Engineering topics

Allen, Patrick G.

Publications and source records attributed to Allen, Patrick G..

6 records

DOE OSTI2022

Redox chemistry of plutonium and plutonium surrogates in vitrified nuclear wastes

Lanthanide borosilicate glasses containing Pu and the analog element, Ce, were subjects of an X-ray absorption spectroscopy investigation to quantify the +3/+4 ratio of the redox-sensitive element. The data show that the dominant oxidation states are +4 for Pu and +3 for Ce. The data also indicate that the reductive potential of glasses can be quantified, although allowances must be made for glass composition, from a solution chemistry method adapted to glass chemistry. These data can therefore be used to formulate glass compositions and processing schedules that lead to knowledge of the oxidation state of Pu in melts. Furthermore, the data show that Ce is a poor analog for Pu behavior in melt and that the suitability of surrogates can be evaluated by this method. The methods demonstrated in this paper can be used to estimate the oxidation states of a range of multi-valent elements as functions of temperature and composition with data from only a single redox couple.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗

DOE OSTI2019

Moisture outgassing from siloxane elastomers containing surface-treated-silica fillers

Abstract The outgassing kinetics from siloxane elastomers is dominated by moisture desorption from the reinforcing silica filler and can be detrimental in moisture-sensitive applications. In this study, a custom 3D printable siloxane rubber (LL50) was analyzed in three different states: after a high temperature vacuum heat treatment, limited re-exposure to moisture after vacuum heat treatment, and in the as-received condition. The outgassing kinetics were extracted using isoconversional and iterative regression analyses. Moisture release by physisorbed and chemisorbed water from the samples have activation energies in the range of 50 kJ/mol (physisorbed type) to 220 kJ/mol (chemisorbed type). Overall, moisture outgassing from LL50 was 10 times lower than that from traditionally prepared siloxane rubbers. The vastly diminished moisture content in LL50 is attributed to the existence of a finite low level of silanol groups that remain on the fumed silica surface even after hydrophobic treatment.

36 MATERIALS SCIENCE↗

DOE OSTI2017

Identification of NpO 2+x in the binary Np-O system

In contrast to UO 2 and PuO 2 , there is no consensus on the existence of mixed valence NpO 2+x , resulting in a gap between NpO 2 and Np 2 O 5 (the highest binary oxide of Np) in the Np-O phase diagram. We now show NpO 2+x via Np L III Extended X-ray Absorption Fine Structure (EXAFS) spectra of three samples of NpO 2 that, analogous to U and Pu, exhibit multisite Np-O distributions with varying numbers of oxygen atoms at 1.87–1.91 Å. Furthermore this is supported by the diffraction pattern of the sample with the largest amount of this oxo-type species that can be refined with both the simple fluorite structure and a trigonal one related to α-U 4 O 9 . The implied Np(V)-bridging oxo moieties as well as possible indications of OH - found by detailed EXAFS analysis suggest that NpO 2+x more closely resembles PuO 2+x than UO 2+x . An additional common characteristic suggested by the EXAFS and X-Ray Diffraction (XRD) is the phase separation into NpO 2 and what would be previously unreported Np 4 O 9(-δ) , indicative of O clustering.

36 MATERIALS SCIENCE↗

DOE OSTI2017

Boron nitride composites

According to one embodiment, a composite product includes: a matrix material including hexagonal boron nitride and one or more borate binders; and a plurality of cubic boron nitride particles dispersed in the matrix material. According to another embodiment, a composite product includes: a matrix material including hexagonal boron nitride and amorphous boron nitride; and a plurality of cubic boron nitride particles dispersed in the matrix material.

36 MATERIALS SCIENCE↗

DOE OSTI2016

Boron nitride composites

According to one embodiment, a composite product includes hexagonal boron nitride (hBN), and a plurality of cubic boron nitride (cBN) particles, wherein the plurality of cBN particles are dispersed in a matrix of the hBN. According to another embodiment, a composite product includes a plurality of cBN particles, and one or more borate-containing binders.

36 MATERIALS SCIENCE↗

DOE OSTI2015

X-ray excited Auger transitions of Pu compounds

X-ray excited Pu core–valence–valence and core–core–valence Auger line-shapes were used in combination with the Pu 4f photoelectron peaks to characterize differences in the oxidation state and local electronic structure for Pu compounds. The evolution of the Pu 4f core-level chemical shift as a function of sputtering depth profiling and hydrogen exposure at ambient temperature was quantified. The combination of the core–valence–valence Auger peak energies with the associated chemical shift of the Pu 4f photoelectron line defines the Auger parameter and results in a reliable method for definitively determining oxidation states independent of binding energy calibration. Results show that PuO{sub 2}, Pu{sub 2}O{sub 3}, PuH{sub 2.7}, and Pu have definitive Auger line-shapes. These data were used to produce a chemical state (Wagner) plot for select plutonium oxides. This Wagner plot allowed us to distinguish between the trivalent hydride and the trivalent oxide, which cannot be differentiated by the Pu 4f binding energy alone.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗