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At least 829 records · Page 46

Excited-State Dynamics of All the Mono-cis and the Major Di-cis Isomers of β-Apo-8′-Carotenal as Revealed by Femtosecond Time-Resolved Transient Absorption Spectroscopy

Cis isomers of carotenoids play important roles in light harvesting and photoprotection in photosynthetic bacteria, such as the reaction center in purple bacteria and the photosynthetic apparatus in cyanobacteria. Carotenoids containing carbonyl groups are involved in efficient energy transfer to chlorophyll in light-harvesting complexes, and their intramolecular charge–transfer (ICT) excited states are known to be important for this process. Previous studies, using ultrafast laser spectroscopy, have focused on the central-cis isomer of carbonyl-containing carotenoids, revealing that the ICT excited state is stabilized in polar environments. However, the relationship between the cis isomer structure and the ICT excited state has remained unresolved. In this study, we performed steady-state absorption and femtosecond time-resolved absorption spectroscopy on nine geometric isomers (7-cis, 9-cis, 13-cis, 15-cis, 13′-cis, 9,13′-cis, 9,13-cis, 13,13′-cis, and all-trans) of β-apo-8′-carotenal, whose structures are well-defined, and discovered correlations between the decay rate constant of the S1 excited state and the S0−S1 energy gap, as well as between the position of the cis-bend and the degree of stabilization of the ICT excited state. Our results demonstrate that the ICT excited state is stabilized in polar environments in cis isomers of carbonyl-containing carotenoids and suggest that the position of the cis-bend plays an important role in the stabilization of the excited state.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

High Power MPD Thruster Development at the NASA Glenn Research Center

Propulsion requirements for large platform orbit raising, cargo and piloted planetary missions, and robotic deep space exploration have rekindled interest in the development and deployment of high power electromagnetic thrusters. Magnetoplasmadynamic (MPD) thrusters can effectively process megawatts of power over a broad range of specific impulse values to meet these diverse in-space propulsion requirements. As NASA's lead center for electric propulsion, the Glenn Research Center has established an MW-class pulsed thruster test facility and is refurbishing a high-power steady-state facility to design, build, and test efficient gas-fed MPD thrusters. A complimentary numerical modeling effort based on the robust MACH2 code provides a well-balanced program of numerical analysis and experimental validation leading to improved high power MPD thruster performance. This paper reviews the current and planned experimental facilities and numerical modeling capabilities at the Glenn Research Center and outlines program plans for the development of new, efficient high power MPD thrusters.

LaPointe, Michael R.↗

Acoustic Database for Turbofan Engine Core-Noise Sources: Volume - I

In this program, a database of dynamic temperature and dynamic pressure measurements were acquired inside the core of a TECH977 turbofan engine to support investigations of indirect combustion noise. Dynamic temperature and pressure measurements were recorded for engine gas dynamics up to temperatures of 3100 degrees Fahrenheit and transient responses as high as 1000 hertz. These measurements were made at the entrance of the high pressure turbine (HPT) and at the entrance and exit of the low pressure turbine (LPT). Measurements were made at two circumferential clocking positions. In the combustor and inter-turbine duct (ITD), measurements were made at two axial locations to enable the exploration of time delays. The dynamic temperature measurements were made using dual thin-wire thermocouple probes. The dynamic pressure measurements were made using semi-infinite probes. Prior to the engine test, a series of bench, oven, and combustor rig tests were conducted to characterize the performance of the dual wire temperature probes and to define and characterize the data acquisition systems. A measurement solution for acquiring dynamic temperature and pressure data on the engine was defined. A suite of hardware modifications were designed to incorporate the dynamic temperature and pressure instrumentation into the TECH977 engine. In particular, a probe actuation system was developed to protect the delicate temperature probes during engine startup and transients in order to maximize sensor life. A set of temperature probes was procured and the TECH977 engine was assembled with the suite of new and modified hardware. The engine was tested at four steady state operating speeds, with repeats. Dynamic pressure and temperature data were acquired at each condition for at least one minute. At the two highest power settings, temperature data could not be obtained at the forward probe locations since the mean temperatures exceeded the capability of the probes. The temperature data were processed using software that accounts for the effects of convective and conductive heat transfer. The software was developed under previous NASA sponsored programs. Compensated temperature spectra and compensated time histories corresponding to the dynamic temperature of the gas stream were generated. Auto-spectral and cross-spectral analyses of the data were performed to investigate spectral features, acoustic circumferential mode content, signal coherence, and time delays. The dynamic temperature data exhibit a wideband and fairly flat spectral content. The temperature spectra do not change substantially with operating speed. The pressure spectra in the combustor and ITD exhibit generally similar shapes and amplitudes, making it difficult to identify any features that suggest the presence of indirect combustion noise. Cross-spectral analysis reveal a strong correlation between pressure and temperature fluctuations in the ITD, but little correlation between temperature fluctuations at the entrance of the HPT and pressure fluctuations downstream of it. Temperature fluctuations at the entrance of the low pressure turbine were an order of magnitude smaller than those at the entrance to the high pressure turbine. Time delay analysis of the temperature fluctuations in the combustor was inconclusive, perhaps due to the substantial mixing that occurs between the upstream and downstream locations. Time delay analysis of the temperature fluctuations in the ITD indicate that they convect at the mean flow speed. Analysis of the data did not reveal any convincing indications of the presence of indirect combustion noise. However, this analysis has been preliminary and additional exploration of the data is recommended including the use of more sophisticated signal processing to explore subtle issues that have been revealed but which are not yet fully understood or explained.

Aeroacoustics↗

An Experimental Method to Measure Gaseous Diffusivity in Tight and Partially Saturated Porous Media via Continuously Monitored Mass Spectrometry

Detection of radioxenon and radioargon produced by underground nuclear explosions is one of the primary methods by which the Comprehensive Nuclear-Test–Ban Treaty (CTBT) monitors for nuclear activities. However, transport of these noble gases to the surface via barometric pumping is a complex process relying on advective and diffusive processes in a fractured porous medium to bring detectable levels to the surface. To better understand this process, experimental measurements of noble gas and chemical surrogate diffusivity in relevant lithologies are necessary. However, measurement of noble gas diffusivity in tight or partially saturated porous media is challenging due to the transparent nature of noble gases, the lengthy diffusion times, and difficulty maintaining consistent water saturation. Here, the quasi-steady-state Ney–Armistead method is modified to accommodate continuous gas sampling via effusive flow to a mass spectrometer. An analytical solution accounting for the cumulative sampling losses and induced advective flow is then derived. Experimental results appear in good agreement with the proposed theory, suggesting the presence of retained groundwater reduces the effective diffusivity of the gas tracers by 10–1000 times. Finally, by using a mass spectrometer, the method described herein is applicable to a broad range of gas species and porous media.

47 OTHER INSTRUMENTATION↗

Phase field-volumetric lattice Boltzmann model of ion uptake in porous nuclear waste form materials under continuous flow

The flow field within the mesopores of sorbent particles plays a crucial role in radionuclide diffusion and ion uptake kinetics, thus, impacting the overall performance of porous nuclear waste form materials. To fundamentally understand the influence of microstructures and material properties on the radionuclide absorption and retention processes requires a coupled multi-physics model that considers the advection and diffusion within the flow field, the reaction at liquid-solid interfaces, and finally, the solid-state diffusion within a complex nanoporous medium. Here, this study employs the volumetric lattice Boltzmann method (VLBM) to accurately and efficiently calculate the steady state velocity field inside the mesopores of sorbent particles. The obtained velocity field is then utilized to calculate the advection of ions in the steady flow. A phase field (PF) model of ion uptake is used to describe the reaction occurring at the solid-liquid interface and diffusion inside the porous medium. The integrated PF-VLBM model is verified in terms of the mass conservation and numerical efficiency and validated qualitatively with experimental observation data. Then, it is applied to study the influence of thermodynamic and kinetic properties, as well as flow field conditions on the ion uptake kinetics. The numerical results demonstrate that the ion uptake kinetics in porous particles has three distinct stages, which is in agreement with the observations in continuous flow experiments. In the first stage, the kinetics is predominantly controlled by the flow field and ion diffusivity in the liquid phase. The kinetics in the second stage is primarily governed by ion diffusivity in the solid phase. In the third stage the system reaches a dynamic equilibrium with a net zero uptake flux at the interface. It is also found that porous structures significantly affect the efficiency and capacity of ion uptake. The simulation results can help to understand the physics behind the observed ion uptake kinetics in experiments and to facilitate the development of constitutive equations that can account for heterogeneous microstructures in engineering performance codes.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Methods of measurement for semiconductor materials, process control, and devices

The development of methods of measurement for semiconductor materials, process control, and devices is discussed. The following subjects are also presented: (1) demonstration of the high sensitivity of the infrared response technique by the identification of gold in a germanium diode, (2) verification that transient thermal response is significantly more sensitive to the presence of voids in die attachment than steady-state thermal resistance, and (3) development of equipment for determining susceptibility of transistors to hot spot formation by the current-gain technique.

Bullis, W. M.↗

An ultrasonic flowmeter for measuring dynamic liquid flow

A novel oscillating pipe system was developed to provide dynamic calibration wherein small sinusoidal signals with amplitudes of 0.5 to 10% of the steady-state flow were added to the steady-state flow by oscillating the flowmeter relative to the fixed pipes in the flow system. Excellent agreement was obtained between the dynamic velocities derived from an accelerometer mounted on the oscillating pipe system and those sensed by the flowmeter at frequencies of 7, 19, and 30 Hz. Also described were the signal processing techniques used to retrieve the small sinusoidal signals which were obscured by the fluid turbulence.

Carpini, T. D.↗

Development of tunable high pressure CO2 laser for lidar measurements of pollutants and wind velocities, January 1976 to December 1977

A tunable multiatmospheric pulsed CO2 laser with emphasis on experimental features and supporting theoretical analyses important to differential absorption lidar and Doppler lidar measurement of pollutants and wind velocities is reported. The energy deposition and the means to produce the uniform high density plasma in the multiatmospheric medium, through UV preionization of an organic seed gas is discussed. Design features of the pulsed CO2 laser are presented. The radiative processes which are operative and prevent the laser from breaking into oscillations in a large number of modes over its broad amplification bandwidth are described. The mode competition for the transient pulsed laser oscillation in a standing wave and traveling wave ring laser configuration is discussed and contrasted with the approach to steady state oscillations. The latter findings are important to transient injection locking for production of a highly stable pulsed CO2 laser output.

Javan, A.↗

Preliminary results of the mission profile life test of a 30 cm Hg bombardment thruster

Long term tests were performed on a 30 cm Hg bombardment thruster and a power processing unit to determine lifetime characteristics. The thruster performance data and other operational characteristics taken at various times during the test segment are presented and evaluated with the life limiting mechanisms: discharge chamber erosion, deposition and spalling, external erosion, cathode degradation, and propellant isolator leakage. The control algorithms for thruster start up, steady state operation, throttle, detection and correction of off normal conditions, and shutdown are discussed.

Bechtel, R. T.↗

Escape of atmospheres and loss of water

The properties and limitations of several loss processes for atmospheric gases are presented and discussed. They include thermal loss (Jeans and hydrodynamic); nonthermal loss (all processes involve charged particles); and impact erosion, including thermal escape from a molten body heated by rapid accretion. Hydrodynamic escape, or 'blowoff', is of particular interest because it offers the prospect of processing large quantities of gas and enriching the remainder in heavy elements and isotopes. In a second part, the water budgets and likely evolutionary histories of Venus, Earth and Mars are assessed. Although it is tempting to associate the great D/H enrichment on Venus with loss of a large initial endowment, a steady state with juvenile water (perhaps from comets) is equally probable.

Hunten, D. M.↗

Automated simulation as part of a design workstation

A development project for a design workstation for advanced life-support systems (called the DAWN Project, for Design Assistant Workstation), incorporating qualitative simulation, required the implementation of a useful qualitative simulation capability and the integration of qualitative and quantitative simulation such that simulation capabilities are maximized without duplication. The reason is that to produce design solutions to a system goal, the behavior of the system in both a steady and perturbed state must be represented. The Qualitative Simulation Tool (QST), on an expert-system-like model building and simulation interface toll called ScratchPad (SP), and on the integration of QST and SP with more conventional, commercially available simulation packages now being applied in the evaluation of life-support system processes and components are discussed.

Cantwell, Elizabeth↗

Rapid Switching and Modulation by use of Coupled VCSELs

Devices incorporating coupled vertical-cavity surface-emitting lasers (VCSELs) have been proposed as means to effect unprecedentedly rapid modulation and/or switching of light beams in advanced optical communication and information-processing systems. A basic device according to the proposal would comprise two or more VCSELs (1) positioned so close to each other that they are coupled and (2) connected to a current source that biases them at a steady current above the threshold current for lasing. The operation of VCSELs under the conditions stated above has been simulated computationally with an algorithm that solves an approximation of the Maxwell-Bloch equations. (These are nonlinear coupled partial differential equations that model the relevant aspects of the physics of semiconductor lasers.) The results of the simulations show that the intensities of the beams oscillate, out of phase relative to each other, at a frequency that is typically of the order of tens of gigahertz. In particular, one simulation was performed for two coupled VCSELs, each having a circular aperture 5.6 microns in diameter, operating at a wavelength of 980 nm. The results of the simulation showed that the intensities of the two beams oscillated in opposite phase (see Figure 1) at a frequency of 42 GHz. In the far field, the beams were found to be separated by an angle of approx.=8deg. The intensities of the beams were also found to oscillate in the near field, 90deg out of phase with the oscillation in the far field. Figure 2 depicts a simple near-field switching device in which an assembly of microlenses would couple the two oscillating beams to two receivers.

Goorjian, Peter M.↗

Hole Trapping in Halide Perovskites Induces Phase Segregation

Metal halide perovskites have garnered a great deal of attention for their applications in photovoltaics, LEDs, and radiation detection. The ease of solution processing high-quality perovskite semiconductors with large absorption coefficients and tolerance to native defects is decidedly attractive. Additionally, the ability to precisely tune the band gap of halide perovskites through compositional alloying of the halide ion is of particular interest for a range of applications, especially for tandem solar cells. However, under steady state light irradiation, an initially homogeneous mixed halide perovskite (MHP) will form local domains that are rich in one halide ion (e.g., Br or I). This light-induced phase segregation in MHPs forms iodide-rich domains that act as charge carrier traps and lowers the efficiency of perovskite-based devices. Thus, phase segregation poses a serious challenge to the implementation of MHPs in real-world device settings. Interestingly, when a phase segregated MHP film is placed in the dark, entropic driving forces become dominant and the segregated perovskite remixes and returns to its initially homogeneous state. Several key mechanistic details of phase segregation have been elucidated over the years. However, there are still aspects of halide segregation that are not clear, and there is ongoing debate in the literature as to what are the key factors that contribute to the mechanism. This Account discusses recent results that point to the specific role of hole trapping in phase segregation. Interestingly, generation of holes through above-band-gap excitation or through electrochemical injection increases ion migration and leads to phase segregation. The thermodynamic and redox properties of halide perovskites provide a strong driving force for hole trapping and oxidation of iodide species in MHPs. However, mobile halide species within the perovskite lattice take time to migrate and generate halide-rich domains. When in contact with a nonpolar solvent, the migration of iodine species is further extended to expulsion of iodine from the perovskite film. Thus, the mobility of halides and their susceptibility to hole-induced oxidation play a crucial role in determining the long-term stability of metal halide perovskites. Strategies to gain kinetic control over ion migration to slow phase segregation are needed to overcome these hurdles and achieve stable mixed halide perovskites. Modification of the perovskite composition through introduction of different cations or halide ions, or introduction of low-dimensional perovskite phases may suppress phase segregation. Furthermore, in achieving stability and improving the efficiency of perovskite solar cells and light emitting devices with minimal impacts, suppression of segregation remains the key factor.

36 MATERIALS SCIENCE↗

Atomic force microscopy: Emerging illuminated and operando techniques for solar fuel research

Integrated photoelectrochemical devices rely on the synergy between components to efficiently generate sustainable fuels from sunlight. The micro- and/or nanoscale characteristics of the components and their interfaces often control critical processes of the device, such as charge-carrier generation, electron and ion transport, surface potentials, and electrocatalysis. Understanding the spatial properties and structure–property relationships of these components can provide insight into designing scalable and efficient solar fuel components and systems. These processes can be probed ex situ or in situ with nanometer-scale spatial resolution using emerging scanning-probe techniques based on atomic force microscopy (AFM). In this Perspective, we summarize recent developments of AFM-based techniques relevant to solar fuel research. We review recent progress in AFM for (1) steady-state and dynamic light-induced surface photovoltage measurements; (2) nanoelectrical conductive measurements to resolve charge-carrier heterogeneity and junction energetics; (3) operando investigations of morphological changes, as well as surface electrochemical potentials, currents, and photovoltages in liquids. Opportunities for research covered here include: (1) control of ambient conditions for performing AFM measurements; (2) in situ visualization of corrosion and morphological evolution of electrodes; (3) operando AFM techniques to allow nanoscale mapping of local catalytic activities and photo-induced currents and potentials.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Dynamic pulse-to-pulse thermal load effects in pulse-train-mode self-seeded X-ray free-electron laser

Thermal load has been a haunting factor that undermines the brightness and coherence of the self-seeded X-ray free-electron laser. Additionally, different from uniformly pulsed mode, in pulse train mode a thermal quasi-steady state of the crystal monochromator may not be reached. This leads to a dynamic thermal distortion of the spectral transmission curves and seed quality degradation. In this paper, the pulse-to-pulse thermal load effects on the spectral transmission curves and seed quality are shown, and some instructive information for the tuning process is provided.

47 OTHER INSTRUMENTATION↗

Transmission Electron Microscopy Study on the Effect of Thermal and Electrical Stimuli on Ge2Te3 Based Memristor Devices

Memristor devices fabricated using the chalcogenide Ge 2 Te 3 phase change thin films in a metal-insulator-metal structure are characterized using thermal and electrical stimuli in this study. Once the thermal and electrical stimuli are applied, cross-sectional transmission electron microscopy (TEM) and X-ray energy-dispersive spectroscopy (XEDS) analyses are performed to determine structural and compositional changes in the devices. Electrical measurements on these devices showed a need for increasing compliance current between cycles to initiate switching from low resistance state (LRS) to high resistance state (HRS). The measured resistance in HRS also exhibited a steady decrease with increase in the compliance current. High resolution TEM studies on devices in HRS showed the presence of residual crystalline phase at the top-electrode/dielectric interface, which may explain the observed dependence on compliance current. XEDS study revealed diffusion related processes at dielectric-electrode interface characterized, by the separation of Ge 2 Te 3 into Ge- and Te- enriched interfacial layers. This was also accompanied by spikes in O level at these regions. Furthermore, in-situ heating experiments on as-grown thin films revealed a deleterious effect of Ti adhesive layer, wherein the in-diffusion of Ti leads to further degradation of the dielectric layer. This experimental physics-based study shows that the large HRS/LRS ratio below the current compliance limit of 1 mA and the ability to control the HRS and LRS by varying the compliance current are attractive for memristor and neuromorphic computing applications.

Shallcross, Austin↗

The pressure and energy balance of the cool corona over sunspots

The 22 largest sunspots observed with the Skylab SO55 spectrometer are studied for a relation between their EUV radiation and their umbral size or magnetic classification. The ultimate goal is to determine why the coronal plasma is so cool over a sunspot and how this cool plasma manages to support itself against gravity. Based on the time behavior of the EUV emission, a steady-state model is developed for the pressure and energy balance of the cool coronal-plasma loops over the spots. Analysis of the temperature structure in a typical loop indicates that the loop is exceedingly well insulated from the outside corona, that its energy balance is determined purely by internal heating and cooling processes, and that a heat input of about 0.0001 erg/cu cm per sec is required along the full length of the loop. It is proposed that: (1) coronal material flows steadily across the field lines at the tops of the loops and falls downward along both sides under gravity; (2) the corona is heated by mechanical-energy transport across the very thin transition region immediately over network-cell interiors; and (3) strong magnetic fields tend to inhibit mechanical-energy dissipation in the corona.

Foukal, P. V.↗

Dielectrics for long term space exposure and spacecraft charging: A briefing

Charging of dielectrics is a bulk, not a surface property. Radiation driven charge stops within the bulk and is not quickly conducted to the surface. Very large electric fields develop in the bulk due to this stopped charge. At space radiation levels, it typically requires hours or days for the internal electric fields to reach steady state. The resulting electric fields are large enough to produce electrical failure within the insulator. This type failure is thought to produce nearly all electric discharge anomalies. Radiation also induces bond breakage, creates reactive radicals, displaces atoms and, in general, severely changes the chemistry of the solid state material. Electric fields can alter this process by reacting with charged species, driving them through the solid. Irradiated polymers often lose as much as a percent of their mass, or more, at exposures typical in space. Very different aging or contaminant emission can be induced by the stopped charge electric fields. These radiation effects are detailed.

Frederickson, A. R.↗