Significance and Use
Plutonium dioxide is used in mixtures with uranium dioxide as a nuclear-reactor fuel. In order to be suitable for this purpose, the material must meet certain criteria for plutonium content, isotopic composition, and 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 C757.
An assay is performed to determine whether the material has the minimum plutonium content specified on a dry weight basis.
Determination of the isotopic content of the plutonium in the plutonium dioxide powder is made to establish whether the effective fissile content is in compliance with the purchaser's specifications.
Impurity content is determined to ensure that the maximum concentration limit of certain impurity elements is not exceeded. Determination of impurities is also required for calculation of the equivalent boron content (EBC).
Scope
1.1 These test methods cover procedures for the chemical, mass spectrometric, and spectrochemical analysis of nuclear-grade plutonium dioxide powders and pellets to determine compliance with specifications.
1.2 The analytical procedures appear in the following order:
| Sections | |
| Plutonium Sample Handling | 8 to 10 |
| Plutonium by Controlled-Potential Coulometry | |
| Plutonium by Ceric Sulfate Titration | |
| Plutonium by Amperometric Titration with Iron(II) | |
| Plutonium by Diode Array Spectrophotometry | |
| Nitrogen by Distillation Spectrophotometry Using Nessler Reagent | 11 to 18 |
| Carbon (Total) by Direct Combustion–Thermal Conductivity | 19 to 30 |
| Total Chlorine and Fluorine by Pyrohydrolysis | 31 to 38 |
| Sulfur by Distillation Spectrophotometry | 39 to 47 |
| Plutonium Isotopic Analysis by Mass Spectrometry | |
| Rare Earth Elements by Spectroscopy | 48 to 55 |
| Trace Elements by Carrier–Distillation Spectroscopy | 56 to 63 |
| Impurities by ICP-AES | |
| Impurity Elements by Spark-Source Mass Spectrography | 64 to 70 |
| Moisture by the Coulometric Electrolytic Moisture Analyzer | 71 to 78 |
| Total Gas in Reactor-Grade Plutonium Dioxide Pellets | 79 to 86 |
| Plutonium-238 Isotopic Abundance by Alpha Spectrometry | |
| Americium-241 in Plutonium by Gamma-Ray Spectrometry | |
| Rare Earths By Copper Spark-Spectroscopy | 87 to 96 |
| Plutonium Isotopic Analysis by Mass Spectrometry | 97 to 105 |
| Oxygen-To-Metal Atom Ratio by Gravimetry | 106 to 114 |
1.3 The values stated in SI units are to be regarded as standard. The values given in parentheses are for information only.
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 Sections 6, 15, 24, 111, and 52.9 and 101.5.1 . 8.1 This test method covers the conditions necessary to preserve the integrity of plutonium dioxide samples. Conditions listed here are directed toward the analytical chemist. However, they are just as applicable to any group handling the material. 11.1 This test method covers the determination of 5 to 100 μg/g of nitride nitrogen in 1-g samples of nuclear-grade plutonium dioxide. 19.1 This test method covers the determination of 10 to 200 μg of residual carbon in nuclear-grade plutonium dioxide. 31.1 This test method covers the determination of 5 to 100 μg/g of chlorine and 1 to 100 μg/g of fluorine in 1-g samples of nuclear-grade plutonium dioxide. 39.1 This test method coves the determination of sulfur in the concentration range from 10 to 600 μg/g for samples of nuclear-grade plutonium dioxide powders or pellets. 48.1 This test method covers the determination of dysprosium, europium, gadolinium, and samarium in plutonium dioxide (PuO2) in concentrations of 0.1 to 10 μg/g of PuO2. 56.1 This test method covers the determination of 36 impurity elements in nuclear-grade plutonium dioxide (PuO2). The concentration ranges covered by the method and the analytical lines used for each element are listed in Table 1. TABLE 1 Impurity Elements, Lines, and Concentration Limits A These elements are determined with the aid of a microphotometer. B These elements are analyzed by using a AgCl carrier and PdCl2 as an internal standard. Mix 20 mg of PdCl2 with 10.0 g of AgCl. Add 80 mg of this mixture to 120 mg of PuO2 sample-blend before loading 50-mg charges in a graphite electrode ASTM-Type-S-4 (follow 96.2.2). 71.1 This test method covers the determination of moisture in plutonium dioxide samples. Detection limits are as low as 10 μg. 79.1 This test method covers the measurement of volatiles other than water in reactor-grade plutonium dioxide pellets (16). The lower limit of the test method using the described equipment and a sample of approximately 1 g is 0.01 cm3 per gram of sample at STP conditions. 87.1 This test method covers the determination of rare earths in plutonium dioxide over the range from 10 to 200 μg/g. 97.1 This test method covers the determination of the isotopic composition of plutonium in nuclear-grade plutonium dioxide powders and pellets. 106.1 This test method is applicable to the determination of the oxygen-to-metal atom ratio (O/M) in plutonium dioxide pellets and powders.
FIG. 5 Schematic Diagram of Atmosphere Chamber
Element Wavelength, Ã… Concentration
Range, ppmAl 2567.99A 10–500 Al 3082.68A Ag 3280.68 1–250 As 2349.84 10–250 Au 2427.95 2.5–50 B 2497.73 1–50 Ba 4554.03 2.5–100 (first order) Be 2348.61 0.5–25 Bi 3067.72 2.5–100 Ca 3933.67 10–1000 Cd 2288.02 1–100 Co 2407.25 10–1000 Co 3044.00 Cu 3247.54 1–250 Cr 2835.63A 5–500 Fe 2983.57A 10–1000 Ga 2450.07A 1–500 Ga 2943.64 In 3039.36 2.5–100 K 7664.91 3–1000 (first order) Mg 2802.70 1–1000 Mn 2798.27 5–250 MoB 3132.59 5–250 Ni 3002.49A 10–1000 P 2553.28 100–1000 Pb 2614.18 5–100 Pd 3242.70 2.5–100 Sb 2598.05 2.5–100 Si 2514.32A 10–300 Sn 2863.33 2.5–100 Sr 4607.33 5–100 (first order) Ti 3223.52 5–100 VB 3183.98A 5–100 WB 2724.35A 20–200 Zn 3345.02 10–250 Zr 3438.23 5–100
