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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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At least 37 records · Page 2

Determining hexavalent chromium transport properties in alkaline nuclear waste using nuclear magnetic resonance spectroscopy

This study focuses on the transport properties of hexavalent chromium, specifically the chromate anion, to improve predictive models and environmental remediation strategies for Cr(VI) migration. Using 53 Cr Nuclear Magnetic Resonance (NMR) spectroscopy, the research quantifies chromate in multicomponent electrolytes replicating nuclear waste conditions at the Hanford Site in Washington State. The consistency of the 53 Cr NMR signal integral with chromate concentration, despite varying matrix compositions, establishes it as a reliable concentration indicator. The transport properties of chromate in an alkaline solution were assessed using relaxation-based measurements via saturation recovery and Carr-Purcell-Meiboom-Gill experiments, determining spin-lattice and spin-spin relaxation times. These measurements, combined with the Bloembergen-Purcell-Pound equation, helped estimate the rotational correlation time and the 53 Cr self-diffusion coefficient using Stokes-Einstein-Debye and Stokes-Einstein equations. Direct measurements were obtained through pulsed field gradient stimulated echo 53 Cr NMR spectroscopy. Monte Carlo simulations further estimated uncertainty propagation. The results enhance comprehension of chromate transport and highlight prospects for identifying transport properties of NMR-active nuclei, traditionally considered unreachable.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Optical Spectroscopic Investigation of Hexavalent Actinide Ions in n-Dodecane Solutions of Tri-butyl Phosphate

The extraction of hexavalent actinides An(VI) by tri-butyl phosphate (TBP) was investigated by electronic absorption and vibrational spectroscopies. Through a series of spectral subtractions, vibrational spectra associated with TBP, TBP–HNO3 adducts, and An(VI)–TBP complexes could be isolated. Investigation of U(VI) extracts indicated spectral features consistent with the formation of the expected [UO2(NO3)2(TBP)2] complex, but spectral features of other species were clearly evident. Likewise, multiple species were evident in the electronic absorption and vibrational spectra of TBP phases generated by extraction of Pu(VI). Although definitive characterization of the additional species formed could not be achieved in this work, it is hypothesized that they contain 3:1 TBP-to-An(VI) stoichiometry.

Lumetta, Gregg J.↗

Recommendations for Updating Liquid Discharged Inventory and Transport Modeling Parameters for Cumulative Impacts Evaluation of Hexavalent Chromium in the 200 West Area

The purpose of this environmental calculation file (ECF) is to document information regarding hexavalent chromium (Cr(VI)) inventory discharged in 200 West Area at the Hanford Site and provide data to support predictive transport through the vadose zone and saturated zone for modeling efforts. This document provides a focused evaluation of historical waste stream data and studies to develop estimates of Cr(VI) inventory, discharge fractions, and transport parameters for the 200 West Area waste sites and tank farms during discharge events and for long-term contaminant releases.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

NASA TEERM Hexavalent Chrome Alternatives Projects

This slide presentation reviews the NASA project to select an alternative to hexavalent chrome in the aerospace industry. Included is a recent historic testing and research that the Agency has performed on (1) the external tank, (2) the shuttle orbiter, (3) the Shuttle Rocket Booster, and (4) the Space Shuttle Main Engine. Other related Technology Evaluation for Environmental Risk Mitigation (TEERM) projects are reviewed. The Phase I process of the project performed testing of alternatives the results are shown in a chart for different coating systems. International collaboration was also reviewed. Phase II involves further testing of pretreatment and primers for 6 and 12 months of exposure to conditions at Launch Pad and the beach. Further test were performed to characterize the life cycle corrosion of the space vehicles. A new task is described as a joint project with the Department of Defense to identify a Hex Chrome Free Coatings for Electronics.

Kessel, Kurt↗

NASA TEERM Hexavalent Chrome Alternatives Projects

The overall objective of the Hex Chrome Free Coatings for Electronics project is to evaluate and test pretreatment coating systems not containing hexavalent chrome in avionics and electronics housing applications. This objective will be accomplished by testing strong performing coating systems from prior NASA and DoD testing or new coating systems as determined by the stakeholders. The technical stakeholders have agreed that this protocol will focus specifically on Class 3 coatings. Original Equipment Manufacturers (OEMs), depots, and support contractors have to be prepared to deal with an electronics supply chain that increasingly provides parts with lead-free finishes, some labeled no differently and intermingled with their SnPb counterparts. Allowance of lead-free components presents one of the greatest risks to the reliability of military and aerospace electronics. The introduction of components with lead-free terminations, termination finishes, or circuit boards presents a host of concerns to customers, suppliers, and maintainers of aerospace and military electronic systems such as: 1. Electrical shorting due to tin whiskers 2. Incompatibility of lead-free processes and parameters (including higher melting points of lead-free alloys) with other materials in the system 3. Unknown material properties and incompatibilities that could reduce solder joint reliability

Kessel, Kurt R.↗

Final Test Report: Hexavalent Chrome Free Coatings for Electronics Electromagnetic Interference (EMI) Shielding Effectiveness (SE)

The test results for Salt Spray Resistance, Static Heat and Humidity and Marine Environment can be found in Sections 3.1.3.3, 3.1.4.3 and 3.1.5.3 respectively. In summary, both the Metalast TCP and SurTec 650 Type 2 conversion coatings perform very similar to the incumbent Type 1 conversion coating against both 6061 and 5052 aluminum under all three test conditions. Significant prior work was performed to select the aluminum and conversion coating included within this test cycle; Reference - NASA GSDO Program Hexavalent Chrome Alternatives Final Pretreatments Test Report Task Order: NNH12AA45D September 01, 2013. As illustrated in the data, the 6061 aluminum panels SLIGHTLY out-performed the 5052 aluminum panels. Individual shielding effectiveness graphs for each panel are included within Appendix C and D. One other notable effect found during review of the data is that the Test Panels exposed to B117 Salt Fog reduced in shielding effectiveness significantly more than the Marine Environment Test Panels. The shielding effectiveness of the Marine Test Panels was approximately 20dB higher than the Test Panels that underwent B117 Salt Fog Exposure. The intent of this evaluation was not to maximize shielding effectiveness values. The same Parker Chomerics Cho-Seal 6503 gasket material was used for all panels with aluminum and conversion coating variants. A typical EMI gasket design for corrosive environments would be done quite differently. The intent was to execute a test that would provide the best possible evaluation of different aluminum materials and conversion coatings in corrosive environments. The test program achieved this intent. The fact that the two aluminums and two Type II conversion coatings performed similar to the incumbent Type 1 conversion coating is a positive outcome. It was desired to have an outcome that further differentiation the performance of two aluminum types and two conversion coating types but this could not be extracted by the test results. Further analysis of the test plates may be done by X-Ray Photoelectron Spectroscopy (XPS) or Electrochemical Impedance Spectroscopy (EIS). Feasibility of this is under review.

Kessel, Kurt R.↗

Pre-Demonstration Development of Controlled-Release Corrosion Inhibitors and Healing Agents as Alternatives to Hexavalent Chromium

This Limited Scope Study was directed to achieve the following objectives: (1) Scale-up of materials that can meet MIL-PRF-23377 (solvent-based primer). (2) Provide evidence of resistance to aircraft alkaline cleaners and de-icing fluids. (3) Provide formulation for initial ecological and toxicity screening. (4) Submit an interim report that will provide the basis for a future ESTCP (the Dept. of Defense's (DoD's) Environmental Security Technology Certification Program) demonstration effort.The encapsulation procedure for two corrosion inhibitors was scaled up from lab scale to 2.0 kilograms. This scale will accommodate high volume production of coatings with encapsulated corrosion inhibitors for large surface areas during a follow-on ESTCP demonstration effort. Test results provided evidence of resistance to alkaline cleaners and aircraft de-icing fluids and compliance with MIL-PRF-23377. All the MIL-PRF-23377 requirements were met with the exception of the adhesion requirement, in top coated panels, and the flexibility requirement. Work on solving these two problems will be done prior to validation and demonstration of the technology. An initial ecological and toxicity screening identified several factors that were not critical to the acceptance of the encapsulated corrosion inhibitor. This new technology will lead to environmentally friendly alternatives to hexavalent chromium that will enable DoD to protect its assets. Field demonstration, licensing, qualification, and commercialization will allow its real world utilization. Abstract for Appendix A. Toxicology Report: Corrosion controls a significant problem for military equipment. Many surface treatment materials currently in use on items of military or aerospace materiel contain chromium (VI) as a component, a source of significant human health and environmental hazard. The formulation under evaluation contains no chromium. Most of the proposed components are low to moderate toxicity and are not a significant concern. Two of the formulation components are associated with some cancer hazard - 2-mercaptobenzothiazole and formaldehyde, but both find widespread use in industry and additional investigation is not required for this project.

Calle, Luz Marina↗

Pre-demonstration Development of Controlled-Release Corrosion Inhibitors and Healing Agents as Alternatives to Hexavalent Chromium

This Limited Scope Study was directed to achieve the following objectives:(1) Scale-up of materials that can meet MIL-PRF-23377 (solvent-based primer).(2) Provide evidence of resistance to aircraft alkaline cleaners and deicing fluids.(3) Provide formulation for initial ecological and toxicity screening.(4) Submit an interim report that will provide the basis for a future ESTCP demonstration effort.The encapsulation procedure for two corrosion inhibitors was scaled up from lab scale to 2.0 kg. This scale will accommodate high volume production of coatings with encapsulated corrosion inhibitors for large surface areas during a follow on ESTCP demonstration effort.Test results provided evidence of resistance to alkaline cleaners and aircraft deicing fluids and compliance with MIL-PRF-23377. All the MIL-PRF-23377 requirements were met with the exception of the adhesion requirement, in top coated panels, and the flexibility requirement. Work on solving these two problems will be done prior to validation and demonstration of the technology. An initial ecological and toxicity screening identified several factors that were not critical to the acceptance of the encapsulated corrosion inhibitor. This new technology will lead to environmentally friendly alternatives to hexavalent chromium that will enable DoD to protect its assets. Field demonstration, licensing, qualification, and commercialization will allow its real world utilization.

Calle, L. M.↗

Chemical-Biological Cyclic Process for Hexavalent Chromium Reduction to Trivalent Chromium in Aqueous Medium - 20224

Conventional treatment of chromium contamination focuses on immobilization of the highly toxic and water-soluble form Cr(VI), by reducing it to the relatively less toxic and less mobile trivalent form, Cr(III), using reducing compounds like ferrous sulfate or ferrous iron, Fe(II). The Cr(VI) also respond to biodegradation and subsequent reduction. During the reduction reaction, Fe(II) is oxidized to ferric, Fe(III), which, being at the highest oxidation state, has no ability to reduce Cr(VI), and therefore remediation process terminates. The good news is that metal-reducing bacteria, S. oneidensis MR-1, can regenerate Fe(II) from Fe(III) with the help of an organic electron donor in an appropriate bacterial media. Thus, in the Cr(VI) chemical remediation process, Fe(II) to Fe(III) conversion is reversed by the biological process, regenerating Fe(II) and the Cr(VI) chemical reduction process continues in a cyclic fashion. This study presents the results of regeneration of Fe(II) from fresh Fe(III) as well as from the reaction products of Cr(VI) and Fe(II). Both fresh Fe(III) and reaction product Fe(III) exhibited the same reduction behavior. Fe(II) production increased with the increase of initial concentration of Fe(III), resulting in 87.5% Fe(II) regeneration. The extent of Fe(III) reduction (Fe(II)t/Fe(III)0.hour) was 21 times higher than the extent of Cr(VI) reduction (Cr(VI)t/Cr(VI)0.hour) by S. oneidensis MR-1. In a cyclic process of sequential Cr(VI) addition, the amount of Fe(II) regeneration decreased with the increase in cycle number, a fixed quantity of starting S. oneidensis MR-1 could regenerate Fe(II) at least five times in a ten-hour period. More importantly, regenerated Fe(II) instantly reduced Cr(VI) to Cr(III). So, Fe(II) regeneration with metal-reducing bacteria has a good potential for application in groundwater and wastewater remediation in reducing Cr(VI) to Cr(III). As a comparison of chemical to biological transformation, chemical transformation of Cr(VI) by Fe(II) was almost 600 times greater than that of biological transformation. Therefore a chemical-biological cyclic process offers potential applications for remediation of groundwater and hexavalent chromium contaminated waste sites. (authors)

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Hexavalent Chrome Free Coatings for Electronics Electromagnetic Interference (EMI) Shielding Effectiveness (SE) Interim Test Report

Test specimen configuration was provided by Parker Chomerics. The EMI gasket used in this project was Cho-Seal 6503E. Black oxide alloy steel socket head bolts were used to hold the plates together. Non-conductive spacers were used to control the amount of compression on the gaskets. The following test fixture specifications were provided by Parker Chomerics. The CHO‐TP09 test plate sets selected for this project consist of two aluminum plates manufactured to the specifications detailed in CHO­‐TP09. The first plate, referred to as the test frame, is illustrated in Figure 1. The test frame is designed with a cutout in the center and two alternating bolt patterns. One pattern is used to bolt the test frame to the corresponding test cover plate (Figure 2), forming a test plate set. The second pattern accepts the hardware used to mount the fully assembled test plate set to the main adapter plate (Figure 3).

trivalent chromium↗

A biokinetic model for trivalent or hexavalent chromium in adult humans

Chromium exists in several oxidation states, with the trivalent state (Cr(III)) being the dominant naturally occurring form. Chromium in other oxidation states tends to be converted to the trivalent oxide in the natural environment and in biological systems. Chromium(III) has been shown to be an essential nutrient for humans and several non-human species. Chromium(VI), the second most stable form of chromium, is an important environmental contaminant that is mostly of industrial origin and is associated with lung cancer and nose tumours in chromium workers. This paper proposes a biokinetic model for chromium that addresses the distinctive behaviours of Cr(III) and Cr(VI) following uptake to blood of an adult human. Additionally, the model is based on biokinetic data derived from relatively short-term studies involving administration of chromium tracers to adult human subjects or laboratory animals, supplemented with data on the long-term distribution of chromium in adult humans as estimated from autopsy measurements. The model is part of a comprehensive update of biokinetic models of the International Commission on Radiological Protection, used to project or evaluate radiation doses from occupational intake of radionuclides.

62 RADIOLOGY AND NUCLEAR MEDICINE↗

Metal-organic-framework and walnut shell biochar composites for lead and hexavalent chromium removal from aqueous environments

Extensive research in recent years has explored the realm of porous carbon composites for various applications, including electrochemistry, structural materials, environmental remediation, and more. In particular, the fabrication of porous carbon composites using a metal-organic framework (MOF) and biochar (BC) for aqueous remediation is a fairly new avenue of research. In this study, a MOF-BC composite was synthesized with unmodified and chemically modified BCs using solvothermal synthesis. The composites were used as adsorbents to remediate heavy metals, such as lead (II) and chromium (VI), from aqueous environments. Here, it was verified that the MOF was homogeneously deposited onto the BC's surface using various material characterization techniques. Lead and chromium adsorption studies revealed a high adsorption capacity with greater than 99% removal for lead and ∼65% for chromium, respectively. Impressively, for lead, the highest observed experimental adsorption capacity of the MOF-chemically modified BC composite was 535 mg/g, compared to 240 mg/g for pristine BC. Meanwhile, the adsorption capacity of the same MOF-BC composite for chromium ions was low at 18 mg/g, compared to 80 mg/g for the chemically modified BC. The MOF-BC had a rapid adsorption rate, achieving equilibrium at only 150 min of reaction time for lead ions. MOF-BCs have higher adsorption for cationic lead through physisorption and ion-exchange mechanisms, whereas, for anionic chromium, removal is dominated only by physisorption mechanisms. The outcomes and methodological developments attained in this study offer a novel and compelling approach for synthesizing MOF-BC composites for aqueous remediation applications.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Ligand Control of Oxidation and Crystallographic Disorder in the Isolation of Hexavalent Uranium Mono-Oxo Complexes

Here, the development of high-valent transuranic chemistry requires robust methodologies to access and fully characterize reactive species. We have recently demonstrated that the reducing nature of imidophosphorane ligands supports the two-electron oxidation of U 4+ to U 6+ and established the use of this ligand to evaluate the inverse-trans-influence (ITI) in actinide metal-ligand multiple bond (MLMB) complexes. To extend this methodology and analysis to transuranic complexes, new small-scale synthetic strategies and lower-symmetry ligand derivatives are necessary to improve crys-tallinity and reduce crystallographic disorder. To this end, the synthesis of two new imidophosphorane ligands, [N=P t Bu(pip) 2 ]¯ (NPC 1 ) and [N=P t Bu(pyrr) 2 ]¯ (NPC 2 ) (pip = piperidinyl; pyrr = pyrrolidinyl) is presented, which break pseudo-C 3 axes in the tetravalent complexes, U[NPC 1 ] 4 and U[NPC 2 ] 4 . The reaction of these complexes with two-electron oxygen atom transfer reagents (N 2 O, trimethylamine N-oxide (TMAO) and 2,3:5,6-dibenzo-7-azabicyclo[2.2.1]hepta-2,5-diene (dbabhNO)) yields the U 6+ mono-oxo complexes U(O)[NPC 1 ] 4 and U(O)[NPC 2 ] 4 . This methodology is optimized for direct translation to transuranic elements. Of the two ligands, the NPC 2 framework is most suitable for facilitating detailed bonding analysis and assessment of the ITI. Theoretical evaluation of the U–(NPC) bonding confirms a substantial difference between axially and equatorially-bonded N atoms, revealing mark-edly more covalent U–N ax interactions. The U 6d+5f combined contribution for U–N ax is nearly double that of U–N eq , accounting for ITI shortening and increased bond order of the axial bond. Two distinct N-atom hybridizations in the pyrrolidine/piperidine rings are noted across the complexes, with approximate sp 2 and sp 3 configurations describing the slightly shorter P–N “planar” and slightly longer P–N “pyramidal” bonds, respectively. In all complexes, the NPC 2 ligands feature more planar N atoms than NPC 1 , in accordance with a higher electron-donating capacity of the former.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗