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3,254 records · Page 87

The works of k. e. tsiolkovskiy on rocket technology

K. E. Tsiolkovskiy devoted a rather substantial portion of his works to the problem of flight by means of various reactive devices. We may state without exaggeration that Tsiolkovskiy considered his efforts in this direction to be of prime importance. Up to the time of his death Tsiolkovskiy continuously published articles; notes_ and calculations devoted to a comprehensive analysis of the possibilities and methods of interplanetary communications.

ROCKETRY

Pivotal role of organic adsorbates for the creation of catalytic sites during dry reforming of methane

Inadvertent factors can sometimes be crucial for synthesis of catalysts. The use of polyalcohols is common in the synthesis of heterogeneous catalysts. Interactions between alcohols and heterogeneous catalysts have been shown to induce surface reconstructions that greatly impact catalytic performance. Thus, traces of these alcohol functionalities on the as-synthesized catalysts, combined with heat treatment, could be critical in the generation of catalytic sites. Here, we show that during the synthesis of a Ni–Mo/MgO catalyst using a polyol process, residual ethylene glycol (EG) on the surface plays a significant role in the generation of catalytic sites for dry reforming of methane (DRM). The as-synthesized catalyst presents dispersed cationic Ni. Under DRM reaction conditions, the presence of EG, and H2 generated in situ, promote the generation of co-localized Ni–Mo nanoparticles (NPs). Greater amount of EG in the as-synthesized catalyst prevented sintering, leading to better catalyst stability and higher rates. If the residual EG remaining post-synthesis is removed through calcination, before conducting DRM, NiO NPs are formed and the material is completely inactive for catalyzing the reaction. When using a different support, denoted MgO*, EG also proved indispensable to generate active sites, although Ni–Mo co-localization was not evident, and a combination of DRM-related species was needed to activate the catalyst, not just H2. This work systematically uncovers how the interactions between organic adsorbates, the supported metals and the catalyst support dictate the creation of catalytic active sites.

Polo Garzon, Felipe [ORNL] (ORCID:0000000265076183

Mechanically Accelerated Depolymerization of Entangled Linear Polymer Melts

Mechanical forces can enhance the chemical depolymerization of synthetic polymers when shear flow accelerates chain scission. To quantify the extent of mechanically-accelerated scission, the effect of simple shear flow (duration and strength) with low Weissenberg and Deborah numbers was investigated by considering the impact of applied work in both simple shear and shear dominated mixed flows. Hydrogenated polyisoprene was chosen as a model linear, entangled system. The conditions (strain amplitude, frequency, and shearing time) necessary to increase chain scission were assessed in the rubbery melt. Shear flow accelerated chain scission at higher temperatures, suggesting an activated process. Isothermal scission versus work curves were superposed by applying shift factors a T,S , whose Arrhenius-like temperature dependence gave an apparent activation energy for chain scission of ~ 110 kJ/mol, which is likely a combination of the activation energy of viscosity and bond energy. This work provides a base for quantifying the impact of shear on depolymerization of polymer melts and highlight the connection between viscous dissipation and scission chemistry.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH

Time-Resolved Stochastic Dynamics of Quantum Thermal Machines

Steady-state quantum thermal machines are typically characterized by a continuous flow of heat between different reservoirs. However, at the level of discrete stochastic realizations, heat flow is unraveled as a series of abrupt quantum jumps, each representing an exchange of finite quanta with the environment. Here, in this work, we present a framework that resolves the dynamics of quantum thermal machines into cycles classified as enginelike, coolinglike, or idle. We analyze the statistics of individual cycle types and their durations, enabling us to determine both the fraction of cycles useful for thermodynamic tasks and the average waiting time between cycles of a given type. Central to our analysis is the notion of intermittency, which captures the operational consistency of the machine by assessing the frequency and distribution of idle cycles. Our framework offers a novel approach to characterizing thermal machines, with significant relevance to experiments involving mesoscopic transport through quantum dots.

full counting statistics

Experimental Investigations of Low-Energy (4 to 40 eV) Collisions of O - ( 2 P) Ions and O( 3 P) Atoms With Surfaces

Using a newly-developed, magnetically confined source, low-energy, ground state oxygen negative ions and neutral atoms are generated. The energy range is variable, and atom and neutrals have been generated at energies varying from 2 eV to 40 eV and higher. It was found that the interaction of these low-energy species with a solid magnesium fluoride target leads to optical emissions in the (at least) visible and infrared regions of the spectrum. Researchers describe y details of the photodetachment source, and present spectra of the neutral and ion glows in the wavelength range 250 to 850 nm (for O - ) and 600 to 850 nm (for O), and discuss the variability of the emissions for incident energies between 4 and 40 eV.

A Chutjian

Observational evidence for Criegee intermediate oligomerization reactions relevant to aerosol formation in the troposphere

Criegee intermediates are reactive intermediates that are implicated in transforming the composition of Earth’s troposphere and in the formation of secondary organic aerosol, impacting Earth’s radiation balance, air quality and human health. Yet, direct identification of their signatures in the field remains elusive. Here, from particulate and gas-phase mass-spectrometric measurements in the Amazon rainforest, we identify sequences of masses consistent with the expected signatures of oligomerization of the CH 2 OO Criegee intermediate, a process implicated in ozonolysis-driven aerosol formation. In this study, we assess the potential contributions of oligomerization through laboratory ozonolysis experiments, direct kinetic studies of Criegee intermediate reactions, and high-level theoretical calculations. Global atmospheric models built on these kinetics results indicate that Criegee intermediate chemistry may play a larger role in altering the composition of Earth’s troposphere than is captured in current atmospheric models, especially in areas of high humidity. However, the models still capture only a relatively small fraction of the observed signatures, suggesting considerable underestimates of Criegee intermediate concentrations and reactivity and/or the dominance of other, presently uncharacterized, oxidation mechanisms. Resolving the remaining uncertainties in emission inventories and the effects of atmospheric water vapour on key chemical reactions will be required to definitively assess the role of Criegee intermediate oligomerization reactions.

58 GEOSCIENCES

Mechanism of H 2 plasma-enabled reduction of hematite thin films

Hydrogen plasma is gaining significant interest as a promising pathway for direct iron ore reduction and for lowering process temperatures but the reduction mechanism remains poorly understood. In this work we analyzed the plasma and thermal reduction of thin-film hematite (Fe 2 O 3 ) at temperatures below 340 °C using X-ray diffraction and scanning electron microscopy with energy-dispersive X-ray spectroscopy. Plasma reduced the incubation period by an order of magnitude and increased the reduction rate by a factor of 2.6 compared to thermal reduction. Plasma-produced H-atoms facilitate the formation of numerous iron nucleation sites, bypassing the energetically unfavorable dissociative adsorption of H 2 on iron oxide. These iron nuclei can autocatalyze the reduction of the surrounding hematite via a hydrogen spillover mechanism. Our results demonstrate that plasma-derived H-atoms primarily impact the initial nucleation-limited stage. These new insights provide a mechanistic framework that can aid the implementation and optimization of hydrogen plasma-assisted iron oxide reduction at reduced temperatures.

08 HYDROGEN

Evaluation of Particle Degradation of a Ytterbium Disilicate Gas Turbine Coating in a Combustion Environment

Ytterbium disilicate (Yb2Si2O7) is a state-of-the-art topcoat material used in environmental barrier coatings (EBCs) to protect SiC-SiC composites from water vapor corrosion in gas turbine engines. However, it’s degradation by thermochemical and thermomechanical particle interactions may limit its use in next generation engine systems. Several static furnace tests have been performed on Yb2Si2O7 to elucidate methods of degradation, although dynamic testing in an engine-relevant environment has not been carried out. Ultimately, testing and evaluation of materials that incorporates all environmental damage modes will allow for an accurate assessment of long-term durability and operating lifetime. This work details the investigation of particle-induced erosion and corrosion of Yb2Si2O7 in NASA Glenn’s Erosion Burner Rig Facility. Coating durability was investigated as a function of test temperature, particle size, and deposition rate. Thermal cycling was also incorporated into testing to determine the interplay of heating/cooling cycles with particle degradation. Overall, these analyses will be used to determine coating robustness in an engine relevant environment.

Jamesa L Stokes

Evaluation of Particle Degradation of a Ytterbium Disilicate Gas Turbine Coating in a Combustion Environment

Ytterbium disilicate (Yb2Si2O7) is a state-of-the-art topcoat material used in environmental barrier coatings (EBCs) to protect SiC-SiC composites from water vapor corrosion in gas turbine engines. However, it’s degradation by thermochemical and thermomechanical particle interactions may limit its use in next generation engine systems. Several static furnace tests have been performed on Yb2Si2O7 to elucidate methods of degradation, although dynamic testing in an engine-relevant environment has not been carried out. Ultimately, testing and evaluation of materials that incorporates all environmental damage modes will allow for an accurate assessment of long-term durability and operating lifetime. This work details the investigation of particle-induced erosion and corrosion of Yb2Si2O7 in NASA Glenn’s Erosion Burner Rig Facility. Coating durability was investigated as a function of test temperature, particle size, and deposition rate. Thermal cycling was also incorporated into testing to determine the interplay of heating/cooling cycles with particle degradation. Overall, these analyses will be used to determine coating robustness in an engine relevant environment.

Jamesa L Stokes

Battery reconditioning, summary of TRW experience

The data collected from the results of battery reconditioning accumulated from three different spacecraft programs are summarized. The basic design characteristics of the programs are also presented.

Scott, W. R.