Characterisation and heat treatment of chloride-contaminated and humidified PuO2 samples

Sutherland-Harper, Sophie; Pearce, Carolyn; Campbell, Catherine; Carrott, Mike; Colledge, Hannah; Gregson, Colin; Hobbs, Jeff; Livens, Francis; Kaltsoyannis, Nikolas; Orr, Robin; Sarsfield, Mark; Sims, Howard; Steele, Helen; Vatter, Ian; Walton, Louise; Webb, Kevin; Taylor, Robin

doi:10.1016/j.jnucmat.2018.07.031

Title: Characterisation and heat treatment of chloride-contaminated and humidified PuO₂ samples

Full Record
Other Related Research

Abstract

To mimic the reactions that have occurred between plutonium dioxide (PuO₂) and degraded polyvinyl chloride during prolonged storage, batches of PuO₂ powders with varying specific surface area (4–38 m² g^–1) were exposed to dry hydrogen chloride gas forming a surface-sorbed exchangeable chloride species that was readily leached by dilute caustic solution. One batch was also humidified under a 95% relative humidity atmosphere. Heat treatment at temperatures between 100 and 950 °C steadily reduced the leachable chloride content at least when the initial leachable chloride surface coverage was calculated to be > 0.5 monolayer (ML). Variations between samples are attributed to differences in surface area as well as production route and period of interim storage in air or humidified atmospheres. The data are consistent with surface species and reactions proposed in the literature for HCl adsorption on to TiO₂. This indicates that it is interactions between hydrogen chloride/chloride and water/hydroxyl species on the PuO₂ surface that are key to understanding the behaviour of these materials when heated in a furnace. Furthermore, these data will inform the design of a future thermal stabilisation process for chloride-contaminated PuO₂.

Authors:

Sutherland-Harper, Sophie ^[1];

^[2]; Campbell, Catherine ^[3]; Carrott, Mike ^[3]; Colledge, Hannah ^[3]; Gregson, Colin ^[3];

^[4]; Livens, Francis ^[1];

^[1]; Orr, Robin ^[3]; Sarsfield, Mark ^[3]; Sims, Howard ^[3]; Steele, Helen ^[4]; Vatter, Ian ^[3]; Walton, Louise ^[3]; Webb, Kevin ^[3];

^[3]

Univ. of Manchester, Manchester (United Kingdom)
Univ. of Manchester, Manchester (United Kingdom); Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
National Nuclear Lab., Seascale (United Kingdom)
Sellafield Ltd., Seascale (United Kingdom)

Publication Date:: 2018-07-17

Research Org.:: Pacific Northwest National Lab. (PNNL), Richland, WA (United States)

Sponsoring Org.:: USDOE

OSTI Identifier:: 1461644

Grant/Contract Number:: AC05-76RL01830

Resource Type:: Accepted Manuscript

Journal Name:: Journal of Nuclear Materials

Additional Journal Information:: Journal Volume: 509; Journal Issue: C; Journal ID: ISSN 0022-3115

Publisher:: Elsevier

Country of Publication:: United States

Language:: English

Subject:: 38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEAR CHEMISTRY; Plutonium dioxide; Hydrogen chloride; Thermal treatment; Desorption; Stabilisation

Citation Formats


                    Sutherland-Harper, Sophie, Pearce, Carolyn, Campbell, Catherine, Carrott, Mike, Colledge, Hannah, Gregson, Colin, Hobbs, Jeff, Livens, Francis, Kaltsoyannis, Nikolas, Orr, Robin, Sarsfield, Mark, Sims, Howard, Steele, Helen, Vatter, Ian, Walton, Louise, Webb, Kevin, and Taylor, Robin. Characterisation and heat treatment of chloride-contaminated and humidified PuO2 samples.  United States: N. p., 2018. 
Web.  doi:10.1016/j.jnucmat.2018.07.031.

Copy to clipboard


                    Sutherland-Harper, Sophie, Pearce, Carolyn, Campbell, Catherine, Carrott, Mike, Colledge, Hannah, Gregson, Colin, Hobbs, Jeff, Livens, Francis, Kaltsoyannis, Nikolas, Orr, Robin, Sarsfield, Mark, Sims, Howard, Steele, Helen, Vatter, Ian, Walton, Louise, Webb, Kevin, & Taylor, Robin. Characterisation and heat treatment of chloride-contaminated and humidified PuO2 samples.  United States.  https://doi.org/10.1016/j.jnucmat.2018.07.031

Copy to clipboard


                    Sutherland-Harper, Sophie, Pearce, Carolyn, Campbell, Catherine, Carrott, Mike, Colledge, Hannah, Gregson, Colin, Hobbs, Jeff, Livens, Francis, Kaltsoyannis, Nikolas, Orr, Robin, Sarsfield, Mark, Sims, Howard, Steele, Helen, Vatter, Ian, Walton, Louise, Webb, Kevin, and Taylor, Robin. Tue .  
"Characterisation and heat treatment of chloride-contaminated and humidified PuO2 samples".  United States.  https://doi.org/10.1016/j.jnucmat.2018.07.031.  https://www.osti.gov/servlets/purl/1461644.

Copy to clipboard


                    
@article{osti_1461644,

  title        = {Characterisation and heat treatment of chloride-contaminated and humidified PuO2 samples},

  author       = {Sutherland-Harper, Sophie and Pearce, Carolyn and Campbell, Catherine and Carrott, Mike and Colledge, Hannah and Gregson, Colin and Hobbs, Jeff and Livens, Francis and Kaltsoyannis, Nikolas and Orr, Robin and Sarsfield, Mark and Sims, Howard and Steele, Helen and Vatter, Ian and Walton, Louise and Webb, Kevin and Taylor, Robin},

  abstractNote = {To mimic the reactions that have occurred between plutonium dioxide (PuO2) and degraded polyvinyl chloride during prolonged storage, batches of PuO2 powders with varying specific surface area (4–38 m2 g–1) were exposed to dry hydrogen chloride gas forming a surface-sorbed exchangeable chloride species that was readily leached by dilute caustic solution. One batch was also humidified under a 95% relative humidity atmosphere. Heat treatment at temperatures between 100 and 950 °C steadily reduced the leachable chloride content at least when the initial leachable chloride surface coverage was calculated to be > 0.5 monolayer (ML). Variations between samples are attributed to differences in surface area as well as production route and period of interim storage in air or humidified atmospheres. The data are consistent with surface species and reactions proposed in the literature for HCl adsorption on to TiO2. This indicates that it is interactions between hydrogen chloride/chloride and water/hydroxyl species on the PuO2 surface that are key to understanding the behaviour of these materials when heated in a furnace. Furthermore, these data will inform the design of a future thermal stabilisation process for chloride-contaminated PuO2.},

  doi          = {10.1016/j.jnucmat.2018.07.031},

  journal      = {Journal of Nuclear Materials},

  number       = C,

  volume       = 509,

  place        = {United States},

  year         = {2018},

  month        = {7}

}

Copy to clipboard

Journal Article:

Free Publicly Available Full Text

Accepted Manuscript (DOE)

Publisher's Version of Record

https://doi.org/10.1016/j.jnucmat.2018.07.031

Other availability

Search WorldCat to find libraries that may hold this journal

Citation Metrics:

Cited by: 6 works

Citation information provided by
Web of Science

Save / Share:

Export Metadata

Save to My Library

Similar Records in DOE PAGES and OSTI.GOV collections:

Characterisation and heat treatment of chloride-contaminated and humidified PuO2 samples

Journal Article Sutherland-Harper, Sophie ; Pearce, Carolyn I. ; Campbell, Catherine ; ... - Journal of Nuclear Materials

To mimic the reactions that have occurred between plutonium dioxide (PuO2) and degraded polyvinyl chloride during prolonged storage, batches of PuO2 powders with varying specific surface area (4-38m2 g1) were exposed to dry hydrogen chloride gas forming a surface-sorbed exchangeable chloride species that was readily leached by dilute caustic solution. One batch was also humidified under a 95% relative humidity atmosphere. Heat treatment at temperatures between 100 and 950 C steadily reduced the leachable chloride content at least when the initial leachable chloride surface coverage was calculated to be > 0.5 monolayer (ML). Variations between samples are attributed to differencesmore »« less
https://doi.org/10.1016/j.jnucmat.2018.07.031
Interactions of HCl and H2O with the surface of PuO2

Journal Article Sutherland-Harper, Sophie ; Livens, Francis R. ; Pearce, Carolyn I. ; ... - Journal of Nuclear Materials

In order to explore the potential of heat treatment to decontaminate chloride-contaminated legacy plutonium dioxide (PuO2) powders from the UK stockpile, samples retrieved from storage have been heated in air from 400 to 950 C. These samples also contain high levels of other adsorbed gases from the atmosphere, including water. The amounts of chloride remaining on the PuO2 particles after heat treatment (measured by a caustic leaching process) decrease whilst the amounts of volatilised chloride increase with increasing heat treatment temperature. Clear evidence for a non-leachable (strongly bound) chloride species on the PuO2 surface is found from the thermal treatments.more »« less
https://doi.org/10.1016/j.jnucmat.2019.02.036
TECHNICAL BASIS FOR DOE STANDARD 3013 EQUIVALENCY SUPPORTING REDUCED TEMPERATURE STABILIZATION OF OXALATE-DERIVED PLUTONIUM OXIDE PRODUCED BY THE HB-LINE FACILITY AT SAVANNAH RIVER SITE

Technical Report Duffey, J ; Livingston, R ; Berg, J ; ...

The HB-Line (HBL) facility at the Savannah River Site (SRS) is designed to produce high-purity plutonium dioxide (PuO{sub 2}) which is suitable for future use in production of Mixed Oxide (MOX) fuel. The MOX Fuel Fabrication Facility (MFFF) requires PuO{sub 2} feed to be packaged per the U.S. Department of Energy (DOE) Standard 3013 (DOE-STD-3013) to comply with the facility's safety basis. The stabilization conditions imposed by DOE-STD-3013 for PuO{sub 2} (i.e., 950 C for 2 hours) preclude use of the HBL PuO{sub 2} in direct fuel fabrication and reduce the value of the HBL product as MFFF feedstock. Consequently,more »« less
https://doi.org/10.2172/1045619

Full Text Available
MOISTURE AND SURFACE AREA MEASUREMENTS OF PLUTONIUM-BEARING OXIDES

Journal Article Crowder, M ; Duffey, J ; Livingston, R ; ... - Journal of Alloys and Compounds

To ensure safe storage, plutonium-bearing oxides are stabilized at 950 C for at least two hours in an oxidizing atmosphere. Stabilization conditions are expected to decompose organic impurities, convert metals to oxides, and result in moisture content below 0.5 wt%. During stabilization, the specific surface area is reduced, which minimizes readsorption of water onto the oxide surface. Plutonium oxides stabilized according to these criteria were sampled and analyzed to determine moisture content and surface area. In addition, samples were leached in water to identify water-soluble chloride impurity content. Results of these analyses for seven samples showed that the stabilization processmore »« less
https://doi.org/10.1016/j.jallcom.2009.09.161

Full Text Available
Effects of ¹⁸O Exchange on Neutron Emission Rates of Aging ²³⁸PuO₂ LWRHUs

Technical Report Morrison, Jack Raymond ; Mulford, Roberta Nancy

The Lightweight Radioisotope Heater Unit (LWRHU) provides about 1 Watt of thermal power to critical electrical and mechanical systems in the extreme temperatures of space, maintaining the operating temperature of the spacecraft’s scientific and general operating equipment. Los Alamos National Laboratory (LANL) designed and tested the LWRHU in the 1970s through early 1980s. The first production campaign at LANL was in the early 1980s in support of the Galileo mission in which over 100 LWRHUs were manufactured. In the mid-1990s, almost 200 LWRHUs were manufactured in support of the Cassini mission. After the primary Cassini manufacturing campaign, the Department ofmore »« less
https://doi.org/10.2172/1813829

Full Text Available

Similar Records

Title: Characterisation and heat treatment of chloride-contaminated and humidified PuO2 samples

Abstract

Citation Formats

Title: Characterisation and heat treatment of chloride-contaminated and humidified PuO₂ samples