8 Place the glass tube into a safety container which consists of a 12.7-mm inside diameter black iron pipe with screw caps
on each end. The caps can be tightened with finger tip control.
23.9 Insert the assembly into a 300°C muffle furnace with the top end of the assembly elevated and heat for 6 h.
23.10 Remove the assembly from the muffle furnace and place into a tray, keeping the same end of the assembly elevated.
23.11 Allow the assembly to cool to room temperature.
23.12 Withdraw the glass tube from the safety container and file a notch about 13 mm from one end of the tube.
NOTE 2—Contents of the tube may be under pressure.
23.13 Heat a glass rod to red heat, then place the rod on the notch. This action should crack the glass tube; however, a light
tap may be needed to complete the break.
23.14 Pipet 4 mL of water into the glass tube and mix using a vortex mixer.
23.15 Filter the solution through filter paper (15.3). Catch the filtrate in a 60-mL separatory funnel.
23.16 Wash the paper with 15-mL of 2 M HNO . Catch the wash in the separatory funnel.
23.17 Add 10 mL of 5 % 2-ethyl-1,3 hexanediol solution to the separatory funnel and shake for 2 min.
23.18 Drain the organic (lower) layer into a clean 100-mL beaker.
23.19 Repeat 22.1723.17 and 22.1823.18.
23.20 Transfer the 2-ethyl-1,3 hexanediol solution to a clean 60-mL separatory funnel.
23.21 Extract the boron by shaking for 2-min with a NaOH solution containing the amount of sodium calculated to give a B/Na
ratio of two and a volume sufficient to give 1 mg B/mL.
23.22 Discard the organic phase.
23.23 Wash the aqueous phase with two 5-mL portions of CHCl . Discard the organic wash.
23.24 Transfer the aqueous phase containing the boron to a 50-mL quartz or TFE-fluorocarbon beaker.
23.25 Evaporate the solution to a volume of about 1 mL.
23.26 Add 0.
...