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At least 217 records · Page 12

Composite-Material Tanks with Chemically Resistant Liners

Lightweight composite-material tanks with chemically resistant liners have been developed for storage of chemically reactive and/or unstable fluids . especially hydrogen peroxide. These tanks are similar, in some respects, to the ones described in gLightweight Composite-Material Tanks for Cryogenic Liquids h (MFS-31379), NASA Tech Briefs, Vol. 25, No. 1 (January, 2001), page 58; however, the present tanks are fabricated by a different procedure and they do not incorporate insulation that would be needed to prevent boil-off of cryogenic fluids. The manufacture of a tank of this type begins with the fabrication of a reusable multisegmented aluminum mandrel in the shape and size of the desired interior volume. One or more segments of the mandrel can be aluminum bosses that will be incorporated into the tank as end fittings. The mandrel is coated with a mold-release material. The mandrel is then heated to a temperature of about 400 F (approximately equal to 200 C) and coated with a thermoplastic liner material to the desired thickness [typically approxiamtely equal to 15 mils (approximately equal to 0.38 mm)] by thermal spraying. In the thermal-spraying process, the liner material in powder form is sprayed and heated to the melting temperature by a propane torch and the molten particles land on the mandrel. The sprayed liner and mandrel are allowed to cool, then the outer surface of the liner is chemically and/or mechanically etched to enhance bonding of a composite overwrap. The etched liner is wrapped with multiple layers of an epoxy resin reinforced with graphite fibers; the wrapping can be done either by manual application of epoxy-impregnated graphite cloth or by winding of epoxy-impregnated filaments. The entire assembly is heated in an autoclave to cure the epoxy. After the curing process, the multisegmented mandrel is disassembled and removed from inside, leaving the finished tank. If the tank is to be used for storing hydrogen peroxide, then the liner material should be fluorinated ethylene/propylene (FEP), and one or more FEP O ring(s) should be used in the aluminum end fitting(s). This choice of materials is dictated by experimental observations that pure aluminum and FEP are the only materials suitable for long-term storage of hydrogen peroxide and that other materials tend to catalyze the decomposition of hydrogen peroxide to oxygen and water. Other thermoplastic liner materials that are suitable for some applications include nylon 6 and polyethylene. The processing temperatures for nylon 6 are lower than those for FEP. Nylon 6 is compatible with propane, natural gas, and other petroleum-based fuels. Polyethylene is compatible with petroleum- based products and can be used for short-term storage of hydrogen peroxide.

DeLay, Thomas K.↗

Bubble-Free Frontal Polymerization of Acrylates via Redox-Initiated Free Radical Polymerization

Thermal frontal polymerization (FP) of acrylate monomers mixed with conventional peroxide initiators leads to significant bubble formation at the polymerizing front, limiting their practical applications. Redox initiators present a promising alternative to peroxide initiators, as they prevent the formation of gaseous byproducts during initiator decomposition and lower the front temperature, thereby enabling bubble-free FP. In this study, we investigate the FP of acrylate monomers of varying functionalities, including methyl methacrylate (MMA), 1,6-hexanediol diacrylate (HDDA), and trimethylolpropane triacrylate (TMPTA), using N,N -dimethylaniline/benzoyl peroxide (DMA/BPO) redox couple at room temperature and compare their front behavior, pot life, and bubble formation with those of same resin systems mixed with a conventional peroxide initiator, Luperox 231. The use of redox couples in FP of acrylates shows promise for rapid, energy-efficient manufacturing of polyacrylates and can enable new applications such as 3D printing and composite manufacturing.

36 MATERIALS SCIENCE↗

The synthesis of higher oxides of alkali and alkaline earth metals in an electric discharge: Theoretical and experimental studies

Potassium hydroxide was subjected to the products of an electrical discharge sustained in oxygen and produced both potassium peroxide and superoxide. The conversion to higher oxides was shown to strongly depend upon the particle size of KOH, the position of KOH in the discharge zone, and the operating conditions of the discharge. Similar experiments were performed with hydroxides of lithium and calcium which do not form superoxides, but are converted to peroxides. The yields of peroxides were shown to strongly depend upon the operating conditions of the discharge. The absence of superoxides and the presence of peroxides of lithium and calcium was explained from the consideration of relative thermodynamic stability of the oxides of lithium and calcium. Thermogravimetric analysis was shown to provide a more accurate means for determining the amount of KO2 than previous methods.

Bell, A. T.↗

Development of biological and nonbiological explanations for the Viking label release data

The plausibility that hydrogen peroxide, widely distributed within the Mars surface material, was responsible for the evocative response obtained by the Viking Labeled Release (LR) experiment on Mars was investigated. Although a mixture of gamma Fe2O3 and silica sand stimulated the LR nutrient reaction with hydrogen peroxide and reduced the rate of hydrogen decomposition under various storage conditions, the Mars analog soil prepared by the Viking Inorganic Analysis Team to match the Mars analytical data does not cause such effects. Nor is adequate resistance to UV irradiation shown. On the basis of the results and consideration presented while the hydrogen peroxide theory remains the most, if not only, attractive chemical explanation of the LR data, it remains unconvincing on critical points. Until problems concerning the formation and stabilization of hydrogen peroxide on the surface of Mars can be overcome, adhere to the scientific evidence requires serious consideration of the biological theory.

Source record↗

Organometallic catalysts for primary phosphoric acid fuel cells

A continuing effort by the U.S. Department of Energy to improve the competitiveness of the phosphoric acid fuel cell by improving cell performance and/or reducing cell cost is discussed. Cathode improvement, both in performance and cost, available through the use of a class of organometallic cathode catalysts, the tetraazaannulenes (TAAs), was investigated. A new mixed catalyst was identified which provides improved cathode performance without the need for the use of a noble metal. This mixed catalyst was tested under load for 1000 hr. in full cell at 160 to 200 C in phosphoric acid H3PO4, and was shown to provide stable performance. The mixed catalyst contains an organometallic to catalyze electroreduction of oxygen to hydrogen peroxide and a metal to catalyze further electroreduction of the hydrogen peroxide to water. Cathodes containing an exemplar mixed catalyst (e.g., Co bisphenyl TAA/Mn) operate at approximately 650 mV vs DHE in 160 C, 85% H3PO4 with oxygen as reactant. In developing this mixed catalyst, a broad spectrum of TAAs were prepared, tested in half-cell and in a rotating ring-disk electrode system. TAAs found to facilitate the production of hydrogen peroxide in electroreduction were shown to be preferred TAAs for use in the mixed catalyst. Manganese (Mn) was identified as a preferred metal because it is capable of catalyzing hydrogen peroxide electroreduction, is lower in cost and is of less strategic importance than platinum, the cathode catalyst normally used in the fuel cell.

Walsh, Fraser↗

Investigation of new hypergol scrubber technology

The ultimate goal of this work is to minimize the liquid waste generated from the scrubbing of hypergolic vent gases. In particular, nitrogen tetroxide, a strong oxidizer used in hypergolic propellant systems, is currently scrubbed with a sodium hydroxide solution resulting in a hazardous liquid waste. This study investigated the use of a solution of potassium hydroxide and hydrogen peroxide for the nitrogen textroxide vent scrubber system. The potassium nitrate formed would be potentially usable as a fertilizer. The hydrogen peroxide is added to convert the potassium nitrite that is formed into more potassium nitrate. Smallscale laboratory tests were conducted to establish the stability of hydrogen peroxide in the proposed scrubbing solution and to evaluate the effectiveness of hydrogen peroxide in converting nitrite to nitrate.

Glasscock, Barbara H.↗

Process and Equipment for Nitrogen Oxide Waste Conversion to Fertilizer

The present invention describes a process for converting vapor streams from sources containing at least one nitrogen-containing oxidizing agent therein to a liquid fertilizer composition comprising the steps of: (1) directing a vapor stream containing at least nitrogen-containing oxidizing agent to a first contact zone; (2) contacting said vapor stream with water to form nitrogen oxide(s) from said at least one nitrogen- containing oxidizing agent; (3) directing said acid(s) as a second stream to a second contact zone; (4) exposing said second stream to hydrogen peroxide which is present within said second contact zone in a relative amount of at least 0.1% by weight of said second stream within said second contact zone to convert at least some of any nitrogen oxide species or ions other than in the nitrite form present within said second stream to nitrate ion; (5) sampling said stream within said second contact zone to determine the relative amount of hydrogen peroxide within said second contact zone; (6) adding hydrogen peroxide to said second contact zone when a level on hydrogen peroxide less than 0.1% by weight in said second stream is determined by said sampling; (7) adding a solution comprising potassium hydroxide to said second stream to maintain a pH between 6.0 and 11.0 within said second stream within said second contact zone to form a solution of potassium nitrate; and (8) removing sais solution of potassium nitrate from said second contact zone.

Lueck, Dale E.↗

Process for Nitrogen Oxide Waste Conversion to Fertilizer

The present invention describes a process for converting vapor streams from sources containing at least one nitrogen-containing oxidizing agent therein to a liquid fertilizer composition comprising the steps of: a) directing a vapor stream containing at least one nitrogen-containing oxidizing agent to a first contact zone; b) contacting said vapor stream with water to form nitrogen oxide(s) from said at least one nitrogen-containing oxidizing agent; c) directing said acid(s) as a second stream to a second contact zone; d) exposing said second stream to hydrogen peroxide which is present within said second contact zone in a relative amount of at least 0.1% by weight of said second stream within said second contact zone to convert at least some of any nitrogen oxide species or ions other than in the nitrate form present within said second stream to nitrate ion; e) sampling said stream within said second contact zone to determine the relative amount of hydrogen peroxide within said second contact zone; f) adding hydrogen peroxide to said second contact zone when a level of hydrogen peroxide less than 0.1 % by weight in said second stream is determined by said sampling; g) adding a solution comprising potassium hydroxide to said second stream to maintain a pH between 6.0 and 11.0 within said second stream within said second contact zone to form a solution of potassium nitrate; and h) removing said solution of potassium nitrate from said second contact zone.

Lueck, Dale E.↗

The preparation of calcium superoxide for air breathing and scrubbing applications

There is interest in the preparation of high-purity calcium superoxide as an oxygen source for breathing apparatus because both the available oxygen and the capacity for carbon dioxide removal, per unit weight of superoxide, are higher than that of a number of other chemical oxygen sources. A review of earlier findings shows that the general method used by Vol'nov and coworkers for the decomposition of calcium peroxide diperoxyhydrate can yield preparations containing more than 58.4% calcium superoxide maximum predicted for an equimolar disproportionation reaction. The decomposition of solid calcium peroxide diperoxyhydrate is studied using an apparatus that allows good control of the critical reaction parameters. The removal of water from decomposing calcium peroxide diperoxyhydrate, before the same water has an opportunity to back react with the calcium superoxide formed in the reaction, constitutes the rationale of the experiments. Even with allowance for the anomalies observed in the analytical results, the yields appear to be in the 65+ percent range, and optimization of the experimental variables is still being pursued.

Ballou, E. V.↗

Effects of Microheterogeneity in Hen Egg-White Lysozyme Crystallization

In earlier sodium dodecylsulfate polyacylamide gel electrophoresis (SDS-PAGE) studies it has been found that commonly utilized commercial hen egg-white lysozyme (HEWL) preparations contained 0.2-0.4 mol% covalently bound dimers. Here it is shown, using high-performance capillary electrophoresis (HPCE), that HEWL contains, in addition, two differently charged monomers in comparable amounts. To explore the origin of these microheterogeneous contaminants, purified HEWL (PHEWL) has been oxidized with hydrogen peroxide (0.0026-0.88 M) at various pH levels between 4.5 and 12.0. Optical densitometry of oxidized PHEWL (OHEWL) bands in SDS PAGE gels shows that hydrogen peroxide at 0.88 M in acetate buffer pH 4.5 increased the amount of dimers about sixfold over that in commercial HEWL. OHEWL had, in addition to one of the two monomer forms found in HEWL and PHEWL, three other differently charged monomer forms, each of them representing about 25% of the preparation. SDS-PAGE analysis of OHEWL yielded two closely spaced dimer bands with M(sub r) = 28 000 and 27 500. In addition, larger HEWL oligomers with M, = 1.7 million and 320 000 were detected by gel-filtration fast protein liquid chromatography with multiangle laser light scattering detection. Non-dissociating PAGE in large pore size gels at pH 4.5 confirmed the presence of these large oligomers in HEWL and OHEWL. Increased microheterogeneity resulted in substantial effects on crystal growth and nucleation rate. On addition of 10 microgram(exp -1) mg ml(exp -1) OHEWL to 32 mg ml(exp -1) HEWL crystallizing solutions, both the number and size of forming crystals decreased roughly proportionally to the concentration of the added microheterogeneity. The same effect was observed in HEWL solutions on addition of 0.03-9,3 M Hydrogen peroxide. Repartioning of the dimer during crystallzation aat various temperatures between 277 and 293 K was analyzed by SDS-PAGE. The crystals contained <= 25 % weight by volume of the oligomers in the solution, with no apparent temperature dependence of the repartioning.

Thomas, B. R.↗

Atmospheric H2O2 measurement: comparison of cold trap method with impinger bubbling method

Collection of atmospheric H2O2 was performed by a cold trap method using dry ice-acetone as the refrigerant. The air was drawn by a pump into a glass gas trap immersed in the dry ice-acetone slush in a dewar flask at a flow rate of 2.5 l min-1 for approximately 2 h. Collection efficiency was > 99% and negligible interferences by O3, SO2 or organic matter with the collected H2O2 in the trap were observed. This method was compared with the air impinger bubbling method which has been previously described (Kok et al., 1978a, b, Envir. Sci. Technol. 12, 1072-1080). The measured total peroxide (H2O2 + organic peroxide) values in a series of aim samples collected by the impinger bubbling method (0.06-3.7 ppb) were always higher than those obtained by the cold trap method (0.02-1.2 ppb). Laboratory experiments suggest that the difference in values between the two methods probably results from the aqueous phase generation of H2O2 and organic peroxide in the impinger solution by a reaction of atmospheric O3 with olefinic and aromatic compounds. If these O3-organic compound reactions which occur in the impinger also occur in aqueous droplets in the atmosphere, the process could be very important for aqueous phase generation of H2O2 in clouds and rainwater.

NASA Discipline Exobiology↗

UV Induced Oxidation of Nitric Oxide

Nitric oxide in a gaseous stream is converted to nitrogen dioxide using oxidizing species generated at least in part using in situ UV radiation sources. The sources of the oxidizing species include oxygen and/or hydrogen peroxide. The oxygen may be a component of the gaseous stream or added to the gaseous stream, preferably near a UV radiation source, and is converted to ozone by the UV irradiation. The hydrogen peroxide is decomposed through a combination of vaporization and UV irradiation. The hydrogen peroxide is preferably stored at stable concentration levels, i.e., approximately 50% by volume and increased in concentration in a continuous process preceding vaporization within the flow channel of the gaseous stream and in the presence of the UV radiation sources.

Parrish, Clyde, F.↗

Emission control system

Methods and apparatus utilizing hydrogen peroxide are useful to reduce NOx, SOx and mercury (or other heavy metal) emissions from combustion flue gas streams. Continuous concentration of hydrogen peroxide to levels approaching or exceeding propellant-grade hydrogen peroxide facilitates increased system efficiency. In this manner, combustion flue gas streams can be treated for the removal of NOx, SOx and heavy metals, while isolating useful by-products streams of sulfuric acid and nitric acid as well as solids for the recovery of the heavy metals.

Parrish, Clyde F.↗

Emission control system

Methods and apparatus utilizing hydrogen peroxide are useful to reduce SOx and mercury (or other heavy metal) emissions from combustion flue gas streams. The methods and apparatus may further be modified to reduce NOx emissions. Continuous concentration of hydrogen peroxide to levels approaching or exceeding propellant-grade hydrogen peroxide facilitates increased system efficiency. In this manner, combustion flue gas streams can be treated for the removal of SOx and heavy metals, while isolating useful by-products streams of sulfuric acid as well as solids for the recovery of the heavy metals. Where removal of NOx emissions is included, nitric acid may also be isolated for use in fertilizer or other industrial applications.

Parrish, Clyde F.↗

Probing Sensitivity of Discharge Characteristics to Model Selection using Uncertainty Quantification in an aprotic Li-Oxygen Battery

Currently, there are several models in the literature, such as kinetic models, microstructural models, and mass transport models that describe a Li-air battery's discharge behavior. Many of these models are calibrated and tested at low current densities and cannot be easily transferred to high current densities. Even at low current densities, there is no quantitative method for a researcher to choose a reaction kinetic model such as classical Butler-Volmer and its derivatives, and modified Marcus-Hush-Chidsey, a resistance model for lithium peroxide such as electron transport via tunneling or linear resistivity, a surface coverage model (lithium peroxide growth) such as partial coverage or full coverage, and mass transport model (discussed in Ref. [1]). Also, it is time-consuming to test different models at high current density (1C) due to a lack of well-tested models and well-calibrated model parameters. For this presentation, we will develop an analytical model, which acts as a surrogate model for a sophisticated finite element model to predict discharge time and discharge voltage. Next, we use an uncertainty quantifying technique called reduced-order stochastic optimization [2, 3] to determine the uncertainty in model parameters for rate kinetics, lithium peroxide resistivity, and parasitic resistance. Finally, a finite element simulation is performed to determine the error introduced by the surrogate model and its influence on the uncertainty in the model parameters.

M Mehta↗

Space flight and oxidative stress

Space flight is associated with an increase in oxidative stress after return to 1g. The effect is more pronounced after long-duration space flight. The effects lasts for several weeks after landing. In humans there is increased lipid peroxidation in erythrocyte membranes, reduction in some blood antioxidants, and increased urinary excretion of 8-iso-prostaglandin F(2alpha) and 8-oxo-7,8 dihydro-2 deoxyguanosine. Isoprostane 8-iso-prostaglandin F(2alpha) and 8-oxo-7,8 dihydro-2 deoxyguanosine are markers for oxidative damage to lipids and DNA, respectively. The changes have been attributed to a combination of the energy deficiency that occurs during flight and substrate competition for amino acids occurring between repleting muscle and other tissues during the recovery phase. The observations in humans have been complemented by rodent studies. Most rodent studies showed increased production of lipid peroxidation products postflight and decreased antioxidant enzyme activity postflight. The rodent observations were attributed to the stress associated with reentry into Earth's gravity. Decreasing the imbalance between the production of endogenous oxidant defenses and oxidant production by increasing the supply of dietary antioxidants may lessen the severity of the postflight increase in oxidative stress.

long duration↗

Reactions of Studtite UO 4 ·4H 2 O in Alkali Hydroxides: Isolation of Single-Crystal Uranate Phases under Mild Hydrothermal Conditions

Uranyl peroxide complexes, particularly studtite (UO 4 ·4H 2 O), are important phases within the nuclear fuel cycle, forming through radiolysis-induced reactions on the surfaces of spent fuel and in waste environments. Studtite has been identified in Hanford’s irradiated fuel storage basins, Chornobyl’s corium lavas, and is anticipated on Fukushima’s fuel debris. While its formation and stability have been extensively studied, the reactivity of UO 4 ·4H 2 O in highly alkaline environments such as those encountered in high-level nuclear waste remains underexplored. These environments contain molar concentrations of [OH - ] and present a chemically dynamic and reactive environment where actinide behavior is not well understood. Reported here are investigations of uranium reactions in concentrated alkali hydroxides under mild hydrothermal conditions (<200 °C) that have resulted in the isolation of the alkali metal uranates Li 2 UO 4 , α-Na 2 UO 4 , γ-Na 2 U 2 O 7 , and K 2 U 2 O 7 . In contrast to conventional solid-state methods (>800 °C) that typically yield polycrystalline powders, our approach enables the isolation of these uranates as single crystals, allowing us to provide single-crystal structure solutions of certain uranates for the first time. Our findings match the results of high-level waste tank sampling, confirming that sodium diuranate (Na 2 U 2 O 7 ) is the most persistent uranium phase, potentially forming through reactions of uranyl peroxide intermediates with NaOH under radiolytic and highly alkaline conditions.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗