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

  • Author(s): Guo, Xiaofeng
  • Boukhalfa, Hakim
  • Mitchell, Jeremy N
  • Ramos, Michael
  • Gaunt, Andrew J
  • Migliori, Albert
  • Roback, Robert C
  • Navrotsky, Alexandra
  • Xu, Hongwu
  • et al.

Published Web Location

https://doi.org/10.1063/1.5093567
Abstract

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). This capability has thus laid the foundation for thermodynamic studies of other Pu-bearing phases in the future.

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