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At least 307 records · Page 17

Sulfur chemistry in dense interstellar clouds

A model is presented for the gas phase chemistry of molecules containing sulfur in dense interstellar clouds. The sulfur chemistry is different from that used in previous models as a result of an extensive search of the recent literature and the availability of new laboratory data. The changes have a significant effect on the calculated abundance of sulfur compounds. The linked chemistry of sulfur and oxygen in the present model requires a severe depletion of sulfur and low fractional abundances of both O and O2 in the dense clouds. In contrast, the high abundance of SO and the low abundance of CS relative to SO in the HVS in the KL may indicate an oxygen-rich, high temperature environment compared to OMC-1. The formation of S-H bonds is slow because of the absence of radiative association between S(+) and H2. The present model underestimates the abundance of H2S unless a radiative association reaction between HS(+) and H2 is postulated.

Prasad, S. S.↗

Structural verification of an aged composite reflector

A structural verification program applied to qualifying two heritage composite antenna reflectors for flight on the TOPEX satellite is outlined. The verification requirements and an integrated analyses/test approach employed to meet these requirements are described. Structural analysis results and qualification vibration test data are presented and discussed. It was determined that degradation of the composite and bonding materials caused by long-term exposure to an uncontrolled environment had not severely impaired the integrity of the reflector structures. The reflectors were assessed to be structurally adequate for the intended TOPEX application.

Lou, Michael C.↗

Advanced Environmental Barrier Coating and SA Tyrannohex SiC Composites Integration for Improved Thermomechanical and Environmental Durability

The development of 2700 degF capable environmental barrier coating (EBC) systems, particularly, the Rare Earth "Hafnium" Silicon bond coat systems, have significantly improved the temperature capability and environmental stability of SiC/SiC Ceramic Matrix Composite Systems. We have specifically developed the advanced 2700 degF EBC systems, integrating the EBC to the high temperature SA Tyrannohex SiC fiber composites, for comprehensive performance and durability evaluations for potential turbine engine airfoil component applications. The fundamental mechanical properties, environmental stability and thermal gradient cyclic durability performance of the EBC - SA Tyrannohex composites were investigated. The paper will particularly emphasize the high pressure combustion rig recession, cyclic thermal stress resistance and thermomechanical low cycle fatigue testing of uncoated and environmental barrier coated Tyrannohex SiC SA composites in these simulated turbine engine combustion water vapor, thermal gradients, and mechanical loading conditions. We have also investigated high heat flux and flexural fatigue degradation mechanisms, determined the upper limits of operating temperature conditions for the coated SA composite material systems in thermomechanical fatigue conditions. Recent progress has also been made by using the self-healing rare earth-silicon based EBCs, thus enhancing the SA composite hexagonal fiber columns bonding for improved thermomechanical and environmental durability in turbine engine operation environments. More advanced EBC- composite systems based on the new EBC-Fiber Interphases will also be discussed.

Tyrannohex SiC Ceramics↗

Effects of Basalt Composition on a Martian Analogue Magma-Sediment Hydrothermal System Studied Through Thermochemical Modeling

High-temperature hydrothermal systems have been identified on Mars associated with both hypervelocity impacts and magmatic activity on Mars’s early history [1, 2]. These processes may have produced habitable environments by providing heat, energy, and volatile species necessary to support microbial life [3, 4]. Hydrothermal systems formed after the intrusion of mafic magmas in sedimentary rocks are of particular interest when investigating the habitability of high-temperature aqueous environments on Mars [5, 6],because during magma-sediment contact metamorphism bond fluids (e.g. in ice, pore spaces, minerals) are mobilized favoring the alteration of the country rocks and the release of bio-essential elements [7, 8]. The chemistry and mineralogy of these systems on Mars are not well constrained and, for this reason, terrestrial analogues need to be investigated. Costello et al. [5] and Crandall et al. [6] have studied a mafic dike intruding the Jurassic Entrada sandstone (Colorado Plateau, UT). The intrusion has produced a hydrothermal system with Cl-CO2 rich fluids and near-neutral pH, which induced chemical and mineralogical changes in the dike and in the sediments [5, 6]. The system reached temperatures higher than 700 °C around the contact zone [6], but lower temperatures (< 200 °C) were reached as the system cooled down [5] making the environment potentially habitable [6]. However, previous studies do not consider compositional differences between the terrestrial dike and basaltic rocks on Mars [9, 10] making difficult a direct comparison between alteration mineralogy and brine chemistry of terrestrial and martian systems. Here, we use thermochemical modelling to investigate how differences in bulk dike composition will affect secondary mineral assemblages and fluid chemistry.

S Cogliati↗

A silicon micromachined piezoresistive accelerometer for health and condition monitoring

Silicon micromachining etching techniques were utilized to batch-fabricate hundreds of general purpose microaccelerometers on a single silicon substrate. Piezoresistive sensing elements were aligned to the back-side patterns using an IR mask aligner and then diffused into the areas of maximum stress. Capping of the two-arm cantilever beam structure was achieved using a combination of electrostatic bonding and low temperature glass films. Overrange protection, critical damping, and overall protection from the outside environment are achieved by controlling the cavity depths of the top and bottom covers. Temperature compensation, amplification, and filtering are performed by a companion LSI chip that is interfaced to the accelerometer by conventional wire-bonding techniques.

Walsh, Kevin M.↗

Polarized metal–metal multiple bonding and reactivity of phosphinoamide-bridged heterobimetallic group IV/cobalt compounds

Heterobimetallic complexes are studied for their ability to mimic biological systems as well as active sites in heterogeneous catalysts. While specific interest in early/late heterobimetallic systems has fluctuated, they serve as important models to fundamentally understand metal–metal bonding. Specifically, the polarized metal–metal multiple bonds formed in highly reduced early/late heterobimetallic complexes exemplify how each metal modulates the electronic environment and reactivity of the complex as a whole. In this Perspective, we chronicle the development of phosphinoamide-supported group IV/cobalt heterobimetallic complexes. This combination of metals allows access to a low valent Co −I center, which performs a rich variety of bond activation reactions when coupled with the pendent Lewis acidic metal center. Conversely, the low valent late transition metal is also observed to act as an electron reservoir, allowing for redox processes to occur at the d 0 group IV metal site. Most of the bond activation reactions carried out by phosphinoamide-bridged M/Co −I (M = Ti, Zr, Hf) complexes are facilitated by cleavage of metal–metal multiple bonds, which serve as readily accessible electron reservoirs. Comparative studies in which both the number of buttressing ligands as well as the identity of the early metal were varied to give a library of heterobimetallic complexes are summarized, providing a thorough understanding of the reactivity of M/Co −I heterobimetallic systems

Hunter, Nathanael H.↗

Iron impurities in Si3N4 processing

The atomic environment of iron impurities is investigated during the processing cycle of reaction-bonding silicon nitride (RBSN). Several analysis techniques are utilized, including X-ray photoelectron spectroscopy (XPS), extended X-ray absorption fine structure (EXAFS), and electron spin resonance (ESR), to examine iron impurities in the starting silicon powder, in sintered silicon compacts, and in RBSN materials. Results indicate that iron impurities in as-received metallurgical grade silicon powder are incorporated in the silicon bulk as a highly distorted FeSi2 compound. No surface iron or iron-based particulate is observed in the starting material. Upon sintering, the iron environment becomes an ordered FeSi2 structure. In the RBNS material, the FeSi2 structure is again distorted, as observed by both EXAFS and ESR.

Bouldin, C. E.↗

NR-150 adhesive development

A polyimide precursor adhesive solution, code-named NR-056X, was developed. It reproducibly gives low void, high strength bond lines at both room temperature and 589K (600 F) using either titanium or graphite/polyimide composite adherends having 12.7 mm (1/2 in.) overlaps. Lap shear samples prepared using this adhesive and composite adherends based on graphite/NR-150B2 were shown to have a high degree of resistance to such adverse environments as air at 589K (600 F), high humidity, methyl ethyl ketone and jet fuel. Bond line toughness was illustrated by the complete resistance to cracking in the wedge-crack propagation test. The available evidence indicates that wide area composite to composite or composite to metal bonding should be feasible.

Blatz, P. S.↗

The SrrAB two-component system regulates Staphylococcus aureus pathogenicity through redox sensitive cysteines

Staphylococcus aureus infections can lead to diseases that range from localized skin abscess to life-threatening toxic shock syndrome. The SrrAB two-component system (TCS) is a global regulator of S. aureus virulence and critical for survival under environmental conditions such as hypoxic, oxidative, and nitrosative stress found at sites of infection. Despite the critical role of SrrAB in S. aureus pathogenicity, the mechanism by which the SrrAB TCS senses and responds to these environmental signals remains unknown. Bioinformatics analysis showed that the SrrB histidine kinase contains several domains, including an extracellular Cache domain and a cytoplasmic HAMP-PAS-DHp-CA region. In this work, we show that the PAS domain regulates both kinase and phosphatase enzyme activity of SrrB and present the structure of the DHp-CA catalytic core. Importantly, this structure shows a unique intramolecular cysteine disulfide bond in the ATP-binding domain that significantly affects autophosphorylation kinetics. In vitro data show that the redox state of the disulfide bond affects S. aureus biofilm formation and toxic shock syndrome toxin-1 production. Moreover, with the use of the rabbit infective endocarditis model, we demonstrate that the disulfide bond is a critical regulatory element of SrrB function during S. aureus infection. Our data support a model whereby the disulfide bond and PAS domain of SrrB sense and respond to the cellular redox environment to regulate S. aureus survival and pathogenesis.

59 BASIC BIOLOGICAL SCIENCES↗

Extreme Thermal Stabilization of Carborane–Cyanate Composites via B–N Dative-Bonded Boroxine Barriers

Enhancing the thermal stability of cyanate ester (CE) resins is crucial for high-temperature aerospace applications. This study elucidates the degradation mechanisms of CE composites reinforced with carborane additives, focusing on the formation of boron–nitrogen (B–N) dative bonds and their role in improving thermal resistance. Using thermogravimetric analysis, we examined char formation and evolved gases at multiple degradation stages. Reaction sequences and char products were characterized via Fourier transform infrared spectroscopy (FTIR), solid-state 13C and 11B NMR, and evolved gas analysis using mass spectrometry and FTIR. The solid-state 11B NMR was instrumental in detecting various boron oxidation states and the formation of B–N dative bonds during decomposition. These bonds facilitate cross-linking in the char phase, enhancing material integrity at elevated temperatures. However, in inert environments, the volatility of boron additives like carborane limits their effectiveness. These findings advance the understanding of CE composite degradation mechanisms and offer critical insights for developing high-temperature-resistant materials for aerospace applications.

Fourier transform infrared spectroscopy↗

Residual Stresses in Thermal Barrier Coatings for a Cu-8Cr-4Nb Substrate System

Analytical calculations were conducted to determine the thermal stresses developed in a coated copper-based alloy, Cu-8%(at.%)Cr-4%Nb (designated as GRCop-84), after plasma spraying and during heat-up in a simulated rocket engine environment. Finite element analyses were conducted for two coating systems consisting of a metallic top coat, a pure copper bond coat and the GRCop-84. The through thickness temperature variations were determined as a function of coating thickness for two metallic coatings, a Ni-17%(wt%)Cr-6%Al-0.5%Y alloy and a Ni-50%(at.%)Al alloy. The residual stresses after low-pressure plasma spraying of the NiCrAlY and NiAl coatings on GRCop-84 substrate were also evaluated. These analyses took into consideration a 50.8 mm copper bond coat and the effects of an interface coating roughness. The through the thickness thermal stresses developed in coated liners were also calculated after 15 minutes of exposure in a rocket environment with and without an interfacial roughness.

Ghosn, Louis J.↗

Defect Termination in the UiO-66 Family of Metal–Organic Frameworks: The Role of Water and Modulator

The defect concentration in the prototypical metal–organic framework UiO-66 can be well controlled during synthesis, leading to precisely tunable physicochemical properties for this structure. However, there has been a long-standing debate regarding the nature of the compensating species present at the defective sites. Here, we present unambiguous spectroscopic evidence that the missing-linker defect sites in an ambient environment are compensated with both carboxylate and water (bound through intermolecular hydrogen bonding), which is further supported by ab initio calculations. In contrast to the prevailing assumption that the monocarboxylate groups (COO – ) of the modulators form bidentate bonding with two Zr 4+ sites, COO – is found to coordinate to an open Zr 4+ site in an unidentate mode. The neighboring Zr 4+ site is terminated by a coordinating H 2 O molecule, which helps to stabilize the COO – group. Lastly, this finding not only provides a new understanding of defect termination in UiO-66, but also sheds light on the origin of its catalytic activity.

36 MATERIALS SCIENCE↗

The effect of water on colloidal quantum dot solar cells

Almost all surfaces sensitive to the ambient environment are covered by water, whereas the impacts of water on surface-dominated colloidal quantum dot (CQD) semiconductor electronics have rarely been explored. Here, strongly hydrogen-bonded water on hydroxylated lead sulfide (PbS) CQD is identified. The water could pilot the thermally induced evolution of surface chemical environment, which significantly influences the nanostructures, carrier dynamics, and trap behaviors in CQD solar cells. The aggravation of surface hydroxylation and water adsorption triggers epitaxial CQD fusion during device fabrication under humid ambient, giving rise to the inter-band traps and deficiency in solar cells. To address this problem, meniscus-guided-coating technique is introduced to achieve dense-packed CQD solids and extrude ambient water, improving device performance and thermal stability. Our works not only elucidate the water involved PbS CQD surface chemistry, but may also achieve a comprehensive understanding of the impact of ambient water on CQD based electronics.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Corrosion resistant thermal barrier coating

A thermal barrier coating system for protecting metal surfaces at high temperature in normally corrosive environments is described. The thermal barrier coating system includes a metal alloy bond coating, the alloy containing nickel, cobalt, iron, or a combination of these metals. The system further includes a corrosion resistant thermal barrier oxide coating containing at least one alkaline earth silicate. The preferred oxides are calcium silicate, barium silicate, magnesium silicate, or combinations of these silicates.

Levine, S. R.↗

Marking Electrical Wiring With Condition Indicators

A method is provided for marking electrical Wiring with condition indicators. One or more markers are added to one or both of the insulative material and a surface of an electrical conductor such that it bonds thereto. Each marker is capable of emanating into a surrounding atmospheric environment as a gaseous effluent in response to a specific condition experienced by the electrical conductor.

Yost, William T.↗

Environmental Barrier Coating Development for SiC/SiC Ceramic Matrix Composites: Recent Advances and Future Directions

This presentation briefly reviews the SiC/SiC major environmental and environment-fatigue degradations encountered in simulated turbine combustion environments, and thus NASA environmental barrier coating system evolution for protecting the SiC/SiC Ceramic Matrix Composites for meeting the engine performance requirements. The presentation will review several generations of NASA EBC materials systems, EBC-CMC component system technologies for SiC/SiC ceramic matrix composite combustors and turbine airfoils, highlighting the temperature capability and durability improvements in simulated engine high heat flux, high pressure, high velocity, and with mechanical creep and fatigue loading conditions. This paper will also focus on the performance requirements and design considerations of environmental barrier coatings for next generation turbine engine applications. The current development emphasis is placed on advanced NASA candidate environmental barrier coating systems for SiC/SiC CMCs, their performance benefits and design limitations in long-term operation and combustion environments. The efforts have been also directed to developing prime-reliant, self-healing 2700F EBC bond coat; and high stability, lower thermal conductivity, and durable EBC top coats. Major technical barriers in developing environmental barrier coating systems, the coating integrations with next generation CMCs having the improved environmental stability, erosion-impact resistance, and long-term fatigue-environment system durability performance will be described. The research and development opportunities for turbine engine environmental barrier coating systems by utilizing improved compositions, state-of-the-art processing methods, and simulated environment testing and durability modeling will be briefly discussed.

Environmental Barrier Coatings↗

Acousto-optic signature analysis for inspection of the orbiter thermal protection tile bonds

The goal of this research is to develop a viable NDE technique for the inspection of orbiter thermal protection system (TPS) tile bonds. Phase 2, discussed here, concentrated on developing an empirical understanding of the bonded and unbonded vibration signatures of acreage tiles. Controlled experiments in the laboratory have provided useful information on the dynamic response of TPS tiles. It has been shown that several signatures are common to all the pedigree tiles. This degree of consistency in the tile-SIP (strain isolation pad) dynamic response proves that an unbond can be detected for a known tile and establish the basis for extending the analysis capability to arbitrary tiles for which there are no historical data. The field tests of the noncontacting laser acoustic sensor system, conducted at the Kennedy Space Center (KSC), investigated the vibrational environment of the Orbiter Processing Facility (OPF) and its effect on the measurement and analysis techniques being developed. The data collected showed that for orbiter locations, such as the body flap and elevon, the data analysis scheme, and/or the sensor, will require modification to accommodate the ambient motion. Several methods were identified for accomplishing this, and a solution is seen as readily achievable. It was established that the tile response was similar to that observed in the laboratory. Of most importance, however, is that the field environment will not affect the physics of the dynamic response that is related to bond condition. All of this information is fundamental to any future design and development of a prototype system.

Rodriguez, Julio G.↗