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At least 793 records · Page 44

Redox Mediated Control of Electrochemical Potential in Liquid Cell Electron Microscopy

Liquid cell electron microscopy enables the study of nanoscale transformations in solvents with high spatial and temporal resolution, but for the technique to achieve its potential requires a new level of control over the reactivity caused by radical generation under electron beam irradiation. An understanding of how to control electron-solvent interactions is needed to further advance the study of structural dynamics for complex materials at the nanoscale. Additionally, we developed an approach that scavenges radicals with redox species that form well-defined redox couples and control the electrochemical potential in situ . This approach enables the observation of electrochemical structural dynamics at near-atomic resolution with precise control of the liquid environment. Analysis of nanocrystal etching trajectories indicates that this approach can be generalized to several chemical systems. The ability to simultaneously observe heterogeneous reactions at near-atomic resolution and precisely control the electrochemical potential enables the fundamental study of complex nanoscale dynamics with unprecedented detail.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Control of a Thrust Alignment Table for Modeling the Coning Dynamics of a Spinning Spacecraft with a Follower Force

This document presents a system controlling the motion of a spherical air bearing used in the modeling of spacecraft dynamics and controls in a laboratory environment. The system is part of the Spinning Rocket Simulator (SRS), used to simulate the coning of spacecraft during a thrusting stage. The reaction force at the spherical air bearing supporting the spacecraft model must coincide with the thrust axis of the model for proper simulation. Therefore, the bearing is translated in a circular path to introduce a centrifugal force. This horizontal force along with the gravitational reaction force at the bearing combines to simulate the direction of the spacecraft's thrust force. The control system receives attitude information from the spacecraft model via a laser beam embedded in the model that impinges on a photosensitive array. The non-linear system is controlled using high-speed lookup tables and digital techniques. A vector-controlled motor and a stepper motor are given the necessary signals to accurately control the turntable and platform supporting the air bearing. Preliminary performance data is presented. Mechanical elements of the table and platform are described in detail. A wireless (RF) data path for all devices on the spacecraft model to an off-table command computer is also described.

Halsmer, Dominic↗

Mechanisms of deterioration of intermediate moisture food systems

A study of shelf stability in intermediate moisture foods was made. Major efforts were made to control lipid oxidation and nonenzymatic browning. In order to determine means of preventing these reactions, model systems were developed having the same water activity content relationship of intermediate moisture foods. Models were based on a cellulose-lipid and protein-lipid system with glycerol added as the humectant. Experiments with both systems indicate that lipid oxidation is promoted significantly in the intermediate moisture range. The effect appeared to be related to increased mobility of either reactants or catalysts, since when the amount of water in the system reached a level where capillary condensation occurred and thus free water was present, the rates of oxidation increased. With added glycerol, which is water soluble and thus increases the amount of mobile phase, the increase in oxidation rate occurs at a lower relative humidity. The rates of oxidation were maximized at 61% RH and decreased again at 75% RH probably due to dilution. No significant non-enzymatic browning occurred in the protein-lipid systems. Prevention of oxidation by the use of metal chelating agents was enhanced in the cellulose system, whereas, with protein present, the lipid soluble chain terminating antioxidants (such as BHA) worked equally as well. Preliminary studies of foods adjusted to the intermediate moisture range bear out the results of oxidation in model systems. It can be concluded that for most fat containing intermediate moisture foods, rancidity will be the reaction most limiting stability.

Labuza, T. P.↗

Design, characterization, and control of the NASA three degree of freedom reaction compensation platform

Increasing research is being done into industrial uses for the microgravity environment aboard orbiting space vehicles. However, there is some concern over the effects of reaction forces produced by moving objects, especially motors, robotic actuators, and astronauts. Reaction forces produced by the movement of these objects may manifest themselves as undesirable accelerations in the space vehicle making the vehicle unusable for microgravity applications. It is desirable to provide compensation for such forces using active means. This paper presents the design and experimental evaluation of the NASA three degree of freedom reaction compensation platform, a system designed to be a testbed for the feasibility of active attenuation of reaction forces caused by moving objects in a microgravity environment. Unique 'linear motors,' which convert electrical current directly into rectilinear force, are used in the platform design. The linear motors induce accelerations of the displacer inertias. These accelerations create reaction forces that may be controlled to counteract disturbance forces introduced to the platform. The stated project goal is to reduce reaction forces by 90 percent, or -20 dB. Description of the system hardware, characterization of the actuators and the composite system, and design of the software safety system and control software are included.

Birkhimer, Craig↗

Digital Maskless Photolithographic Patterning of DNA-Functionalized Poly(ethylene glycol) Diacrylate Hydrogels with Visible Light Enabling Photodirected Release of Oligonucleotides

Soft biomaterials possessing structural hierarchy have growing applications in lab-on-chip devices, artificial tissues, and micromechanical and chemomechanical systems. The ability to integrate sets of biomolecules, specifically DNA, within hydrogel substrates at precise locations could offer the potential to form and modulate complex biochemical processes with DNA-based molecular switches in such materials and provide a means of creating dynamic spatial patterns, thus enabling spatiotemporal control of a wide array of reaction-diffusion phenomena prevalent in biological systems. In this paper, we develop a means of photopatterning two-dimensional DNA-functionalized poly(ethylene glycol) diacrylate (PEGDA) hydrogel architectures with an aim toward these applications. While PEGDA photopatterning methods are well-established for the fabrication of hydrogels, including those containing oligonucleotides, the photoinitiators typically used have significant crosstalk with many UV-photoswitchable chemistries including nitrobenzyl derivatives. We demonstrate the digital photopatterning of PEGDA-co-DNA hydrogels using a blue light-absorbing (470 nm peak) photoinitiator system and macromer comprised of camphorquinone, triethanolamine, and poly(ethylene glycol) diacrylate ($M$ n = 575) that minimizes absorption in the UV-A wavelength range commonly used to trigger photoswitchable chemistries. We demonstrate this method using digital maskless photolithography within microfluidic devices that allows for the reliable construction of multidomain structures. The method achieves feature resolutions as small as 25 μm, and the resulting materials allow for lateral isotropic bulk diffusion of short single-stranded (ss) DNA oligonucleotides. Finally, we show how the use of these photoinitiators allows for orthogonal control of photopolymerization and UV-photoscission of acrylate-modified DNA containing a 1-(2-nitrophenyl) ethyl spacer to selectively cleave DNA from regions of a PEGDA substrate.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Confined Lithium–Sulfur Reactions in Narrow-Diameter Carbon Nanotubes Reveal Enhanced Electrochemical Reactivity

Here, we demonstrate an unusual electrochemical reaction of sulfur with lithium upon encapsulation in narrow-diameter (subnanometer) single-walled carbon nanotubes (SWNTs). Our study provides mechanistic insight on the synergistic effects of sulfur confinement and Li + ion solvation properties that culminate in a new mechanism of these sub-nanoscale-enabled reactions (which cannot be solely attributed to the lithiation–delithiation of conventional sulfur). Two types of SWNTs with distinct diameters, produced by electric arc (EA-SWNTs, average diameter 1.55 nm) or high-pressure carbon monoxide (HiPco-SWNTs, average diameter 1.0 nm), are investigated with two comparable electrolyte systems based on tetraethylene glycol dimethyl ether (TEGDME) and 1,4,7,10,13-pentaoxacyclopentadecane (15-crown-5). Electrochemical analyses indicate that a conventional solution-phase Li–S reaction occurs in EA-SWNTs, which can be attributed to the smaller solvated [Li(TEGDME)] + and [Li(15-crown-5)] + ions within the EA-SWNT diameter. In stark contrast, the Li–S confined in narrower diameter HiPco-SWNTs exhibits unusual electrochemical behavior that can be attributed to a solid-state reaction enabled by the smaller HiPco-SWNT diameter compared to the size of solvated Li + ions. Our results of the electrochemical analyses are corroborated and supported with various spectroscopic analyses including operando Raman, X-ray photoelectron spectroscopy, and first-principles calculations from density functional theory. Taken together, our findings demonstrate that the controlled solid-state lithiation–delithiation of sulfur and an enhanced electrochemical reactivity can be achieved by sub-nanoscale encapsulation and one-dimensional confinement in narrow-diameter SWNTs.

25 ENERGY STORAGE↗

Modeling of control forces for kinematical constraints in the dynamics of multibody systems: A new approach

Conventionally kinematical constraints in multibody systems are treated similar to geometrical constraints and are modeled by constraint reaction forces which are perpendicular to constraint surfaces. However, in reality, one may want to achieve the desired kinematical conditions by control forces having different directions in relation to the constraint surfaces. The conventional equations of motion for multibody systems subject to kinematical constraints are generalized by introducing general direction control forces. Conditions for the selections of the control force directions are also discussed. A redundant robotic system subject to prescribed end-effector motion is analyzed to illustrate the methods proposed.

Ider, Sitki Kemal↗

Boosting the sodium storage behaviors of carbon materials in ether-based electrolyte through the artificial manipulation of microstructure

The porous carbon blacks rationally designed by a facile yet efficient NH 3 thermal etching route have been investigated as anode materials in an ether-based electrolyte for sodium-ion batteries. The as-synthesized CBN35 carbon black with a 35% weight loss after NH3 thermal etching exhibited a large specific charge capacity of 352 mAh g -1 at 50 mA g -1 and a superior rate capability of 101 mAh g -1 at 16000 mA g -1 , due to its highest microporosity, an appropriate surface area, a desirable microstructure, and a promising hybrid intercalation mechanism. Impressively, even cycled at 1600 mA g -1 over 3200 cycles, an outstanding reversible capacity of 103 mAh g -1 with a negligible 0.0162% capacity loss per cycle can still be achieved. Based on the multimodal characterizations including the structural probes of phase evolution for carbon materials, the electrochemical techniques, and the surface-sensitive XAS measurements, the exceptional electrochemical properties should stem from several merits of modified carbon black system. While the particular microporous structure provides relatively more accessible sodium storage sites, a novel hybrid intercalation mechanism in ether-based electrolyte would incorporate the sodium ion insertion into the disordered structure with the solvated sodium ion species co-intercalation into the graphitic phase. In addition to the diffusion-controlled redox reactions, the noticeable surface-induced pseudocapacitive reactions also significantly contribute to the charge storage upon sodiation and guarantee the rapid migrations of sodium ions/solvated compounds. In conclusion, this system further features a controlled emergence of a robust but thin solid electrolyte interphase layer, which could suppress the side reactions of active electrode with reactive electrolyte, maintain the fragile porous structure upon cycling, and facilitate the migrations of sodium ions and solvated sodium ion compounds.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Analysis of 100-lb(sub f) (445-N) LO2-LCH4 Reaction Control Engine Impulse Bit Performance

Recently, liquid oxygen-liquid methane (LO2-LCH4) has been considered as a potential green propellant alternative for future exploration missions. The Propulsion and Cryogenic Advanced Development (PCAD) project was tasked by NASA to develop this propulsion combination to enable safe and cost-effective exploration missions. To date, limited experience with such combinations exist, and as a result a comprehensive test program is critical to demonstrating with the viability of implementing such a system. The NASA Glenn Research Center conducted a test program of a 100-lbf (445-N) reaction control engine (RCE) at the Center s Altitude Combustion Stand (ACS), focusing on altitude testing over a wide variety of operational conditions. The ACS facility includes unique propellant conditioning feed systems (PCFS), which allow precise control of propellant inlet conditions to the engine. Engine performance as a result of these inlet conditions was examined extensively during the test program. This paper is a companion to the previous specific impulse testing paper, and discusses the pulsed-mode operation portion of testing, with a focus on minimum impulse bit (MIB) and repeatable pulse performance. The engine successfully demonstrated target MIB performance at all conditions, as well as successful demonstration of repeatable pulse widths. Some anomalous conditions experienced during testing are also discussed, including a double pulse phenomenon, which was not noted in previous test programs for this engine.

Marshall, William M.↗

Satellite Attitude Control Utilizing the Earth's Magnetic Field

A study was conducted to determine the feasibility of a satellite attitude fine-control system using the interaction of the earth's magnetic field with current-carrying coils to produce torque. The approximate intensity of the earth's magnetic field was determined as a function of the satellite coordinates. Components of the magnetic field were found to vary essentially sinusoidally at approximately twice orbital frequency. Amplitude and distortion of the sinusoidal components were a function of satellite orbit. Two systems for two-axis attitude control evolved from this study, one using three coils and the other using two coils. The torques developed by the two systems differ only when the component of magnetic field along the tracking line is zero. For this case the two-coil system develops no torque whereas the three-coil system develops some effective torque which allows partial control. The equations which describe the three-coil system are complex in comparison to those of the two-coil system and require the measurement of all three components of the magnetic field as compared with only one for the two-coil case. Intermittent three-axis torquing can also be achieved. This torquing can be used for coarse attitude control, or for dumping the stored momentum of inertia reaction wheels. Such a system has the advantage of requiring no fuel aboard the satellite. For any of these magnetic torquing schemes the power required to produce the magnetic moment and the weight of the coil seem reasonable.

White, John S.↗

Summary of Altitude Pulse Testing of a 100-lbf L02/LCH4 Reaction Control Engine

Recently, liquid oxygen-liquid methane (LO2/LCH4) has been considered as a potential "green" propellant alternative for future exploration missions. The Propulsion and Cryogenic Advanced Development (PCAD) project has been tasked by NASA to develop this propulsion combination to enable safe and cost effective exploration missions. To date, limited experience with such combinations exist, and as a result a comprehensive test program is critical to demonstrating the viability of implementing such a system. The NASA Glenn Research Center has conducted a test program of a 100-lbf (445-N) reaction control engine (RCE) at the center s Altitude Combustion Stand (ACS), focusing on altitude testing over a wide variety of operational conditions. The ACS facility includes a unique propellant conditioning feed system (PCFS) which allows precise control of propellant inlet conditions to the engine. Engine performance as a result of these inlet conditions was examined extensively during the test program. This paper is a companion to the previous specific impulse testing paper, and discusses the pulsed mode operation portion of testing, with a focus on minimum impulse bit (I-bit) and repeatable pulse performance. The engine successfully demonstrated target minimum impulse bit performance at all conditions, as well as successful demonstration of repeatable pulse widths. Some anomalous conditions experienced during testing are also discussed, including a double pulse phenomenon which was not noted in previous test programs for this engine.

Marshall, William M.↗

Enhanced pozzolanic reactivity in hydrogen-form zeolites as supplementary cementitious materials

Pozzolans rich in silica and alumina react with lime to form cementing compounds and are incorporated into portland cement as supplementary cementitious materials (SCMs). However, pozzolanic reactions progress slower than portland cement hydration, limiting their use in modern construction due to insufficient early-age strength. Hence, alternative SCMs that enable faster pozzolanic reactions are necessary including synthetic zeolites, which have high surface areas and compositional purity that indicate the possibility of rapid pozzolanic reactivity. Synthetic zeolites with varying cation composition (Na-zeolite, H-zeolite), SiO 2 /Al 2 O 3 ratio, and framework type were evaluated for pozzolanic reactivity via Ca(OH) 2 consumption using ion exchange and in-situ X-ray diffraction experiments. Na-zeolites exhibited limited exchange reactions with KOH and Ca(OH) 2 due to the occupancy of acid sites by Na + and hydroxyl groups. Meanwhile, H-zeolites readily adsorbed K + and Ca 2+ from a hydroxide solution by exchanging cations with H + at Brønsted acid sites or cation adsorption at vacant acid sites. By adsorbing cations, the H-zeolite reduced the pH and increased Ca 2+ solubility to promote pozzolanic reactions in a system where Ca(OH) 2 dissolution/diffusion was a rate limiting factor. High H-zeolite reactivity resulted in 0.8 g of Ca(OH) 2 consumed per 1 g of zeolites after 16 h of reaction versus 0.4 g of Ca(OH) 2 consumed per 1 g of Na-zeolite. The H-zeolite modulated the pore fluid alkalinity and created a low-density amorphous silicate phase via mechanisms analogous to two-step C-S-H nucleation experiments. Finally, controlling these reaction mechanisms is key to developing next generation pozzolanic cementitious systems with comparable hydration rates to portland cement.

36 MATERIALS SCIENCE↗

Design Development of the Apollo Lunar Module

The lunar module autopilot is a first generation digital control system design. The two torque sources available for the control function of the descent stage configuration consist of 16 reaction jets and a slow, gimbaled, throttlable engine. Design history, the design requirements, criteria, constraints, and general design philosophy of the control system development are reviewed. Comparative flight test results derived from design testing are presented.

Cox, K. L.↗

Algorithm Optimally Allocates Actuation of a Spacecraft

A report presents an algorithm that solves the following problem: Allocate the force and/or torque to be exerted by each thruster and reaction-wheel assembly on a spacecraft for best performance, defined as minimizing the error between (1) the total force and torque commanded by the spacecraft control system and (2) the total of forces and torques actually exerted by all the thrusters and reaction wheels. The algorithm incorporates the matrix vector relationship between (1) the total applied force and torque and (2) the individual actuator force and torque values. It takes account of such constraints as lower and upper limits on the force or torque that can be applied by a given actuator. The algorithm divides the aforementioned problem into two optimization problems that it solves sequentially. These problems are of a type, known in the art as semi-definite programming problems, that involve linear matrix inequalities. The algorithm incorporates, as sub-algorithms, prior algorithms that solve such optimization problems very efficiently. The algorithm affords the additional advantage that the solution requires the minimum rate of consumption of fuel for the given best performance.

Motaghedi, Shi↗

Space Telescope pointing control

The Space Telescope Pointing Control System is used to slew the optical axis of the telescope from one target star region of the celestial sphere to the next, and to maintain precision pointing on the target star. A digital computer is employed in the processing of attitude and rate sensor data, in order to generate torque commands for the reaction wheels. The System comprises four major elements: a command generator, the electronic control system, attitude update processing, and momentum management. Emphasis is given to control-related flexibility effects of the Space Telescope's solar cell array and vehicle, and the acquisition methodology and development testing employed, in addition to Pointing Control System design features.

Dougherty, H.↗

Development of an advanced solid amine humidity and CO2 control system for potential Space Station Extravehicular Activity application

A system for removing metabolic carbon dioxide and water vapor from breathing air within a space suit during NASA Space Station EVA is discussed. The solid amine compound used is packed within a water-cooled metal foam matrix heat-exchanger to remove the exothermic heat of chemical reaction. Details of the design of a canister for humidity and carbon dioxide control and performance of the system are presented.

Nalette, Timothy A.↗

Development of a molecular beam technique to study early solar system silicon reactions

Silicon monoxide is one of the major gas phase silicon bearing components observed in astronomical environments. Silicon oxide serves as the major rock forming material for terrestrial and meteoritic bodies. It is known that several gas phase reactions produce mass independent isotopic fractionations which possess the same delta(O-17)/delta(O-18) ratio observed in Allende inclusions. The general symmetry dependence of the chemically produced mass independent isotopic fractionation process suggests that there are several plausible reactions which could occur in the early solar system which may lead to production of the observed meteoritic oxygen isotopic anomalies. An important component in exploring the role of such processes is the need to experimentally determine the isotopic fractionations for specific reactions of relevance to the early solar system. It has already been demonstrated that atomic oxygen reaction with CO, a major nebular oxygen bearing species, produces a large (approximately 90 percent), mass independent isotopic fractionation. The next hurdle regarding assessing the involvement of symmetry dependent isotopic fractionation processes in the pre-solar nebula is to determine isotopic fractionation factors associated with gas phase reactions of metallic oxides. In particular, a reaction such as O + SiO yields SiO2 is a plausible nebular reaction which could produce a delta(O-17) is approximately delta(O-18) fractionation based upon molecular symmetry considerations. While the isotopic fractionations during silicate evaporation and condensation have been determined, there are no isotopic studies of controlled, gas phase nucleation processes. In order to carefully control the reaction kinetics, a molecular beam apparatus has been constructed. This system produces a supersonic, collimated beam of SiO molecules which is reacted with a second beam of oxygen atoms. An important feature of molecular beams is that they operate at sufficiently low pressures and high temperatures in the jet that avalanche nucleation and clustering processes may be avoided.

Dong, Q. W.↗

Stochasticity and positive feedback enable enzyme kinetics at the membrane to sense reaction size

Here, we present detailed kinetic analyses of a panel of soluble lipid kinases and phosphatases, as well as Ras activating proteins, acting on their respective membrane surface substrates. The results reveal that the mean catalytic rate of such interfacial enzymes can exhibit a strong dependence on the size of the reaction system—in this case membrane area. Experimental measurements and kinetic modeling reveal how stochastic effects stemming from low molecular copy numbers of the enzymes alter reaction kinetics based on mechanistic characteristics of the enzyme, such as positive feedback. For the competitive enzymatic cycles studied here, the final product—consisting of a specific lipid composition or Ras activity state—depends on the size of the reaction system. Furthermore, we demonstrate how these reaction size dependencies can be controlled by engineering feedback mechanisms into the enzymes.

59 BASIC BIOLOGICAL SCIENCES↗