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At least 325 records · Page 18

Surface Gibbs free energy analyses of Sr segregation in lanthanum strontium iron oxide

Sr surface segregation in mixed-cation oxides often causes degradation of chemical or electrochemical performance. In this work, the thermodynamic driving force for Sr segregation is investigated to explain the Sr segregation behavior in La0.5Sr0.5FeO3 (LSF). Specifically, Density Functional Theory is used to calculate the surface Gibbs free energy of various surface terminations of cubic (100) LSF as a function of chemical potential and temperature. Here, SrO-terminated surfaces are predicted to be dominant, promoting Sr segregation at high temperatures and low oxygen partial pressure.

08 HYDROGEN↗

Hole Hopping through Cytochrome P450

High-potential iron–oxo species are intermediates in the catalytic cycles of oxygenase enzymes. They can cause heme degradation and irreversible oxidation of nearby amino acids. We have proposed that there are protective mechanisms in which hole hopping from oxidized hemes through tryptophan/tyrosine chains generates a surface-exposed amino-acid oxidant that could be rapidly disarmed by reaction with cellular reductants. In investigations of cytochrome P450 BM 3 , we identified Trp96 as a critical residue that could play such a protective role. This Trp is cation-π paired with Arg398 in 81% of mammalian P450s. Here we report on the effect of the Trp/Arg cation-π interaction on Trp96 formal potentials as well as on electronic coupling strengths between Trp96 and the heme both for wild type cytochrome P450 and selected mutants. Mutation of Arg398 to His, which decreases the Trp96 formal potential, increases Trp-heme electronic coupling; however, surprisingly, the rate of phototriggered electron transfer from a Ru-sensitizer (through Trp96) to the P450 BM 3 heme was unaffected by the Arg398His mutation. We conclude that Trp96 has moved away from Arg398, suggesting that the protective mechanism for P450s with this Trp-Arg pair is conformationally gated.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Poly(lactic acid)-Based Ink for Biodegradable Printed Electronics With Conductivity Enhanced through Solvent Aging

Biodegradable electronics is a rapidly growing field, and the development of controllably biodegradable, high-conductivity materials suitable for additive manufacturing under ambient conditions remains a challenge. Here, printable conductive pastes that employ poly(lactic acid) (PLA) as a binder and tungsten as a conductor are demonstrated. These composite conductors can provide enhanced stability in applications where moisture may be present, such as environmental monitoring or agriculture. Post-processing the printed traces using a solvent-aging technique increases their conductivity by up to 2 orders of magnitude, with final conductivities approaching 5000 S/m. Such techniques could prove useful when thermal processes including heating or laser sintering are limited by the temperature constraints of typical biodegradable substrates. Finally, both accelerated oxidative and hydrolytic degradation of the printed composite conductors are examined, and a fully biodegradable capacitive soil moisture sensor is fabricated and tested.

36 MATERIALS SCIENCE↗

CuCr 2 O 4 particle growth and evolution across sol–gel routes and calcination profiles

CuCr 2 O 4 spinel is a candidate coating material for central receivers in concentrating solar power to protect structural alloys against high temperature oxidation and related degradation. Coating performance and microstructure of dip-coated and sintered coatings is dictated by the initial particle size of the CuCr 2 O 4 and sintering temperature, but can be compromised by particle agglomeration. Here in this study, sub-micron particles were synthesised through the Pechini and modified Pechini sol–gel methods. Phase composition was confirmed via X-ray diffraction. Particle growth during calcination of the nanoparticles at different temperatures (650°C, 750°C, 850°C) and times (between 1 and 24 h) was measured via laser diffraction and scanning electron microscopy. The modified Pechini method displayed evidence of smaller particle sizes and greater agglomeration. The kinetics of particle growth observed are consistent with a diffusion limited inhibited grain growth model.

36 MATERIALS SCIENCE↗

Distinct microbiomes underlie divergent responses of methane emissions from diverse wetland soils to oxygen shifts

Abstract Hydrological shifts in wetlands, a globally important methane (CH4) source, are critical constraints on CH4 emissions and carbon-climate feedbacks. A limited understanding of how hydrologically driven oxygen (O2) variability affects microbial CH4 cycling in diverse wetlands makes wetland CH4 emissions uncertain. Transient O2 exposure significantly stimulated anoxic CH4 production in incubations of Sphagnum peat from a temperate bog by enriching for polyphenol oxidizers and polysaccharide degraders, enhancing substrate flow toward methanogenesis under subsequent anoxic conditions. To assess whether shifts in soil microbiome structure and function operate similarly across wetland types, here we examined the sensitivity of different wetland soils to transient oxygenation. In slurry incubations of Sphagnum peat from a minerotrophic fen, and sediments from a freshwater marsh and saltmarsh, we examined temporal shifts in microbiomes coupled with geochemical characterization of slurries and incubation headspaces. Oxygenation did not affect microbiome structure and anoxic CH4 production in mineral-rich fen-origin peat and freshwater marsh soils. Key taxa linked to O2-stimulated CH4 production in the bog-origin peat were notably rare in the fen-origin peat, supporting microbiome structure as a primary determinant of wetland response to O2 shifts. In contrast to freshwater wetland experiments, saltmarsh geochemistry—particularly pH—and microbiome structure were persistently and significantly altered postoxygenation, albeit with no significant impact on greenhouse gas emissions. These divergent responses suggest wetlands may be differentially resistant to O2 fluctuations. With climate change driving greater O2 variability in wetlands, our results inform mechanisms of wetland resistance and highlight microbiome structure as a potential resiliency biomarker.

Reji, Linta (ORCID:0000000213376782)↗

X-ray fluorescence mapping of brain tissue reveals the profound extent of trace element dysregulation in stroke pathophysiology

Abstract The brain is a privileged organ with regard to its trace element composition and maintains a robust barrier system to sequester this specialized environment from the rest of the body and the vascular system. Stroke is caused by loss of adequate blood flow to a region of the brain. Without adequate blood flow ischaemic changes begin almost immediately, triggering an ischaemic cascade, characterized by ion dysregulation, loss of function, oxidative damage, cellular degradation, and breakdown of the barrier that helps maintain this environment. Ion dysregulation is a hallmark of stroke pathophysiology and we observe that most elements in the brain are dysregulated after stroke. X-ray fluorescence-based detection of physiological changes in the neurometallome after stroke reveals profound ion dysregulation within the lesion and surrounding tissue. Not only are most elements significantly dysregulated after stroke, but the level of dysregulation cannot be predicted from a cell-level description of dysregulation. X-ray fluorescence imaging reveals that the stroke lesion retains <25% of essential K+ after stroke, but this element is not concomitantly elevated elsewhere in the organ. Moreover, elements like Na+, Ca2+, and Cl− are vastly elevated above levels available in normal brain tissue (>400%, >200%, and >150%, respectively). We hypothesize that weakening of the blood–brain barrier after stroke allows elements to freely diffuse down their concentration gradient so that the stroke lesion is in equilibrium with blood (and the compartments containing brain interstitial fluid and cerebrospinal fluid). The change observed for the neurometallome likely has consequences for the potential to rescue infarcted tissue, but also presents specific targets for treatment.

Biochemistry & Molecular Biology↗

Changes in active-site geometry on X-ray photoreduction of a lytic polysaccharide monooxygenase active-site copper and saccharide binding

The recently discovered lytic polysaccharide monooxygenases (LPMOs) are Cu-containing enzymes capable of degrading polysaccharide substrates oxidatively. The generally accepted first step in the LPMO reaction is the reduction of the active-site metal ion from Cu 2+ to Cu + . Here we have used a systematic diffraction data collection method to monitor structural changes in two AA9 LPMOs, one from Lentinus similis (LsAA9_A) and one from Thermoascus auranti­acus (TaAA9_A), as the active-site Cu is photoreduced in the X-ray beam. For LsAA9_A, the protein produced in two different recombinant systems was crystallized to probe the effect of post-translational modifications and different crystallization conditions on the active site and metal photoreduction. We can recommend that crystallographic studies of AA9 LPMOs wishing to address the Cu 2+ form use a total X-ray dose below 3 × 10 4 Gy, while the Cu + form can be attained using 1 × 10 6 Gy. In all cases, we observe the transition from a hexa­coordinated Cu site with two solvent-facing ligands to a T-shaped geometry with no exogenous ligands, and a clear increase of the θ 2 parameter and a decrease of the θ 3 parameter by averages of 9.2° and 8.4°, respectively, but also a slight increase in θ T . Thus, the θ 2 and θ 3 parameters are helpful diagnostics for the oxidation state of the metal in a His-brace protein. On binding of cello-oligosaccharides to LsAA9_A, regardless of the production source, the θ T parameter increases, making the Cu site less planar, while the active-site Tyr—Cu distance decreases reproducibly for the Cu 2+ form. Thus, the θ T increase found on copper reduction may bring LsAA9_A closer to an oligosaccharide-bound state and contribute to the observed higher affinity of reduced LsAA9_A for cellulosic substrates.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Characterization of dissipative regions of a N-doped superconducting radio-frequency cavity

We report radio-frequency measurements of quality factors and temperature mapping of a nitrogen doped Nb superconducting RF cavity. Cavity cutouts of hot and cold spots were studied with low temperature scanning tunneling microscopy and spectroscopy, X-ray photoelectron spectroscopy and secondary electron microscopy. Temperature mapping revealed a substantial reduction of the residual resistance upon cooling the cavity with a greater temperature gradient and hysteretic losses at the quench location, pointing to trapped vortices as the dominant source of residual surface resistance. Analysis of the tunneling spectra in the framework of a proximity effect theory shows that hot spots have a reduced pair potential and a wider distribution of the contact resistance between the Nb and the top Nb oxide. Alone, these degraded superconducting properties account for a much weaker excess dissipation as compared with the vortex contribution. Based on the correlation between the quasiparticle density of states and temperature mapping, we suggest that degraded superconducting properties may facilitate vortex nucleation or settling of trapped flux during cooling the cavity through the critical temperature.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗

The effect of Tricresyl-Phosphate (TCP) as an additive on wear of Iron (Fe)

The effect of tricresyl phosphate (TCP) as an antiwear additive in lubricant trimethyol propane triheptanoate (TMPTH) was investigated. The objective was to examine step loading wear by use of surface analysis, wetting, and chemical bonding changes in the lubricant. The investigation consisted of steploading wear studies by a pin or disk tribometer, the effects on wear related to wetting by contact angle and surface tension measurements of various liquid systems, the chemical bonding changes between lubricant and TCP chromatographic analysis, and by determining the reaction between the TCP and metal surfaces through wear scar analysis by Auger emission spectroscopy (AES). The steploading curve for the base fluid alone shows rapid increase of wear rate with load. The steploading curve for the base fluid in presence of 4.25 percent by volume TCP under dry air purge has shown a great reduction of wear rate with all loads studied. It has also been found that the addition of 4.25 percent by volume TCP plus 0.33 percent by volume water to the base lubricant under N2 purge also greatly reduces the wear rate with all loads studied. AES surface analysis reveals a phosphate type wear resistant film, which greatly increases load-bearing capacity, formed on the iron disk. Preliminary chromatographic studies suggest that this film forms either because of ester oxidation or TCP degradation. Wetting studies show direct correlation between the spreading coefficient and the wear rate.

Ghose, Hiren M.↗

Exposure time considerations in high temperature low cycle fatigue

The Conventional Strainrange Partitioning (CSRP) method for High-Temperature, Low-Cycle Fatigue (HTLCF) life prediction has its origins in the modeling of first-order, creep-fatigue waveform effects while treating as second-order effects, the influence of metallurgical or environmental time dependencies. Procedures are proposed to include the latter explicitly in the inelastic strainrange--life relations. For brevity, only the CP life relation will be presented in detail. The exposure-time effect within the CP inelastic strainrange (tensile creep reversed by compressive plasticity) was determined by tensile stresshold-time experiments for 316 SS at 816 C. Reductions in CP cyclic life of a factor of about two were observed with an increase in exposure time or a corresponding decrease in creep rate by a factor of about 100. The CP life relation has been modified to be expressed in terms of either Steady State Creep Rate (SSCR) or Exposure Time (ET). The applicability and accuracy of the time-dependent CP life relations is demonstrated by conducting verification experiments involving complex hysteresis loops. Metallographic examination revealed time-dependent degradation attributable to oxide formation and precipitation of carbides along grain boundaries.

Kalluri, S.↗

Exposure time considerations in high temperature low cycle fatigue

The Conventional Strainrange Partitioning (CSRP) method for High-Temperature, Low-Cycle Fatigue (HTLCF) life prediction has its origins in the modeling of first-order, creep-fatigue waveform effects while treating as second-order effects, the influence of metallurgical or environmental time dependencies. Procedures are proposed to include the latter explicitly in the inelastic strainrange-life relations. For brevity, only the CP life relation will be presented in detail. The exposure-time effect within the CP inelastic strainrange (tensile creep reversed by compressive plasticity) was determined by tensile stresshold-time experiments for 316 SS at 816 C. Reductions in CP cyclic life of a factor of about two were observed with an increase in exposure time or a corresponding decrease in creep rate by a factor of about 100. The CP life relation has been modified to be expressed in terms of either Steady State Creep Rate (SSCR) or Exposure Time (ET). The applicability and accuracy of the time-dependent CP life relations is demonstrated by conducting verification experiments involving complex hysteresis loops. Metallographic examination revealed time-dependent degradation attributable to oxide formation and precipitation of carbides along grain boundaries.

Kalluri, S.↗

Mach 5 electroformed nickel nozzle refurbishment FNAS investigation of ultra-smooth surfaces

This task is in support of the Quiet Hypersonic Wind Tunnel effort currently in effect at NASA Langley Research Center, VA. A laminar flow wind tunnel nozzle has been previously fabricated by electroforming pure nickel over a machined and polished two piece stainless steel mandrel. The mandrel was removed leaving the replicate nozzle surface. The nozzle was then pressed into a heavy stainless steel jacket for mounting features and rigidity. The original nickel surface was a replication of the polished mandrel but had degraded due to oxidation. The inside surface requirements are very stringent in order to achieve laminar or quiet flow at the desired pressure and temperature for the specific design of Mach 5. The throat area of the axisymmetric device must have a surface finish with no defects greater than 16 microinches. This requires an rms average background of about four microinches or better for inspection purposes. A coating of nickel-phosphorous alloy was applied by catalytic deposition and then the inside of the nozzle was polished retaining dimensional and surface finish tolerances as specified per drawings supplied. Since the unit is not an optical component, conventional optical inspection methods for surface finish and figure are not readily achieved. Measurements were made using surface profilometry.

Rood, Robert↗

Attenuation of Scattered Thermal Energy Atomic Oxygen

The attenuation of scattered thermal energy atomic oxygen is relevant to the potential damage that can occur within a spacecraft which sweeps through atomic oxygen in low Earth orbit (LEO). Although there can be significant oxidation and resulting degradation of polymers and some metals on the external surfaces of spacecraft, there are often openings on a spacecraft such as telescope apertures, vents, and microwave cavities that can allow atomic oxygen to enter and scatter internally to the spacecraft. Atomic oxygen that enters a spacecraft can thermally accommodate and scatter to ultimately react or recombine on surfaces. The atomic oxygen that does enter a spacecraft can be scavenged by use of high erosion yield polymers to reduce its reaction on critical surfaces and materials. Polyoxymethylene and polyethylene can be used as effective atomic oxygen scavenging polymers.

Banks, Bruce a.↗

Attenuation of Scattered Thermal Energy Atomic Oxygen

The attenuation of scattered thermal energy atomic oxygen is relevant to the potential damage that can occur within a spacecraft which sweeps through atomic oxygen in low Earth orbit (LEO). Although there can be significant oxidation and resulting degradation of polymers and some metals on the external surfaces of spacecraft, there are often openings on a spacecraft such as telescope apertures, vents, and microwave cavities that can allow atomic oxygen to enter and scatter internally to the spacecraft. Atomic oxygen that enters a spacecraft can thermally accommodate and scatter to ultimately react or recombine on surfaces. The atomic oxygen that does enter a spacecraft can be scavenged by use of high erosion yield polymers to reduce its reaction on critical surfaces and materials. Polyoxymethylene and polyethylene can be used as effective atomic oxygen scavenging polymers.

Banks, Bruce A.↗

Sustainably Sourced, Thermally Resistant, Radiation Hard Biopolymer

This material represents a breakthrough in the production, manufacturing, and application of thermal protection system (TPS) materials and radiation shielding, as this represents the first effort to develop a non-metallic, non-ceramic, biomaterial-based, sustainable TPS with the capability to also act as radiation shielding. Until now, the standing philosophy for radiation shielding involved carrying the shielding at liftoff or utilizing onboard water sources. This shielding material could be grown onboard and applied as needed prior to different radiation landscapes (commonly seen during missions involving gravitational assists). The material is a bioplastic material. Bioplastics are any combination of a biopolymer and a plasticizer. In this case, the biopolymer is a starch-based material and a commonly accessible plasticizer. Starch molecules are composed of two major polymers: amylase and amylopectin. The biopolymer phenolic compounds are common to the ablative thermal protection system family of materials. With similar constituents come similar chemical ablation processes, with the potential to have comparable, if not better, ablation characteristics. It can also be used as a flame-resistant barrier for commercial applications in buildings, homes, cars, and heater firewall material. The biopolymer is observed to undergo chemical transformations (oxidative and structural degradation) at radiation doses that are 1,000 times the maximum dose of an unmanned mission (10-25 Mrad), indicating that it would be a viable candidate for robust radiation shielding. As a comparison, the total integrated radiation dose for a three-year manned mission to Mars is 0.1 krad, far below the radiation limit at which starch molecules degrade. For electron radiation, the biopolymer starches show minimal deterioration when exposed to energies greater than 180 keV. This flame-resistant, thermal-insulating material is non-hazardous and may be sustainably sourced. It poses no hazardous waste threats during its lifecycle. The material composition is radiation-tolerant up to megarad doses, indicating its use as a radiation shielding material. It is lightweight, non-metallic, and able to be mechanically densified, permitting a tunable gradient of thermal and radiation protection as needed. The dual-use (thermal and radiation shielding), sustainable nature of this material makes it suitable for both industrial applications as a sustainable/green building material, and for space applications as thermal protection material and radiation shield.

Pugel, Diane↗

Damage Characterization of EBC-SiCSiC Ceramic Matrix Composites Under Imposed Thermal Gradient Testing

Due to their high temperature capabilities, Ceramic Matrix Composite (CMC) components are being developed for use in hot-section aerospace engine applications. Harsh engine environments have led to the development of Environmental Barrier Coatings (EBCs) for silicon-based CMCs to further increase thermal and environmental capabilities. This study aims at understanding the damage mechanisms associated with these materials under simulated operating conditions. A high heat-flux laser testing rig capable of imposing large through-thickness thermal gradients by means of controlled laser beam heating and back-side air cooling is used. Tests are performed on uncoated composites, as well as CMC substrates that have been coated with state-of-the-art ceramic EBC systems. Results show that the use of the EBCs may help increase temperature capability and creep resistance by reducing the effects of stressed oxidation and environmental degradation. Also, the ability of electrical resistance (ER) and acoustic emission (AE) measurements to monitor material condition and damage state during high temperature testing is shown; suggesting their usefulness as a valuable health monitoring technique. Micromechanics models are used to describe the localized stress state of the composite system, which is utilized along with ER modeling concepts to develop an electromechanical model capable of characterizing material behavior.

protective coatings (nonmetallic)↗