The plutonium-oxygen phase diagram

Gardner, E. R.; Markin, T.L.; Street, R.S.

doi:10.1016/0022-1902(65)80259-7

Cited by 110 publications

(59 citation statements)

References 6 publications

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“…5 compares residuals and the index for agreement as defined in Eq. (15). With the variable slope, better representations can be seen especially for lower Am content (1.6%) and higher temperature, 1273 and 1423 K, compared with those of the constant slope case.…”

Section: Resultsmentioning

confidence: 87%

“…These species are selected so as to correspond to the actual phase diagram of the system. For example, Pu 2 O 3 and PuO 2 are selected for the PuO 2−x analysis because they have stoichiometric compositions at the single phase boundaries of the fluorite structure [15]. It is of note for the present method that stoichiometric compositions for these species are not limited to integer values as long as the elemental ratios in the species remain unchanged.…”

Section: Chemical Thermodynamic Analysismentioning

confidence: 99%

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Chemical thermodynamic analysis of americium-containing UO2 and (U,Pu)O2

Osaka

Kurosaki

Yamanaka

2007

Journal of Alloys and Compounds

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Section: Resultsmentioning

confidence: 87%

Section: Chemical Thermodynamic Analysismentioning

confidence: 99%

Chemical thermodynamic analysis of americium-containing UO2 and (U,Pu)O2

Osaka

Kurosaki

Yamanaka

2007

Journal of Alloys and Compounds

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“…The appearance of the mixed-valence higher oxide raises additional questions about the validity of Pu-O phase diagrams that are based on earlier experimental observations [43][44][45]. Initial uncertainties arise from results reported recently for the hydrolysis of plutonium by liquid water at room temperature [8].…”

Section: Resultsmentioning

confidence: 99%

Characterization of the plutonium-water reaction II: Formation of a binary oxide containing Pu(VI)

Stakebake¹,

Larson²,

Haschke

1993

Journal of Alloys and Compounds

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Characterization of products formed by reacting unalloyed plutonium with water vapor at 15 Torr pressure shows that Pu203, PuO2 and a previously unreported binary oxide containing Pu(VI) form on the metal between 200 and 350 °C. Although the reaction produces a uniformly adherent product layer with a thickness of about 5 ~m, localized pits of plutonium hydride cover 15-20% of the oxide-metal interface beneath the layer. Analytical results show that the non-equilibrium product contains layers of three oxide phases at all temperatures. Cubic a-Pu203 appearing at the metal interface is covered by a layer of dioxide. A third oxide formed at the gas-solid interface is identified by X-ray diffraction and X-ray photoelectron spectroscopy as the mixed-valence phase Pu(IV)a_xPu(VI)xO6+ x. Diffraction data suggest that this oxide crystallizes in a fluorite-related NpH2+~ or Sm3H7(Ca2YFT)-type structure. Formation of the higher oxide is supported by X-ray photoelectron spectra, indicating the presence of the Pu(VI) oxidation state. Evaluation of the results yields an oxide composition corresponding to a value of x near 0.5. Estimated thermodynamic data suggests that the oxide is a stable phase in the Pu-O system; experimental observations show that the product is preserved during exposure to air and ultrahigh vacuum. Although formation of PUO2.2 is expected to be a slow process at low temperatures, reaction of PuO2 with moisture adsorbed on its surface may generate large quantities of hydrogen if dioxide is stored for an extended period.

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“…The oxide (4.8 m2 g-' specific surface area) was formed by atmospheric oxidation of electrorefined alpha-phase metal containing approximately 100 ppm Am as the major metallic impurity. The oxide stoichiometry was obtained using the measured lauice parameter(aO = 5.4037 A) of the cubic oxide and a correlaticm of aOwith OPU ratio [T based on data reported by Gardner et al [10]. The PuOZused in PVT studies was prepared by oxidizing weapons-grade gallium alloy in a voIume-calibrated stainless steel system.…”

Section: Experimental Methodsmentioning

confidence: 99%