Sample seal-and-drop device and methodology for high temperature oxide melt solution calorimetric measurements of PuO2

Guo, Xiaofeng; Boukhalfa, Hakim; Mitchell, Jeremy Neal; Ramos, Michael; Gaunt, Andrew James; Migliori, Albert; Roback, Robert Clifford; Navrotsky, Alexandra; Xu, Hongwu

doi:10.1063/1.5093567

Sample seal-and-drop device and methodology for high temperature oxide melt solution calorimetric measurements of PuO₂

Journal Article · Fri Apr 19 00:00:00 EDT 2019 · Review of Scientific Instruments

DOI:https://doi.org/10.1063/1.5093567· OSTI ID:1511630

^[1]; ^[2]; ^[2]; Ramos, Michael ^[2]; ^[2]; ^[2]; ^[2]; Navrotsky, Alexandra ^[3]; ^[2]

Los Alamos National Lab. (LANL), Los Alamos, NM (United States); Washington State Univ., Pullman, WA (United States)
Los Alamos National Lab. (LANL), Los Alamos, NM (United States)
Univ. of California Davis, Davis, CA (United States)

Thermodynamic properties of refractory materials, such as standard enthalpy of formation, heat content, and enthalpy of reaction, can be measured by high temperature calorimetry. In such experiments, a small sample pellet is dropped from room temperature into a calorimeter operating at high temperature (often 700 °C) with or without a molten salt solvent present in an inert crucible in the calorimeter chamber. However, for hazardous (radioactive, toxic, etc.) and/or air-sensitive (hygroscopic, sensitive to oxygen, pyrophoric, etc.) samples, it is necessary to utilize a sealed device to encapsulate and isolate the samples, crucibles, and solvent under a controlled atmosphere in order to prevent the materials from reactions and/or protect the personnel from hazardous exposure during the calorimetric experiments. We have developed a sample seal-and-drop device (calorimetric dropper) that can be readily installed onto the dropping tube of a calorimeter such as the Setaram AlexSYS Calvet-type high temperature calorimeter to fulfill two functions: (i) load hazardous or air-sensitive samples in an air-tight, sealed container and (ii) drop the samples into the calorimeter chamber using an “off-then-on” mechanism. As a case study, we used the calorimetric dropper for measurements of the enthalpy of drop solution of PuO₂ in molten sodium molybdate (3Na₂O · 4MoO₃) solvent at 700 °C. The obtained enthalpy of –52.21 ± 3.68 kJ/mol is consistent with the energetic systematics of other actinide oxides (UO₂, ThO₂, and NpO₂). In conclusion, this capability has thus laid the foundation for thermodynamic studies of other Pu-bearing phases in the future.

View Accepted Manuscript (DOE)

Research Organization:: Energy Frontier Research Centers (EFRC) (United States). Materials Science of Actinides (MSA); Los Alamos National Lab. (LANL), Los Alamos, NM (United States)

Sponsoring Organization:: LDRD; USDOE

Grant/Contract Number:: 89233218CNA000001; SC0001089

OSTI ID:: 1511630

Alternate ID(s):: OSTI ID: 1507808

Report Number(s):: LA-UR--19-21351

Journal Information:: Review of Scientific Instruments, Journal Name: Review of Scientific Instruments Journal Issue: 4 Vol. 90; ISSN 0034-6748

Publisher:: American Institute of Physics (AIP)Copyright Statement

Country of Publication:: United States

Language:: English

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
47 OTHER INSTRUMENTATION
High temperature calorimetry
PuO2
enthalpy of drop solution
radioactive materials
sample seal-and-drop device

Sample seal-and-drop device and methodology for high temperature oxide melt solution calorimetric measurements of PuO2

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References (53)

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Sample seal-and-drop device and methodology for high temperature oxide melt solution calorimetric measurements of PuO₂