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At least 37 records · Page 2

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NASA NTRS1999

Microcalorimetric Measurements of Hydrogen Peroxide Stability

Recent interest in propellants with nontoxic reaction products has led to a resurgence of interest in hydrogen peroxide for various propellant applications. Because hydrogen peroxide is sensitive to contaminants and materials interactions, stability and shelf life are issues. A relatively new, ultrasensitive heat measurement technique, isothermal microcalorimetry, is being used at the White Sands Test Facility to monitor the decomposition of hydrogen peroxide at near ambient temperatures. Isothermal microcalorimetry measures the beat flow from a reaction vessel into a surrounding heat sink. In these applications, microcalorimetry is approximately 1,000 times more sensitive than accelerating rate calorimetry or differential scanning calorimetry for measuring thermal events. Experimental procedures have been developed for the microcalorimetric measurement of the ultra-small beat effects caused by incompatible interactions of hydrogen peroxide. The decomposition rates of hydrogen peroxide at the picomole/sec/gram level have been measured showing the effects of stabilizers and peroxide concentration. Typical measurements are carried out at 40 C over a 24-hour period, This paper describes a method for the conversion of the heat flow measurements to chemical reaction rates based on thermochemical considerations. The reaction rates are used in a study of the effects of stabilizer levels on the decomposition of propellant grade hydrogen peroxide.

Davis, Dennis D.↗

NASA NTRS2002

Oxygen Mass Flow Rate Generated for Monitoring Hydrogen Peroxide Stability

Recent interest in propellants with non-toxic reaction products has led to a resurgence of interest in hydrogen peroxide for various propellant applications. Because peroxide is sensitive to contaminants, material interactions, stability and storage issues, monitoring decomposition rates is important. Stennis Space Center (SSC) uses thermocouples to monitor bulk fluid temperature (heat evolution) to determine reaction rates. Unfortunately, large temperature rises are required to offset the heat lost into the surrounding fluid. Also, tank penetration to accomodate a thermocouple can entail modification of a tank or line and act as a source of contamination. The paper evaluates a method for monitoring oxygen evolution as a means to determine peroxide stability. Oxygen generation is not only directly related to peroxide decomposition, but occurs immediately. Measuring peroxide temperature to monitor peroxide stability has significant limitations. The bulk decomposition of 1% / week in a large volume tank can produce in excess of 30 cc / min. This oxygen flow rate corresponds to an equivalent temperature rise of approximately 14 millidegrees C, which is difficult to measure reliably. Thus, if heat transfer were included, there would be no temperature rise. Temperature changes from the surrounding environment and heat lost to the peroxide will also mask potential problems. The use of oxygen flow measurements provides an ultra sensitive technique for monitoring reaction events and will provide an earlier indication of an abnormal decomposition when compared to measuring temperature rise.

Ross, H. Richard↗

NASA NTRS2004

Hazard Assessment of Personal Protective Clothing for Hydrogen Peroxide Service

Selection of personal protective equipment (PPE) for hydrogen peroxide service is an important part of the hazard assessment process. But because drip testing of chemical protective clothing for hydrogen peroxide service has not been reported for about 40 years, it is of great interest to test new protective clothing materials with new, high-concentration hydrogen peroxide following similar procedures. The suitability of PPE for hydrogen peroxide service is in part determined by observations made when hydrogen peroxide is dripped onto swatches of protective clothing material. Protective clothing material was tested as received, in soiled condition, and in grossly soiled condition. Materials were soiled by pretreating the material with potassium permanganate (KMnO4) solution then drying to promote a reaction. Materials were grossly soiled with solid KMnO4 to greatly promote reaction. Observations of results including visual changes to the hydrogen peroxide and materials, times to ignition, and self-extinguishing characteristics of the materials are reported.

Greene, Ben↗

NASA NTRS2005

APPARATUS AND METHOD FOR TREATING POLLUTANTS IN A GAS USING HYDROGEN PEROXIDE AND UV LIGHT

An apparatus for treating pollutants in a gas may include a source of hydrogen peroxide, and a treatment injector for creating and injecting dissociated hydrogen peroxide into the flow of gas. The treatment injector may further include an injector housing having an inlet, an outlet, and a hollow interior extending there between. The inlet may be connected in fluid communication with the source of hydrogen peroxide so that hydrogen peroxide flows through the hollow interior and toward the outlet. At least one ultraviolet (UV) lamp may be positioned within the hollow interior of the injector housing. The at least one UV lamp may dissociate the hydrogen peroxide flowing through the tube. The dissociated hydrogen peroxide may be injected into the flow of gas from the outlet for treating pollutants, such as nitrogen oxides.

Cooper, Charles David↗

NASA NTRS2006

Concentration of Hydrogen Peroxide

Methods for concentrating hydrogen peroxide solutions have been described. The methods utilize a polymeric membrane separating a hydrogen peroxide solution from a sweep gas or permeate. The membrane is selective to the permeability of water over the permeability of hydrogen peroxide, thereby facilitating the concentration of the hydrogen peroxide solution through the transport of water through the membrane to the permeate. By utilizing methods in accordance with the invention, hydrogen peroxide solutions of up to 85% by volume or higher may be generated at a point of use without storing substantial quantities of the highly concentrated solutions and without requiring temperatures that would produce explosive mixtures of hydrogen peroxide vapors.

Parrish, Clyde F.↗

NASA NTRS2005

Apparatus and method for treating pollutants in a gas using hydrogen peroxide and UV light

An apparatus for treating pollutants in a gas may include a source of hydrogen peroxide, and a treatment injector for creating and injecting dissociated hydrogen peroxide into the flow of gas. The treatment injector may further include an injector housing having an inlet, an outlet, and a hollow interior extending therebetween. The inlet may be connected in fluid communication with the source of hydrogen peroxide so that hydrogen peroxide flows through the hollow interior and toward the outlet. At least one ultraviolet (UV) lamp may be positioned within the hollow interior of the injector housing. The at least one UV lamp may dissociate the hydrogen peroxide flowing through the tube. The dissociated hydrogen peroxide may be injected into the flow of gas from the outlet for treating pollutants, such as nitrogen oxides.

Cooper, Charles David↗

NASA NTRS2010

Coating for components requiring hydrogen peroxide compatibility

The present invention provides a heretofore-unknown use for zirconium nitride as a hydrogen peroxide compatible protective coating that was discovered to be useful to protect components that catalyze the decomposition of hydrogen peroxide or corrode when exposed to hydrogen peroxide. A zirconium nitride coating of the invention may be applied to a variety of substrates (e.g., metals) using art-recognized techniques, such as plasma vapor deposition. The present invention further provides components and articles of manufacture having hydrogen peroxide compatibility, particularly components for use in aerospace and industrial manufacturing applications. The zirconium nitride barrier coating of the invention provides protection from corrosion by reaction with hydrogen peroxide, as well as prevention of hydrogen peroxide decomposition.

Yousefiani, Ali↗

NASA NTRSDate not supplied

Hydrogen Peroxide as a Method for Bioburden Reduction in Facilities with Strict Materials Requirements.

The cleanrooms used to curate NASA’s Astromaterials samples are carefully monitored for particulate and inorganic contamination. The clean labs also have a very limited set of acceptable materials and cleaning agents to further minimize the potential for contamination. Labs are cleaned primarily with isopropyl alcohol. Astromaterials samples are handled with tools made of stainless steel (304 or 316), Teflon, or aluminum alloy (6061). Although our current collections are not particularly susceptible to biological alteration or organic contamination, this will not be the case for new collections from the OSIRIS-REx mission, Hayabusa2, and from Mars Sample Return. Therefore, it is necessary to develop and test methods to reduce the bioburden in astromaterials cleanrooms without introducing unwanted contaminants. We will report on the results of three case studies where 7.5 wt% hydrogen peroxide was prepared from a stock solution of ultrapure 30 wt% hydrogen peroxide (JT Baker) using curation-grade ultrapure water. We followed CDC (Center for Disease Control) guidelines for using hydrogen peroxide as a high level disinfectant. This solution was used to clean a glovebox prior to processing Apollo samples, as well as surfaces in the Antarctic meteorite processing lab and Stardust lab after facilities monitoring indicated an unwanted increase in bioburden. In all three instances, the culturable bioburden was significantly reduced after a 30 min. exposure to the 7.5% hydrogen peroxide solution without a corresponding increase in inorganic or organic contamination. We observed 77 to 100% reductions in the bioburden recovery rate. In one case study, we also performed amplicon DNA sequencing on samples collected from the surfaces before and after cleaning. We observed a significant change in microbial community composition after peroxide cleaning. These results suggest that routine cleaning with hydrogen peroxide could be an effective way to control bioburden in astromaterials cleanrooms and other facilities with strict contamination control requirements.

A B Regberg↗

NASA NTRSDate not supplied

Hydrogen Peroxide as a Method for Bioburden Reduction in Facilities with Strict Materials Requirements

A B Regberg↗

DOE OSTI2020

Dissolution of poorly soluble uranyl phosphate phases in the Metaautunite Subgroup under uranyl peroxide cage cluster forming conditions

Uranyl phosphate minerals are widespread in uranium deposits and usually exhibit very low solubility in aqueous systems. Uranyl phosphates of the autunite group and metaautunite subgroup impact the mobility of uranium in the environment and have inspired groundwater remediation strategies that emphasize their low solubility. The importance of soluble uranium-bearing macro-anions, including nanoscale uranyl peroxide cage clusters, is largely unexplored relative to solubilization of normally low-solubility uranium minerals. Eight synthetic analogs of metaautunite subgroup minerals have been prepared and placed in various alkaline aqueous solutions containing hydrogen peroxide and tetraethylammonium hydroxide. Each uranyl phosphate studied has a topologically identical anionic sheet of uranyl square bipyramids and phosphate tetrahedra combined with various cations (Li + , Na + , K + , Rb + , Cs + , Mg 2+ , Ca 2+ , Ba 2+ ) and water in the interlayer. Uranyl peroxides formed under many of the experimental conditions examined, including solid studtite [(UO 2 )(O 2 )(H 2 O) 2 ](H 2 O) 2 and soluble uranyl peroxide cage clusters containing as many as 28 uranyl ions. Uranyl phosphate solids in contact with solutions in which uranyl peroxide cage clusters formed dissolved extensively or completely. The greatest dissolution of uranyl phosphates occurred in systems that contained cations with larger hydrated radii, Li + and Na + . The details of the uranium speciation in solution depended on the pH and counter cations provided from the interlayers of the uranyl phosphate solids.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2026

Scale-Up of Electrode Coating and Flow-Field for Commercial Hydrogen Peroxide Electrolyzer: Cooperative Research and Development Final Report, CRADA Number CRD-17-00687

Hydrogen peroxide is currently produced at central chemical plants via the anthraquinone oxidation process. This process produces environmental pollutants that are costly to remediate, requires hazardous long distance shipping of highly concentrated peroxide (50% or 70%), and necessitates extra handling costs related to storage and dilution. Peroxygen Systems, Inc. (PSi) is developing breakthrough technology for on-site hydrogen peroxide production. PSi’s on-site on-demand electrolyzer can reduce the cost of producing hydrogen peroxide by 50%, while also completely eliminating the cost and safety issues associated with shipping and handling of high concentration hydrogen peroxide. The challenge for PSi is scaling. To support the next step toward commercialization (customer pilot tests), scaling the prototype into larger single cells and 20-40 cell stacks is required. In addition to internal hardware and flow-field design efforts at PSi, NREL will address three critical problems for this scale-up effort: (1) demonstrating a large scale roll-to-roll (R2R) process to coat uniform electrode materials for 100 cm2 and 500 cm2 stack testing, (2) demonstrating an in-line diagnostic to achieve better electrode quality control, and (3) performing in situ cell/stack testing to better understand and optimize the performance of the flow field design.

28 EE - Advanced Manufacturing Office (EE-5A)↗

NASA NTRSDate not supplied

In-Situ Electrochemical Generation and Utilization of Hydrogen Peroxide for Disinfection

Disinfection needs to meet personal hygiene requirements at the International Space Station (ISS) is currently accomplished through the use of pre-packaged, disposable, wetted wipes, which represent an appreciable carry-along mass and disposal burden. However, as human missions travel further into the solar system the availability of resources to resupply will be diminished. Therefore, next-generation system should use onboard utilities to create on demand disinfectants, thereby reducing the dependence on earth-based supplies and further eliminating storage and disposal problems. Accordingly, we are developing an in-situ approach to electrochemically generate hydrogen peroxide disinfecting solution utilizing onboard life support supplies (Air/Water) to neutralize surface microorganisms present in closed living systems. As discussed within our 2019 and 2021 ICES papers (ICES-2019-38 and ICES-2021-273), we have continued to improve our TRL by scaling the electrochemical generation production process and validating the system in a zero-gravity parabolic loop flight test. In this paper we will demonstrate a system that can achieve over 1 L of >2 w/w% peroxide per day with DI water and air feeds. The hydrogen peroxide solutions generated were sent to NASA for microbial control property characterization. Overall, the electrochemical peroxide generation system offers a more economical and practical alternative, with the disinfectant being generated on demand and in-situ (using available life support materials of Air/Water); and applied to reusable cloths. The specific application of interest to this program is crew contact surfaces in space vehicles, but this technology could be utilized for waste water disinfection, heat exchanger biofouling remediation, and laundry applications. The peroxide generation system will also be able to address Earth-based needs in various settings such as field hospitals, restaurants, military, warehouses, movie theatres, among many others.

hydrogen peroxide↗

NASA NTRSDate not supplied

Numerical Investigation of Heat Transfer and Fluid Flow within Electrochemical Hydrogen Peroxide Generation Unit

Long-term manned space missions require the onboard production of disinfectants essential for maintaining crew health and supporting life systems. Currently, disinfection aboard the International Space Station (ISS) relies on disposable wetted wipes, which are regularly resupplied from Earth. This approach imposes a significant burden on resupply logistics, storage, and waste management. To address these challenges and support future missions, efforts are underway to develop an in-situ solution that electrochemically generates hydrogen peroxide disinfectant using onboard resources. In collaboration with NASA, Faraday Technology, Inc. has advanced this concept through a series of Small Business Innovation Research (SBIR) projects, resulting in the development of a Peroxide Generation Unit (PGU). The PGU can produce up to 3 wt.% hydrogen peroxide on-demand at a rate of 1 liter per day, providing a sustainable alternative to Earth-dependent supplies. The resulting aqueous hydrogen peroxide (H₂O₂) is an effective disinfectant, safe for crew use, compatible with spacecraft systems, and free from volatiles, off-gassing, or residues. This innovation offers a reliable, efficient solution for onboard disinfection, reducing dependence on Earth-based resupply while ensuring the health and safety of space crews. Generating hydrogen peroxide at the required rate needs high voltages and currents, exceeding 20V and 2A respectively, which leads to significant heat generation from Joule heating. This temperature rise poses a risk to sensitive system components, especially critical and expensive membranes that can degrade under thermal stress. To mitigate this risk, the thermal, fluid, and electrical flows within the system are modeled computationally using the commercial software COMSOL. The numerical simulations are validated against experimental data from both sub-scale and alpha-scale systems. Once verified, the model is employed to identify thermal hotspots, investigate their underlying causes, and explore solutions to prevent them.

Life Support Systems (LSS)↗

DOE OSTI2021

Radiation-Induced Solid-State Transformations of Uranyl Peroxides

Single-crystal X-ray diffraction studies of pristine and γ-irradiated Ca 2 [UO 2 (O 2 ) 3 ]·9H 2 O reveal site-specific atomic-scale changes during the solid-state progression from a crystalline to X-ray amorphous state with increasing dose. Following γ-irradiation to 1, 1.5, and 2 MGy, the peroxide group not bonded to Ca 2+ is progressively replaced by two hydroxyl groups separated by 2.7 Å (with minor changes in the unit cell), whereas the peroxide groups bonded to Ca 2+ cations are largely unaffected by irradiation prior to amorphization, which occurs by a dose of 3 MGy. The conversion of peroxide to hydroxyl occurs through interaction of neighboring lattice H 2 O molecules and ionization of the peroxide O–O bond, which produces two hydroxyls, and allows isolation of the important monomer building block, UO 2 (O 2 ) 2 (OH) 2 4– , that is ubiquitous in uranyl capsule polyoxometalates. Steric crowding in the equatorial plane of the uranyl ion develops and promotes transformation to an amorphous phase. In contrast, γ-irradiation of solid Li 4 [(UO 2 )(O 2 ) 3 ]·10H 2 O results in a solid-state transformation to a well-crystallized peroxide-free uranyl oxyhydrate containing sheets of equatorial edge and vertex-sharing uranyl pentagonal bipyramids with likely Li and H 2 O in interlayer positions. The irradiation products of these two uranyl triperoxide monomers are compared via X-ray diffraction (single-crystal and powder) and Raman spectroscopy, with a focus on the influence of the Li + and Ca 2+ countercations. Highly hydratable and mobile Li+ yields to uranyl hydrolysis reactions, while Ca 2+ provides lattice rigidity, allowing observation of the first steps of radiation-promoted transformation of uranyl triperoxide.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2020

The Role of the Organic Solvent Polarity in Isolating Uranyl Peroxide Capsule Fragments

Uranyl peroxide capsules are a fascinating class of polyoxometalates (POMs), discovered only in the 21st century. Understanding the reactivity between peroxide, alkali cations, and uranyl in alkaline solutions is important in nuclear science disciplines including mineralogy, nuclear energy, and legacy nuclear wastes. In this work, we have developed a general procedure to isolate different fragments of the uranyl-peroxide POM capsules, using organic solvents to partially remove K + salts from crude solids of the monomer building block UO 2 (O 2 ) 3 4– (K–U 1 ), leading to stabilization of these reactive fragments. Higher polarity organic solvents remove more K + salts from the crude solid, owed to higher solubility, resulting in more extensive linking of uranyl peroxide building units. By this strategy we have isolated and structurally characterized a dimer K 6 [(UO 2 ) 2 (O 2 ) 4 (OH) 2 ]·7H 2 O (K–U 2 ) and a hexamer face frequently observed in the capsules, K 12 [(UO 2 ) 6 (O 2 ) 9 (OH) 6 ]$·x$H 2 O(K–U 6 ). Comparing experimental and computed Raman spectra shows that these intermediates crystallize by a solid-to-solid transformation, via polymerization of the monomer building block. By small-angle X-ray scattering (SAXS), we track the conversion of the fragments to POM capsules; the reaction rate increases from K–U 1 (days) < K–U 2 (hours) < K–U 6 (instantaneous). This study provides a general synthetic procedure to isolate metastable uranyl peroxide oligomers and control the oligomerization, which will be later applied to systems with the heavier alkalis that are even less stable.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2021

A low power flexible dielectric barrier discharge disinfects surfaces and improves the action of hydrogen peroxide

There is an urgent need for disinfection and sterilization devices accessible to the public that can be fulfilled by innovative strategies for using cold atmospheric pressure plasmas. Here, we demonstrate a successful novel combination of a flexible printed circuit design of a dielectric barrier discharge (flex-DBD) with an environmentally safe chemical reagent for surface decontamination from bacterial contaminants. Flex-DBD operates in ambient air, atmospheric pressure, and room temperature without any additional gas flow at a power density not exceeding 0.5 W/cm 2 . The flex-DBD activation of a 3% hydrogen peroxide solution results in the reduction in the bacterial load of a surface contaminant of > 6log 10 in 90 s, about 3log 10 and 2log 10 better than hydrogen peroxide alone or the flex-DBD alone, respectively, for the same treatment time. We propose that the synergy between plasma and hydrogen peroxide is based on the combined action of plasma-generated OH · radicals in the hydrogen peroxide solution and the reactive nitrogen species supplied by the plasma effluent. A scavenger method verified a significant increase in OH · concentration due to plasma treatment. Novel in-situ FTIR absorption spectra show the presence of O 3 , NO 2 , N 2 O, and other nitrogen species. Ozone dissolving in the H 2 O 2 solution can effectively generate OH · through a peroxone process. The addition of the reactive nitrogen species increases the disinfection efficiency of the hydroxyl radicals and other oxygen species. Hence, plasma activation of a low concentration hydrogen peroxide solution, using a hand-held flexible DBD device results in a dramatic improvement in disinfection.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

DOE OSTI2021

Stability of the peroxide group in BaO 2 under high pressure

Alkaline earth metal peroxides are typical examples of ionic compounds containing polyanions. We herein report a stable BaO 2 phase at high pressure up to 130 GPa found via a first-principles computational structure searches and high-pressure experimental investigations. The identified monoclinic structure (space group C2/m) can be derived by sublattice distortions of Ba atoms and peroxide groups associated with the phonon mode softening of the lower-pressure Cmmm structure. Contrary to the previous expectation of polymerization of the peroxide group at elevated pressure, the new phase retains the peroxide group and interestingly exhibits an insulating behavior demonstrating an increase of the band gap under compression. Our synchrotron XRD measurements could not distinguish between Cmmm and C2/m BaO 2 definitively because the difference in XRD patterns is very subtle. However, our data do not show any sign of polymerization transition up to 120 GPa. Raman spectra of the O-O peroxide vibration show a small anomaly in frequency at 110 GPa, which is qualitatively similar to that predicted theoretically due to the Cmmm to C2/m phase transition thus supporting the predicted transformation.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

NASA NTRS1975

Bactericidal effect of hydrogen peroxide on spacecraft isolates

Results are presented for an experimental study designed to assess the effect of hydrogen peroxide on both sporeforming and nonsporeforming spacecraft isolates as an initial step in determining its suitability for microbiological decontamination of certain United States spacecraft. Survivor data were obtained for eight bacterial isolates (six sporeformers and two nonsporeformers) recovered before launch Mariner 9 and exposed to concentrations of 3, 10, and 15% hydrogen peroxide. The effects of various concentrations of hydrogen peroxide on the spores are presented in tabular form, along with the percentage of survival of nonsporeformers exposed to hydrogen peroxide. No viable vegetative cells were recovered after a 10-min exposure time to any of the three concentration of hydrogen peroxide.

Wardle, M. D.↗