XPS-AES characterization of plutonium oxides and oxide carbide. The existence of plutonium monoxide

Journal Article · Wed Jul 01 00:00:00 EDT 1981 · Inorg. Chem.; (United States)

DOI:https://doi.org/10.1021/ic50221a001· OSTI ID:6205306

Larson, D T; Haschke, J M

The plutonium-oxygen phase diagrams has been clarified by XPS and AES results which show that three oxygen-containing plutonium phases, PuO/sub 2/, ..cap alpha..-Pu/sub 2/O/sub 3/, and PuO/sub x/C/sub y/, are successively formed when oxide-coated plutonium metal is heated in vacuo to 500/sup 0/C. Formation of the oxide carbide is evidenced by the fact that a shift in the Pu(4f/sub 7/2/) binding energy is coincident with changes in the C(1s) photoelectron and C(KLL) Auger spectra, showing that unbound carbon is converted to carbide. The reaction conditions duplicate those at which plutonium monoxide reportedly forms and demonstrate that the NaCl-type surface phase previously identified as PuO is actually PuO/sub x/C/sub y/. The oxide carbide has a spectroscopically determined composition of PuO/sub 0.65+-0.15/C/sub 0.45+-0.15/ and reacts with CO, CO/sub 2/, and O/sub 2/ at low pressures to form PuO/sub 2/ and unbound carbon in a coherent product layer (approx. 20 nm thick) which retards further oxidation. Estimated thermodynamic data for PuO/sub x/C/sub y/ are consistent with the observed formation and oxidation reactions. The Pu(4f/sub 7/2/) binding energies for PuO/sub 2/, ..cap alpha..-Pu/sub 2/O/sub 3/, PuO/sub x/C/sub y/, and Pu are 426.1, 424.4, 423.6, and 422.2 eV, respectively.

• Research Organization: Rockwell International, Golden, CO
• DOE Contract Number: AC04-76DP03533
• OSTI ID: 6205306
• Journal Information: Inorg. Chem.; (United States), Vol. 20:7
• Country of Publication: United States
• Language: English

Related Subjects

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEAR CHEMISTRY
OXYCARBIDES
BINDING ENERGY
PHASE DIAGRAMS
PLUTONIUM COMPOUNDS
PLUTONIUM DIOXIDE
PLUTONIUM OXIDES
AUGER ELECTRON SPECTROSCOPY
HEATING
HIGH TEMPERATURE
OXIDATION
PHOTOELECTRON SPECTROSCOPY
PLUTONIUM
X-RAY SPECTROSCOPY
ACTINIDE COMPOUNDS
ACTINIDES
CARBON COMPOUNDS
CHALCOGENIDES
CHEMICAL REACTIONS
DIAGRAMS
ELECTRON SPECTROSCOPY
ELEMENTS
ENERGY
METALS
OXIDES
OXYGEN COMPOUNDS
SPECTROSCOPY
TRANSURANIUM COMPOUNDS
TRANSURANIUM ELEMENTS
400702* - Radiochemistry & Nuclear Chemistry- Properties of Radioactive Materials