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Title: Sample seal-and-drop device and methodology for high temperature oxide melt solution calorimetric measurements of PuO 2

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 PuO 2 in molten sodium molybdate (3Namore » 2O · 4MoO 3) solvent at 700 °C. The obtained enthalpy of –52.21 ± 3.68 kJ/mol is consistent with the energetic systematics of other actinide oxides (UO 2, ThO 2, and NpO 2). In conclusion, this capability has thus laid the foundation for thermodynamic studies of other Pu-bearing phases in the future.« less

Authors:
ORCiD logo [1]; ORCiD logo [2]; ORCiD logo [2];  [2]; ORCiD logo [2]; ORCiD logo [2]; ORCiD logo [2];  [3]; ORCiD logo [2]
  1. Los Alamos National Lab. (LANL), Los Alamos, NM (United States); Washington State Univ., Pullman, WA (United States)
  2. Los Alamos National Lab. (LANL), Los Alamos, NM (United States)
  3. Univ. of California Davis, Davis, CA (United States)
Publication Date:
Research Org.:
Los Alamos National Lab. (LANL), Los Alamos, NM (United States)
Sponsoring Org.:
USDOE Laboratory Directed Research and Development (LDRD) Program
OSTI Identifier:
1511630
Alternate Identifier(s):
OSTI ID: 1507808
Report Number(s):
LA-UR-19-21351
Journal ID: ISSN 0034-6748
Grant/Contract Number:  
89233218CNA000001; SC0001089; LDRD #20180007 DR
Resource Type:
Accepted Manuscript
Journal Name:
Review of Scientific Instruments
Additional Journal Information:
Journal Volume: 90; Journal Issue: 4; Journal ID: ISSN 0034-6748
Publisher:
American Institute of Physics (AIP)
Country of Publication:
United States
Language:
English
Subject:
47 OTHER INSTRUMENTATION; 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; High temperature calorimetry; sample seal-and-drop device; radioactive materials; PuO2; enthalpy of drop solution

Citation Formats

Guo, Xiaofeng, Boukhalfa, Hakim, Mitchell, Jeremy Neal, Ramos, Michael, Gaunt, Andrew James, Migliori, Albert, Roback, Robert Clifford, Navrotsky, Alexandra, and Xu, Hongwu. Sample seal-and-drop device and methodology for high temperature oxide melt solution calorimetric measurements of PuO2. United States: N. p., 2019. Web. doi:10.1063/1.5093567.
Guo, Xiaofeng, Boukhalfa, Hakim, Mitchell, Jeremy Neal, Ramos, Michael, Gaunt, Andrew James, Migliori, Albert, Roback, Robert Clifford, Navrotsky, Alexandra, & Xu, Hongwu. Sample seal-and-drop device and methodology for high temperature oxide melt solution calorimetric measurements of PuO2. United States. doi:10.1063/1.5093567.
Guo, Xiaofeng, Boukhalfa, Hakim, Mitchell, Jeremy Neal, Ramos, Michael, Gaunt, Andrew James, Migliori, Albert, Roback, Robert Clifford, Navrotsky, Alexandra, and Xu, Hongwu. Fri . "Sample seal-and-drop device and methodology for high temperature oxide melt solution calorimetric measurements of PuO2". United States. doi:10.1063/1.5093567.
@article{osti_1511630,
title = {Sample seal-and-drop device and methodology for high temperature oxide melt solution calorimetric measurements of PuO2},
author = {Guo, Xiaofeng and Boukhalfa, Hakim and Mitchell, Jeremy Neal and Ramos, Michael and Gaunt, Andrew James and Migliori, Albert and Roback, Robert Clifford and Navrotsky, Alexandra and Xu, Hongwu},
abstractNote = {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.},
doi = {10.1063/1.5093567},
journal = {Review of Scientific Instruments},
number = 4,
volume = 90,
place = {United States},
year = {2019},
month = {4}
}

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