ASTM C809-94(2000)
(Test Method)Standard Test Methods for Chemical, Mass Spectrometric, and Spectrochemical Analysis of Nuclear-Grade Aluminum Oxide and Aluminum Oxide-Boron Carbide Composite Pellets
Standard Test Methods for Chemical, Mass Spectrometric, and Spectrochemical Analysis of Nuclear-Grade Aluminum Oxide and Aluminum Oxide-Boron Carbide Composite Pellets
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 7 to 13 Separation of Boron for Mass Spectrometry 14 to 19 Isotopic Composition by Mass Spectrometry 20 to 23 Separation of Halides by Pyrohydrolysis 24 to 27 Fluoride by Ion-Selective Electrode 28 to 30 Chloride, Bromide, and Iodide by Amperometric Microtitrimetry 31 to 33 Trace Elements by Emission Spectroscopy 34 to 46
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 and health practices and determine the applicability of regulatory limitations prior to use. (For specific precautionary statements, see Section 5.)
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Designation:C809–94 (Reapproved 2000)
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.Anumber in parentheses indicates the year of last reapproval.A
superscript epsilon (e) indicates an editorial change since the last revision or reapproval.
1. Scope Nuclear-Grade Uranyl Nitrate Solutions
D1193 Specification for Reagent Water
1.1 These test methods cover procedures for the chemical,
E115 Practice for Photographic Processing in Optical
mass spectrometric, and spectrochemical analysis of nuclear-
Emission Spectrographic Analysis
grade aluminum oxide and aluminum oxide-boron carbide
E116 Practice for Photographic Photometry in Spectro-
composite pellets to determine compliance with specifications.
chemical Analysis
1.2 Theanalyticalproceduresappearinthefollowingorder:
Sections
3. Significance and Use
Boron by Titrimetry 7 to 13
3.1 Aluminum oxide pellets are used in a reactor core as
Separation of Boron for Mass Spectrometry 14 to 19
fillerorspacerswithinfuel,burnablepoison,orcontrolrods.In
Isotopic Composition by Mass Spectrometry 20 to 23
order to be suitable for this purpose, the material must meet
Separation of Halides by Pyrohydrolysis 24 to 27
Fluoride by Ion-Selective Electrode 28 to 30
certain criteria for impurity content. These test methods are
Chloride, Bromide, and Iodide by Amperometric Microtitrimetry 31 to 33
designed to show whether or not a given material meets the
Trace Elements by Emission Spectroscopy 34 to 46
specifications for these items as described in Specification
1.3 The values stated in SI units are to be regarded as the
C785.
standard.
3.1.1 Impurity content is determined to ensure that the
1.4 This standard does not purport to address all of the
maximum concentration limit of certain impurity elements is
safety concerns, if any, associated with its use. It is the
not exceeded.
responsibility of the user of this standard to establish appro-
3.2 Aluminum oxide-boron carbide composite pellets are
priate safety and health practices and determine the applica-
usedinareactorcoreasacomponentinneutronabsorberrods.
bility of regulatory limitations prior to use. (For specific
In order to be suitable for this purpose, the material must meet
precautionary statements, see Section 5.)
certain criteria for boron content, isotopic composition, and
impurity content as described in Specification C784.
2. Referenced Documents
3.2.1 The material is assayed for boron to determine
2.1 ASTM Standards:
whether the boron content is as specified by the purchaser.
C784 Specification for Nuclear-Grade Aluminum Oxide-
3.2.2 Determination of the isotopic content of the boron is
Boron Carbide Composite Pellets 10
made to establish whether the B concentration is in compli-
C785 Specification for Nuclear-Grade Aluminum Oxide
ance with the purchaser’s specifications.
Pellets
3.2.3 Impurity content is determined to ensure that the
C791 TestMethodsforChemical,MassSpectrometric,and
maximum concentration limit of certain impurity elements is
Spectrochemical Analysis of Nuclear-Grade Boron Car-
not exceeded.
bide
C799 Test Methods for Chemical, Mass Spectrometric, 4. Reagents
Spectrochemical, Nuclear, and RadiochemicalAnalysis of
4.1 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 Commit-
These test methods are under the jurisdiction of ASTM Committee C26 on
tee onAnalytical Reagents of theAmerican Chemical Society,
Nuclear Fuel Cycle and are the direct responsibility of Subcommittee C26.03 on
Neutron Absorbers Materials Specifications .
Current edition approved Oct. 15, 1994. Published December 1994. Originally
published as C809–80. Last previous edition C809–80. Annual Book of ASTM Standards, Vol 11.01.
2 4
Annual Book of ASTM Standards, Vol 12.01. Annual Book of ASTM Standards, Vol 03.05.
Copyright © ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959, United States.
C809–94 (2000)
where such specifications are available. Other grades may be 9.4 Glass Boats, borosilicate, 4-mm wide, 3-mm deep,
used, provided it is first ascertained that the reagent is of 40-mm long.
sufficiently high purity to permit its use without lessening the 9.5 Glass Tubing, heavy-wall borosilicate, 5-mm inside
accuracy of the determination. diameter by 250-mm long, sealed at one end.
4.2 Purity of Water— Unless otherwise indicated, reference 9.6 Mixer, vortex type.
towatershallbeunderstoodtomeanreagentwaterconforming 9.7 Glass Blower’s Torch.
to Specification D1193, Type III. 9.8 Iron Pipe,12.7by254-mmlongwiththreadedendcaps.
9.9 Muffle Furnace, capable of operation at 300°C. The
5. Safety Precautions
heated area must be of sufficient size to hold the capped iron
pipe.
5.1 Many laboratories have established safety regulations
governing the use of hazardous chemicals and equipment. The 9.10 pH Meter, with pH electrodes and magnetic stirrer.
9.11 Steam Bath.
users of these test methods should be familiar with such safety
practices. 9.12 Hot Plate.
9.13 Filter Paper, 11 cm, ashless slow filtering for fine
6. Sampling
precipitates.
9.14 Buret, Class A, 25-mL.
6.1 Criteria for sampling aluminum oxide pellets are given
in Specification C785.
10. Reagents
6.2 Criteria for sampling aluminum oxide-boron carbide
composite pellets are given in Specification C784.
10.1 Boric Acid, NIST SRM 951 or its replacement.
10.2 Hydrochloric Acid (HCl),1 N.
BORON BY TITRIMETRY
10.3 Hydrochloric Acid (HCl), 0.1 N.
10.4 Mannitol.
7. Scope
10.5 Nitric Acid (sp gr 1.42)—Concentrated Nitric Acid
7.1 This test method covers the determination of boron in
(HNO ).
aluminum oxide-boron carbide composites. As an alternative,
10.6 Sodium Hydroxide (NaOH) Solution,1 N, carbonate-
the procedure for total boron by titrimetry detailed in Test
free.
Methods C791 may be used.
10.7 Sodium Hydroxide (NaOH) Solution, 0.1 N, carbonate-
free.
8. Summary of Test Method
10.8 Sodium Hydroxide (NaOH) Solution, 0.025 N,
8.1 The sample is crushed, passed through a 100-mesh
carbonate-free, standardized against NIST SRM 951.
screen, weighed in a glass boat, and introduced into a heavy-
wallglasstube.Nitricacidisaddedtothetubeandthecontents
11. Procedure
mixed using a vortex mixer. The tube is sealed, placed into a
11.1 Crush the aluminum oxide/boron carbide composite
safety container, heated for 6 h, cooled to room temperature,
pellet using a diamond mortar until all the sample is passed
opened,andthecontentswashedintoabeaker. Thesolutionis
through a No. 100 (150-µm) screen.
adjusted to pH 9.0 and filtered, then adjusted to pH 3.5 and
11.2 Weigh a 250-mg sample into a glass boat.
boiled to remove CO . Substantially, a pure boric acid is
11.3 Introduce the boat and sample into a heavy-wall glass
obtainedwhichcanbetitratedinthepresenceofmannitolwith
tube, being very careful to prevent any of the sample from
,
a standard solution of sodium hydroxide.
adhering to the wall of the tube near the open end.
11.4 Introduce 0.5 mLof concentrated HNO into the glass
9. Apparatus
tube.
9.1 Analytical Balance, capable of weighing to 6 0.1 mg.
11.5 Mix the sample and acid using the vortex mixer.
9.2 Mortar, diamond (Plattner) (or equivalent).
11.6 Flame the glass tube to remove the moisture from the
9.3 Sieve, No. 100 (150-µm) U.S. Standard Sieve Series,
walls.
76-mm diameter, brass or stainless steel.
11.7 Seal the glass tube. There are two methods available:
11.7.1 Sealing the glass tube may be accomplished by
constriction, then drawing off a short piece of the tube, then
Reagent Chemicals, American Chemical Society Specifications, American
working down the sealed end.
Chemical Society, Washington, DC. For suggestions on the testing of reagents not
11.7.2 Aseal can be made by allowing the open end of the
listed by the American Chemical Society, see Analar Standards for Laboratory
tube to flow together by heating and revolving the tube slowly.
Chemicals, BDH Ltd., Poole, Dorset, U.K., and the United States Pharmacopeia
and National Formulary,U.S.PharmaceuticalConvention,Inc.(USPC),Rockville,
While the tube is red with heat, the tube is warmed enough to
MD.
blow out the seal to a rounded shape.
Wichers,E.,Schlecht,W.G.,andGordon,C.L.,“PreparingRefractoryOxides,
11.8 Place the glass tube into a safety container which
Silicates,andCeramicMaterialsforAnalysisbyHeatingwithAcidsinSealedTubes
consists of a 12.7-mm inside diameter black iron pipe with
at Elevated Temperatures,” Journal of Research of the National Bureau of
Standards, Vol 33, 1944, p. 451.
screw caps on each end. The caps can be tightened with finger
Lerner, M. W., The Analysis of Elemental Boron, New Brunswick Laboratory,
tip control.
U. S. Atomic Energy Commission, TID-25190, November 1970.
11.9 Insert the assembly into a 300°C muffle furnace with
Rodden, C. J., Analysis of Essential Nuclear Reactor Materials, U.S. Atomic
Energy Commission, Washington, DC, Government Printing Office, 1964. the top end of the assembly elevated and heat for 6 h.
C809–94 (2000)
11.10 Remove the assembly from the muffle furnace and SEPARATION OF BORON FOR MASS
place into a tray, keeping the same end of the assembly SPECTROMETRY
elevated.
14. Scope
11.11 Allow the assembly to cool to room temperature.
14.1 This test method covers the separation of boron from
11.12 Withdrawtheglasstubefromthesafetycontainerand
aluminum and other impurities. The isotopic composition of
file a notch about 13 mm from one end of the tube.
the separated boron is measured using another test method
NOTE 1—Contents of the tube may be under pressure.
found herein.
11.13 Heat a glass rod to red heat, then place the rod on the
15. Summary of Test Method
notch.Thisactionshouldcracktheglasstube;however,alight
15.1 Boron is put into solution using a sealed-tube dissolu-
tap may be needed to complete the break.
tion method. It is separated from aluminum and other impuri-
11.14 Wash the contents from the glass tube into a 250-mL
ties by solvent extraction and ion exchange.
beaker;however,ifthealuminumoxideisstucktothewallsof
the tube, shake on a vortex mixer.
16. Interferences
NOTE 2—The matrixAl O does not completely dissolve, but all of the
2 3
16.1 There are no known interferences not eliminated by
boron is in solution.
this separation test method.
11.15 Precipitate the iron and the aluminum by using 1 N
17. Apparatus
sodium hydroxide solution to adjust the pH to 9.0.
11.16 Place the beaker on a steam bath and digest for 1 h. 17.1 Separatory Funnel, 60-mL with TFE-fluorocarbon
stopcock.
11.17 Filter the sample through the filter paper (9.13) and
17.2 Mixer, vortex type.
wash the precipitate with several portions of hot deionized
17.3 Filter Paper, ashless, slow filtering for fine precipi-
water.
tates.
11.18 Adjust the pH between 3.5 and 4.0 using 1 N HCl.
17.4 Ion Exchange Column, borosilicate glass, 5-mm inside
11.19 Cover the solution with a flat watch glass, then place
diameter, 100-mm long with a TFE-fluorocarbon stopcock.
the beaker on a hot plate and boil for about 5 min to remove
17.5 Beaker, 50-mL, quartz or TFE-fluorocarbon.
carbon dioxide.
11.20 Remove the sample from the hot plate and cool to
18. Reagents
room temperature in a water bath.
18.1 Cation Exchange Resin, 80 to 100 mesh. Prepare the
11.21 Adjust the pH of the sample to 5.6 to 5.7 using 0.1 N
resin by treatment with 3 N HCl followed by water wash until
NaOH solution and 0.1 N HCl. Add 1 to3gof mannitol.
the effluent is neutral to pH paper.
11.22 Titrate the sample to pH 8.0 using a 0.025 N NaOH
18.2 Chloroform (CHCl ).
solution.
18.3 2-Ethyl-1,3Hexanediol Solution, 5 volume% in chlo-
11.23 Determine a blank by performing 11.3-11.22 without
roform.
the sample.
18.4 Nitric Acid (HNO ), 2 M.
18.5 Sodium carbonate (Na CO ), powder.
2 3
12. Calculation
18.6 Sodium Hydroxide (NaOH) Solution, 0.1 N,
12.1 Calculate the percent boron in the sample as follows: carbonate-free. Store in a plastic bottle.
~V– B!~N!~A!~100!
19. Procedure
B,% 5 (1)
W
19.1 Prepare an aliquot of sample by following 11.1-11.13.
where:
19.2 Pipet 4 mL of water into the glass tube and mix using
V = millilitres of NaOH solution used in titration of the
a vortex mixer.
sample,
19.3 Filterthesolutionthroughfilterpaper(15.3).Catchthe
B = millilitres of NaOH solution used in titration of the
filtrate in a 60-mL separatory funnel.
blank,
19.4 Wash the paper with 15-mL of 2 M HNO . Catch the
N = normality of the NaOH solution,
wash in the separatory funnel.
A = atomic weight of boron computed for the sample
19.5 Add 10 mL of 5% 2-ethyl-1,3 hexanediol solution to
based upon the measured isotopic composition, and
the separatory funnel and shake for 2 min.
W = milligrams of sample weight.
19.6 Drain the organic (lower) layer into a clean 100-mL
beaker.
13. Precision
13.1 The limit of error at the 95% confidence level for a
single determination is 60.10% absolute.
Dowex 50 38 (or equivalent).
C809–94 (2000)
19.7 Repeat 19.5 and 19.6. SEPARATION OF HALIDES BY
PYROHYDROLYSIS
19.8 Transfer the 2-ethyl-1,3 hexanediol solution to a clean
60-mL separatory funnel.
24. Scope
19.9 Extract the boron by shaking for 2-min with a NaOH
24.1 This test method covers the separation of up to 100 µg
solution containing the amount of sodium calculated to give a
of halides per gram of sample. The separated halides are
B/Na ratio of two and a volume sufficient to give 1 mg B/mL.
measured using other test methods found herein.
19.10 Discard the organic phase.
25. Summary of Test Method
19.11 Wash the aqueous phase with two 5-mL portions of
CHCl . Discard the organic wash.
25.1 A stream of moist gas is passed over a mixture of
19.12 Transfer the aqueous phase containing the boron to a
powdered sample and U O accelerator heated at 1000 to
3 8
50-mL quartz or TFE-fluorocarbon beaker.
1100°C. The pyrohydrolytic reaction releases the halides as
19.13 Evaporate the solution to a volume of about 1 mL. their respective acids, which volatilize and collect in the
condensate.
19.14 Add 0.5 mL of ion exchange resin to the beaker and
swirl.
26. Interferences
NOTE 3—AdditionoftheresintothebeakerpreventsformationofCO
26.1 Interferencesarenotexpected.Theconditionsgivenin
bubbles on the resin column in the subsequent step.
this test method for pyrohydrolysis must be controlled to
ensure comp
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