ASTM C696-99(2005)

NOTICE: This standard has either been superseded and replaced by a new version or withdrawn.
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Designation:C696–99(Reapproved2005)
Standard Test Methods for
Chemical, Mass Spectrometric, and Spectrochemical
Analysis of Nuclear-Grade Uranium Dioxide Powders and
Pellets
This standard is issued under the fixed designation C696; 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 (´) indicates an editorial change since the last revision or reapproval.
1. Scope
Uranium Isotopic Analysis by Mass Spectrometry
Sections
1.1 These test methods cover procedures for the chemical,
mass spectrometric, and spectrochemical analysis of nuclear-
C1413 Test Method for Isotopic Analysis of Hydro-
lysed Uranium Hexafluoride and Uranyl Nitrate Solu-
grade uranium dioxide powders and pellets to determine
tions By Thermal Ionization Mass Spectrometry
compliance with specifications.
1.2 Theanalyticalproceduresappearinthefollowingorder:
2. Referenced Documents
Sections
2.1 ASTM Standards:
2 C753 Specification for Nuclear-Grade, Sinterable Uranium
Uranium by Ferrous Sulfate Reduction in Phosphoric
Acid and Dichromate Titration Method
Dioxide Powder
C1267 Test Method for Uranium By Iron (II) Reduc-
C761 Test Methods for Chemical, Mass Spectrometric,
tion In Phosphoric Acid Followed By Chromium
Spectrochemical, Nuclear, and RadiochemicalAnalysis of
(VI) Titration In The Presence of Vanadium
Uranium and Oxygen Uranium Atomic Ratio by the 7-13 Uranium Hexafluoride
Ignition (Gravimetric) Impurity Correction Method
C776 Specification for Sintered Uranium Dioxide Pellets
Carbon (Total) by Direct Combustion-Thermal Con-
C1267 Test Method for Uranium by Iron (II) Reduction in
ductivity Method
C1408 Test Method for Carbon (Total) in Uranium
PhosphoricAcid Followed by Chromium (VI) Titration in
Oxide Powders and Pellets By Direct Combus-
the Presence of Vanadium
tion- Infrared Detection Method
C1287 Test Method for Determination of Impurities in
Total Chlorine and Fluorine by Pyrohydrolysis 14-20
Ion- Selective Electrode Method
Nuclear Grade Uranium Compounds by Inductively
Moisture by the Coulometric, Electrolytic Moisture 21-28
Coupled Plasma Mass Spectrometry
Analyzer Method
C1347 Practice for Preparation and Dissolution of Uranium
Nitrogen by the Kjeldahl Method 29-36
Isotopic Uranium Composition by Multiple-Filament
Materials for Analysis
Surface Ionization Mass Spectrometric Method
C1408 Test Method for Carbon (Total) in Uranium Oxide
Spectrochemical Determination of Trace Elements in 37-44
Powders and Pellets By Direct Combustion-Infrared De-
High-Purity Uranium Dioxide
Silver, Spectrochemical Determination of, by Gallium 45 to 46
tection Method
OxideCarrier D-C Arc Technique
C1413 Test Method for Isotopic Analysis of Hydrolyzed
Rare Earths by Copper Spark-Spectrochemical
Method Uranium Hexafluoride and Uranyl Nitrate Solutions by
Impurity Elements by a Spark-Source Mass Spectro-
Thermal Ionization Mass Spectrometry
graphic Method
3 D1193 Specification for Reagent Water
C761 Test Method for Chemical, Mass Spectromet-
ric, Spectrochemical, Nuclear, and Radiochemical E115 PracticeforPhotographicProcessinginOpticalEmis-
Analysis of Uranium Hexafluoride
sion Spectrographic Analysis
C1287 Test Method for Determination of Impurities
E130 Practice for Designation of Shapes and Sizes of
In Uranium Dioxide By Inductively Coupled
Plasma Mass Spectrometry
Graphite Electrodes
Surface Area by Nitrogen Absorption Method 47-53
E402 Test Method for SpectrographicAnalysis of Uranium
Total Gas in Reactor-Grade Uranium Dioxide Pellets
Thorium and Rare Earth Elements by Spectroscopy
Hydrogen by Inert Gas Fusion 54-63
Discontinued January 1999. See C696–80.
For referenced ASTM standards, visit the ASTM website, www.astm.org, or
These test methods are under the jurisdiction of ASTM Committee C26 on contact ASTM Customer Service at service@astm.org. For Annual Book of ASTM
Nuclear Fuel Cycle and are the direct responsibility of Subcommittee C26.05 on Standards volume information, refer to the standard’s Document Summary page on
Methods of Test. the ASTM website.
Current edition approved June 1, 2005. Published December 2005. Originally Discontinued as of May 30, 1980.
approved in 1972. Last previous edition approved in 1999 as C696–99. DOI: Withdrawn. The last approved version of this historical standard is referenced
10.1520/C0696-99R05. on www.astm.org.
Copyright © ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959, United States.
C696–99 (2005)
Oxide (U O ) by Gallium Oxide-Carrier Technique URANIUM BY FERROUS SULFATE REDUCTION IN
3 8
PHOSPHORIC ACID AND DICHROMATE
TITRATION METHOD
3. Significance and Use
This test method was withdrawn in January 1999 and
3.1 Uranium dioxide is used as a nuclear-reactor fuel. In
replaced by Test method C1267.
order to be suitable for this purpose, the material must meet
certain criteria for uranium content, stoichiometry, isotopic
URANIUM AND OXYGEN TO URANIUM ATOMIC
composition, and impurity content. These test methods are
RATIO BY THE IGNITION (GRAVIMETRIC)
designed to show whether or not a given material meets the
IMPURITY CORRECTION METHOD
specifications for these items as described in Specifications
C753 and C776.
7. Scope
3.1.1 An assay is performed to determine whether the
7.1 This test method covers the determination of uranium
material has the minimum uranium content specified on a dry
and the oxygen to uranium atomic ratio in nuclear-grade
weight basis.
uranium dioxide powder and pellets.
3.1.2 The stoichiometry of the oxide is useful for predicting
its sintering behavior in the pellet production process. 8. Summary of Test Method
3.1.3 Determination of the isotopic content of the uranium 8.1 A weighed portion of UO is dried under reduced
intheuraniumdioxidepowderismadetoestablishwhetherthe pressure in a nitrogen atmosphere, desiccated, and weighed.
effective fissile content is in compliance with the purchaser’s ThedriedoxideisthenconvertedtoU O byignitionat900°C
3 8
specifications. (8, 9).
3.1.4 Impurity content is determined to ensure that the
9. Interferences
maximum concentration limit of certain impurity elements is
not exceeded. Determination of impurities is also required for 9.1 The weight of U O is corrected for the nonvolatile
3 8
impurities present as determined by spectrographic analysis.
calculation of the equivalent boron content (EBC).
An extended ignition time may be required if significant
amounts of anions that are difficult to decompose are present.
4. Reagents
4.1 Purity of Reagents—Reagent grade chemicals shall be
10. Apparatus
used in all tests. Unless otherwise indicated, it is intended that
10.1 Vacuum Oven, capable of maintaining and controlling
all reagents shall conform to the specifications of the Commit-
temperatures to 180°C and equipped with double stopcocks
tee onAnalytical Reagents of theAmerican Chemical Society,
and a vacuum gage (range from 0 to 102 kPa (0 to 30 in. Hg)).
where such specifications are available. Other grades may be
10.2 Drying Tower—Prepare a U-tube filled with a carbon
used, provided it is first ascertained that the reagent is of
dioxide absorbent and a suitable moisture absorbent, that is,
sufficiently high purity to permit its use without lessening the
anhydrous magnesium perchlorate Mg(ClO ) .
4 2
accuracy of the determination.
10.3 MuffleFurnace,capableofmaintainingandcontrolling
4.2 Purity of Water—Unlessotherwiseindicated,references
temperatures to 1000°C.
towatershallbeunderstoodtomeanreagentwaterconforming
to Specification D1193.
11. Procedure
11.1 Transfer approximately 5 to 10 g of UO powder or up
5. Safety Precautions
to 50 g of pellets to a tared platinum crucible and weigh to
5.1 Proper precautions should be taken to prevent inhala- within 0.1 mg.
tion, or ingestion of uranium dioxide powders or dust during
11.2 Place the crucible in a vacuum oven set at room
grinding or handling operations. temperature, seal the oven, and reduce the pressure to approxi-
mately 95 to 102 kPa (28 to 30 in. Hg).
6. Sampling 11.3 Closethevacuumvalveandslowlyflushtheovenwith
dry nitrogen.
6.1 Criteria for sampling this material are given in Specifi-
11.4 Close the nitrogen inlet and reduce the pressure to 95
cation C753 and Specification C776.
to 102 kPa (28 to 30 in. Hg). Repeat the nitrogen flush as in
6.2 Samples can be dissolved using the appropriate disso-
step 11.3 to give a total of three flushes.
lution techniques described in Practice C1347, but final deter-
11.5 Closethenitrogeninletvalve,reducethepressureto95
mination of applicability must be made by the user.
to 102 kPa (28 to 30 in. Hg), set the temperature at 45°C for
powder samples or 160°C for pellets, and maintain these
conditions for 4 h. After 4 h of heating turn off the heat and
6 allow the oven to cool to room temperature while under
Reagent Chemicals, American Chemical Society Specifications, American
Chemical Society, Washington, DC. For suggestions on the testing of reagents not reduced pressure.
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. Ascarite has been found satisfactory for this purpose.
C696–99 (2005)
TABLE 1 Conversion Factors for Impurity Correction
11.6 Turn off the vacuum valve and slowly introduce dry
nitrogen until the oven door can be opened. Impurity Assumed Oxide Form Gravimetric Factor
11.7 Transfer the crucible to a desiccator and cool. Remove
Al Al O 1.89
2 3
Ba BaO 1.12
the crucible and weigh immediately (8).
Be BeO 2.78
11.8 Place the crucible containing the dried oxide in a
Bi Bi O 1.11
2 3
muffle furnace set at 900°C. Ignite powder samples for 3 h.
Ca CaO 1.40
Cd CdO 1.14
Pellets should be preheated at 500°C for 3 h, then ignited 3 h
Co Co O 1.41
2 3
at 900°C.
Cr Cr O 1.46
2 3
11.9 Remove the crucible from the furnace, allow to cool in
Cu CuO 1.25
Fe Fe O 1.43
2 3
the air 2 to 3 min then place the crucible in a desiccator and
Li Li O 2.15
cool to room temperature. Weigh the crucible and repeat steps
Mg MgO 1.66
11.8 and 11.9 until a constant weight is obtained.
Mn MnO 1.58
Mo MoO 1.50
11.10 Submit the ignited sample for spectrographic analy- 3
Na Na O 1.35
sis.
Ni NiO 1.27
PP O 2.29
2 5
12. Calculation
Pb PbO 1.15
Sb Sb O 1.26
2 4
12.1 Loss on Vacuum Drying—Calculate as follows based
Si SiO 2.14
on original sample:
Sn SnO 1.27
Ti TiO 1.67
Loss,wt% 5[~S 2 W !/S] 3100 (1)
VV O 1.79
2 5
Zn ZnO 1.24
where:
Zr ZrO 1.35
S = initial sample mass, and Ta Ta O 1.22
2 5
WWO 1.26
W = sample mass after vacuum drying, g.
12.2 Uranium Content—Calculate as follows:
U,wt% 5[~0.8480 ~W 2 W I!/S! 3100] 20.01% ~Note1! (2)
2 2
CARBON (TOTAL) BY DIRECT COMBUSTION-
where:
THERMAL CONDUCTIVITY METHOD
0.8480 = U O to uranium conversion factor for natural
3 8
This test method was withdrawn in January 1999 and
uranium.Correctionsmustbemadeinthisfactor
replaced by Test Method C1408
as the uranium isotopic abundance deviates from
natural uranium,
TOTAL CHLORINE AND FLUORINE BY
W = grams of U O after ignition,
2 3 8
PYROHYDROLYSIS ION-SELECTIVE ELECTRODE
S = initial sample mass, and
METHOD
I = total grams of all impurity-element oxides per
gram of ignited U O (Note 2).
3 8
14. Scope
NOTE 1—All nonvolatile impurity values reported as less than the
14.1 This test method covers the determination of chlorine
threshold of detection are considered to contribute a total correction of
andfluorineinnuclear-gradeuraniumdioxide.Witha1to10-g
0.01 % to the uranium percent.
sample, concentrations of 5 to 200 µg/g of chlorine and 1 to
NOTE 2—See Table 1 to obtain conversion factors for many common
200 µg/g of fluorine are determined without interference.
impurity elements encountered.
12.3 Oxygen-to-Uranium Ratio—Calculate as follows from
15. Summary of Test Method
the original sample, U wt %:
15.1 The halogens are separated from powdered uranium
O/U 5[~100 2 U wt % 2 Z 2n!~A!#/[15.999~U! wt%# (3)
dioxidebypyrohydrolysisinaquartztubewithastreamofwet
oxygen at a temperature of 900 to 1000°C (10, 11, 12, 13).
where:
Chloride and fluoride are volatilized as acids, absorbed in a
A = atomic mass of uranium based on isotopic abundance,
buffersolution,andmeasuredwithion-selectiveelectrodes(13,
O = atom % of oxygen,
14, 15).
U = atom % of uranium,
n = moisture content, %, and
16. Apparatus
Z = total impurities correction, %.
16.1 Pyrohydrolysis Equipment—A suitable assembly of
13. Precision and Accuracy
apparatus is shown in Fig. 1.
13.1 ForatomicratiosofO/Uintherangefrom2.00to2.10 16.1.1 Gas Flow Regulator and Flowmeter.
16.1.2 Hot Plate, used to warm the water saturating the
the standard deviation was found to be 0.007 absolute at 95%
confidence level. sparge gas to 50 to 80°C.
C696–99 (2005)
FIG. 1 Pyrohydrolysis Apparatus
FIG. 2 Quartz Reaction Tube
16.1.3 CombustionTubeFurnace,havingaboreofabout32 17. Reagents
mm (1 ⁄4 in.), a length of about 305 mm (12 in.), and the
17.1 Accelerator, U O halogen-free,canbeusedbutaflux
3 8
capability of maintaining a temperature of 1000°C.
of sodium tungstate (Na WO ) with tungsten trioxide (WO )
2 4 3
16.1.4 Quartz Reaction Tube (Fig. 2)—The exit end should
may be used to advantage (10, 11). Special preparation of the
not extend over 51 mm (2 in.) beyond the furnace with a
mixture is necessary.
ground joint connecting to the delivery tube.The delivery tube
NOTE 3—Dehydrate 165 g of Na WO in a large platinum dish.
2 4
extendsintoapolyethyleneabsorptionvesselwithatipcapable
Transfer the dried material to a mortar, add 116 g of WO , and grind the
of giving a stream of fine bubbles.
mixture to ensure good mixing. Transfer the mixture into a platinum dish
16.1.5 Combustion Boat—Aplatinum or quartz boat with a
and heat with a burner for 2 h. Cool the melt, transfer the flux to a mortar
1 1
10-ml capacity (89 to 102 mm (3 ⁄2 to 4 in.) long, 12.7 mm ( ⁄2
andgrindtoacoarsepowder.Storethefluxinanairtightbottle.Mixabout
in.) wide, and 9.53 mm ( ⁄8 in.) high).
8 g of flux with each portion of sample to be pyrohydrolyzed.
16.1.6 Absorption Vessel—A 50-mL polyethylene graduate
17.2 Buffer Solution—Dissolve 0.1 g potassium acetate
or tube is satisfactory.
(KC H O ) in water, add 0.050 mL of acetic acid (CH CO H,
2 3 2 3 2
16.2 Ion-Specific Electrodes—A fluoride-specific activity
sp gr 1.05), and dilute to 1 litre.
8 9
electrode ; chloride-specific electrode.
17.3 Chloride, Standard Solution (1 mL = 100 µg Cl)—
16.3 pH Meter an
...