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At least 1,099 records · Page 61

Dehydration Pathway Study of Ultrathin Ni (OH) 2 Probed via In Situ X-Ray Photoelectron Spectromicroscopy

In this work, the conversion of ultrathin 2D-Ni (OH) 2 to NiO is studied using in situ X-ray absorption near edge spectroscopy at the Ni L 3 and O K edges and using variable photon energy X-ray photoelectron spectroscopy at the Ni 2p 3/2 and O 1s edges. The Ni L 3 X-ray absorption spectroscopy and corresponding 2p 3/2 X-ray photoelectron spectroscopy show the oxidation state of the Ni atom to be Ni 2+ in the course of the reaction; however, the film surface and oxygen defect structure show the presence of a large metallic Ni component before the complete disappearance of the hydroxide phase indicating oxygen vacancy formation before the completion of water desorption. O 1s spectral changes during heat treatment under ultrahigh vacuum, O 2 dosing, and H 2 O dosing suggest the spectral features are due to water desorption and adsorption. Furthermore, by comparing the relative probe depths of X-ray photoelectron spectroscopy and X-ray absorption spectroscopy, it is determined that the surface, at each step in the dehydration process, consists of a combination of Ni, NiO, and Ni (OH) 2 phases, which each contain a mixture of adsorbed hydroxyl groups. Repeated dosing with H 2 O, studied with O 1s X-ray photoelectron spectroscopy, suggests that the dissociation of water facilitates the formation of oxygen vacancies.

36 MATERIALS SCIENCE↗

Infrared transmissive concentrated photovoltaics for coupling solar electric energy conversion to solar thermal energy utilization

The use of photovoltaic (PV) cells to convert solar energy to electricity is becoming increasingly prevalent; however, there are still significant limitations associated with the widespread adoption of PV cells for electricity needs. There is a clear need for a high efficiency solar power system that supplies electricity at a competitive cost and that provides for an on-demand supply of electricity as well as energy storage. By combining aspects of concentrated solar power and concentrated photovoltaics, the present invention provides a device that enables the conversion of sunlight to electricity at very high efficiencies and that enables the transmission of thermal energy to heat storage devices for later use. The disclosed device enables transmissive CPV through the use of a multijunction PV cell mounted on a transparent base. The use of a multijunction cell allows for highly efficient absorption of light above the bandgap of the lowest bandgap subcell. The transparent base permits transmission of a high percentage of the remaining light below the bandgap of the lowest bandgap subcell. The present invention also discloses a method of generating electricity through the use of a transmissive CPV device. Sunlight is concentrated onto one or more surfaces of the device. High energy light is absorbed by a multijunction PV cell and converted directly to electricity, while low energy light is transmitted through the device into a thermal storage device, which may then be coupled to a heat engine to generate dispatchable electricity.

Escarra, Matthew David↗

Heat storage in alloy transformations

Heats of transformation of eutectic alloys were measured for many binary and ternary systems by differential scanning calorimetry and thermal analysis. Only the relatively cheap and plentiful elements Mg, Al, Si, P, Ca, Cu, Zn were considered. A method for measuring volume change during transformation was developed using x-ray absorption in a confined sample. Thermal expansion coefficients of both solid and liquid states of aluminum and of its eutectics with copper and with silicon also were determined. Preliminary evaluation of containment materials lead to the selection of silicon carbide as the initial material for study. Possible applications of alloy PCMs for heat storage in conventional and solar central power stations, small solar receivers and industrial furnace operations are under consideration.

Birchenall, C. E.↗

Line Profile Measurements of Atomic Oxygen at 1300 A with a VUV Raman Shifter

We are currently developing an atomic oxygen diagnostic to study the degree of oxygen dissociation in ground-based facilities. The absorption of the (sub 3)P - (sup 3)S(sup 0) resonance triplet in the vacuum ultraviolet is a direct measure of the ground state number density of atomic oxygen. Although the integrated line strength is well known for these transitions, the line profile is not. We report the results of a series of experiments in which the line profile is measured in shock-heated oxygen. An ArF excimer laser and a hydrogen Raman shifter generate tunable VUV radiation at the resonance wavelength. The test gas is dissociated oxygen, generated in the Electric Arc Shock Tube (EAST) Facility at NASA-Ames Research Center. By measuring the absorption of known concentrations of atomic oxygen, we are able to study the absorption line profile. The results will serve as a calibration to apply this diagnostic in other flowfields.

Sharma, Surendra P.↗

Following CO and H Insertion into Ru–C Bonds with X-ray Photoelectron and Absorption Spectroscopies

Insertion reactions play a central role in the catalytic synthesis of ethanol and higher alcohols. X-ray photoelectron and absorption spectroscopies have been used to follow migratory CO insertion and C─C coupling in a cis-[Ru(2,2′-bipyridine) 2 (CO)(CH 3 )] + complex heated in a vacuum or exposed to CO. Heating of the Ru complex in a vacuum to temperatures above 50 °C induced spontaneous migration of CO into the Ru─CH 3 bond to yield a ─COCH 3 ligand. In conclusion, after adding CO to the background gas, the CO insertion reaction was seen at room temperature, opening the door for the synthesis of ethanol and more energy dense liquids.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Probing disorder in high-pressure cubic tin (IV) oxide: a combined x-ray diffraction and absorption study

The transparent conducting oxide, SnO2, shows promise as an optoelectronic material, with predicted tailorable properties through pressuremediated band gap opening. While such electronic properties are typically modeled assuming perfect ordering, this work employs extended x-ray absorption fine structure (EXAFS) spectroscopy to probe anion disordering. We present high-pressure cubic (Pa3) SnO2 at 44.5GPa thoroughly annealed with direct CO2 laser heating, and extract Sn–O distances from EXAFS to reveal a high degree of disorder in O positions. This observation is in contrast with x-ray diffraction (XRD), which suggest a high degree of order. The use of CO2 laser heating allows for direct observations of displacement of light anions in a sample that is without anisotropic strain.

diamond anvil cell↗

Indoor test for thermal performance evaluation of Lenox-Honeywell solar collector

The test procedures used and the test results obtained from an evaluation test program conducted on a double-covered liquid solar collector under simulated conditions are presented. The test article was a flat plate solar collector using liquid as the heat transfer medium. The absorber plate was steel with the copper tubes bonded on the upper surface. The plate was coated with black chrome with an absorptivity factor of .95 and emissivity factor of .12. A time constant test and incident angle modifier test were conducted to determine the transient effect and the incident angle effect on the collector.

Shih, K.↗

Determination of the Rate Coefficients of the SO2 plus O plus M yields SO3 plus M Reaction

Rate coefficients of the title reaction R(sub 31) (SO2 +O+M yields SO3 +M) and R(sub 56) (SO2 + HO2 yields SO3 +OH), important in the conversion of S(IV) to S(VI),were obtained at T =970-1150 K and rho (sub ave) = 16.2 micro mol/cubic cm behind reflected shock waves by a perturbation method. Shock-heated H2/ O2/Ar mixtures were perturbed by adding small amounts of SO2 (1%, 2%, and 3%) and the OH temporal profiles were then measured using laser absorption spectroscopy. Reaction rate coefficients were elucidated by matching the characteristic reaction times acquired from the individual experimental absorption profiles via simultaneous optimization of k(sub 31) and k(sub 56) values in the reaction modeling (for satisfactory matches to the observed characteristic times, it was necessary to take into account R(sub 56)). In the experimental conditions of this study, R(sub 31) is in the low-pressure limit. The rate coefficient expressions fitted using the combined data of this study and the previous experimental results are k(sub 31,0)/[Ar] = 2.9 10(exp 35) T(exp ?6.0) exp(?4780 K/T ) + 6.1 10(exp 24) T(exp ?3.0) exp(?1980 K/T ) cm(sup 6) mol(exp ?2)/ s at T = 300-2500 K; k(sub 56) = 1.36 10(exp 11) exp(?3420 K/T ) cm(exp 3)/mol/s at T = 970-1150 K. Computer simulations of typical aircraft engine environments, using the reaction mechanism with the above k(sub 31,0) and k(sub 56) expressions, gave the maximum S(IV) to S(VI) conversion yield of ca. 3.5% and 2.5% for the constant density and constant pressure flow condition, respectively. Moreover, maximum conversions occur at rather higher temperatures (?1200 K) than that where the maximum k(sub 31,0) value is located (approximately 800 K). This is because the conversion yield is dependent upon not only the k(sup 31,0) and k(sup 56) values (production flux) but also the availability of H, O, and HO2 in the system (consumption flux).

Hwang, S. M.↗

Athermal Energy Loss from X-rays Deposited in Thin Superconducting Films on Solid Substrates

When energy is deposited in a thin-film cryogenic detector, such as from the absorption of an X-ray, an important feature that determines the energy resolution is the amount of athermal energy that can be lost to the heat bath prior to the elementary excitation systems coming into thermal equilibrium. This form of energy loss will be position-dependent and therefore can limit the detector energy resolution. An understanding of the physical processes that occur when elementary excitations are generated in metal films on dielectric substrates is important for the design and optimization of a number of different types of low temperature detector. We have measured the total energy loss in one relatively simple geometry that allows us to study these processes and compare measurements with calculation based upon a model for the various di.erent processes. We have modeled the athermal phonon energy loss in this device by finding an evolving phonon distribution function that solves the system of kinetic equations for the interacting system of electrons and phonons. Using measurements of device parameters such as the Debye energy and the thermal di.usivity we have calculated the expected energy loss from this detector geometry, and also the position-dependent variation of this loss. We have also calculated the predicted impact on measured spectral line-shapes, and shown that they agree well with measurements. In addition, we have tested this model by using it to predict the performance of a number of other types of detector with di.erent geometries, where good agreement is also found.

Kozorezov, Alexander G.↗

Deuterium retention characteristics in Li film by coating and during flowing liquid Li limiter operation in experimental advanced superconducting tokamak

Lithium (Li) is a promising low-Z material for particle recycling and impurity control to improve plasma performance in fusion devices. In the experimental advanced superconducting tokamak (EAST), Li coating has become a routine method for wall conditioning, and a flowing liquid Li (FLiLi) limiter has been successfully tested several times. Deuterium retention characteristics in the Li film coated on the international thermonuclear experimental reactor-like tungsten divertor and FLiLi during plasma discharges, which is important for the utilization of Li in future fusion devices, were investigated in EAST. It is found that the absorption of the fuel particles by Li coatings decreases gradually, and recycling gradually increases over a series of discharges. The maximum net amount of deuterium retained reached ~0.8 g, corresponding to 12% deuterium in the Li. Furthermore, this corresponds to a whole day's worth of shots with a total of 87 plasma discharges and a total of ~640s plasma time after 11.75 g Li was deposited. Compared to the Li coating, it is shown that FLiLi continuously traps fuel particles and achieves a higher deuterium retention ratio over both the short- and long-term, leading to lower recycling. Meanwhile, it is also observed that the fuel particle retention ratio increases when FLiLi is closer to the plasma. This result is likely due to higher plasma heating power and limiter temperature, which cause an increased Li efflux from FLiLi due to a higher limiter temperature, which then redeposits on the other plasma-facing surfaces and increases fuel particle absorption. It is estimated that ≥ 80% of the retained D particles are captured by the continual renewal of the Li redeposition film during the FLiLi operation. This investigation would also be useful for D/T retention in future fusion devices if Li is used as a plasma-facing component.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

Distinct Surface and Bulk Thermal Behaviors of LiNi 0.6 Mn 0.2 Co 0.2 O 2 Cathode Materials as a Function of State of Charge

Understanding how structural and chemical transformations take place in particles under thermal conditions can inform designing thermally robust electrode materials. Such a study necessitates the use of diagnostic techniques that are capable of probing the transformations at multiple length scales and at different states of charge (SOC). In this study, the thermal behavior ofLiNi 0.6 Mn 0.2 Co 0.2 O 2 (NMC-622) was examined as a function of SOC, using an array of bulk and surface-sensitive techniques. In general, thermal stability decreases as lithium content is lowered and conversion in the bulk to progressively reduced metal oxides (spinels, rock salt) occurs as the temperature is raised. Hard X-ray absorption spectroscopy (XAS) and X-ray Raman spectroscopy (XRS) experiments, which probe the bulk, reveal that Ni and Co are eventually reduced when partially delithiated samples (regardless of the SOC) are heated, although Mn is not. Surface-sensitive synchrotron techniques, such as soft XAS and transmission X-ray microscopy (TXM), however, reveal that for 50% delithiated samples, apparent oxidation of nickel occurs at particle surfaces under some circumstances. This is partially compensated by reduction of cobalt but may also be a consequence of redistribution of lithium ions upon heating. TXM results indicate the movement of reduced nickel ions into particle interiors or oxidized nickel ions to the surface or both. These experiments illustrate the complexity of the thermal behavior of NMC cathode materials. The study also informs the importance of investigating the surface and bulk difference as a function of SOC when studying the thermal behaviors of battery materials.

25 ENERGY STORAGE↗

Bioavailable soil Pb minimized by in situ transformation to plumbojarosite

Exposure to lead (Pb) during early life has persistent adverse health effects. During childhood, ingestion of bioavailable Pb in contaminated soils can be a major route of Pb absorption. Remediation to alter physiochemical properties of soil-borne Pb can reduce Pb bioavailability. Our laboratory-based approach for soil Pb remediation uses addition of iron (Fe) sulfate and application of heat to promote formation of plumbojarosite (PLJ), a sparingly soluble Pb-Fe hydroxysulfate mineral. We treated two soils with anthropogenic Pb contamination and samples of clean topsoil spiked with various Pb compounds (i.e., carbonate, chloride, phosphate [P], or sulfate) to convert native Pb species to PLJ and used a mouse assay to assess relative bioavailability (RBA) of Pb in untreated (U) and remediated soils. Bone and blood Pb levels were significantly lower (P < 0.001, Student's t test) in mice that consumed diets amended with remediated soils than with U soils. Estimated RBA for Pb in both remediated natural soils and Pb-mineral spiked soils were reduced by >90% relative to Pb RBA for U soils, which is substantially more effective than other soil amendments, including P. X-ray absorption spectroscopy showed that >90% of all Pb species in remediated soils were converted to PLJ, and ingested PLJ was not chemically transformed during gastrointestinal tract transit. Post treatment neutralization of soil pH did not affect PLJ stability, indicating the feasibility in field conditions. These results suggest that formation of PLJ in contaminated soils can reduce the RBA of Pb and minimize this medium’s role as a source of Pb exposure for young children.

59 BASIC BIOLOGICAL SCIENCES↗

Flare heating and ionization of the low solar chromosphere. I - Inversion methods for Mg I 4571 and 5173

Various methods of inverting solar Mg I 4571 and 5173 spectral line observations are examined to find the best method of using these lines to calculate the vertical temperature and electron density structure around the temperature minimum region. Following a perturbation analysis by Mein (1971), a Fredholm integral equation of the first kind is obtained which can be inverted to yield these temperature and density structures as a function of time. Several inversion methods are tested and compared. The methods are used to test data as well as to a subset of observations of these absorption lines taken on February 3, 1986 before and during a solar flare. A small but significant increase is found in the temperature and a relatively large increase in the electron density during this flare. The observations are inconsistent with heating and ionization by an intense beam of electrons and with ionization by UV photoionization of Si I.

Metcalf, Thomas R.↗

Spatially and temporally resolved plasma parameter estimations of laser heated MagLIF relevant gas pipes at NIF

The ability to control laser pre-heat is an integral part of the inertial confinement fusion concept known as Magnetized Liner Inertial Fusion. This process is studied at the National Ignition Facility (NIF) where 4 of the 192 laser beams are propagated through a 1-cm long gas cell where they deposit >20 kJ of energy into the gaseous fuel via inverse bremsstrahlung absorption. This process ionizes the gas, producing a plasma that follows behind the laser front and expands over the radius of the cell. Emission from this plasma, as viewed by a gated x-ray detector, can be used to build spatially and temporally resolved estimations of the pre-heat plasma's density and temperature profiles. This can then be used to estimate the plasma pressure, internal energy, and radiation losses. Estimations show the evolution of the plasma in magnetized and unmagnetized gas cells filled with ambient temperature neopentane (C5H12) +1% Ar, as well as unmagnetized cryogenically cooled (32 K) deuterium +1% Ne filled targets. This analysis shows the effects of initial gas-fill density, composition, and axial magnetization on the time-dependent plasma parameters. Previously, these parameters at the NIF had not been experimentally characterized, and these estimations provided a potential new means of testing radiation magneto-hydrodynamic predictive capability models. Results in unmagnetized targets have strong agreement with simulations. However, in targets with a 19 T applied axial magnetic field, this method yields electron temperatures up to 100% hotter than those predicted by HYDRA codes.

Bremsstrahlung↗

Digital Light Process 3D Printing of Magnetically Aligned Liquid Crystalline Elastomer Free–forms

Liquid crystalline elastomers (LCEs) are anisotropic soft materials capable of large dimensional changes when subjected to a stimulus. The magnitude and directionality of the stimuli-induced thermomechanical response is associated with the alignment of the LCE. Recent reports detail the preparation of LCEs by additive manufacturing (AM) techniques, predominately using direct ink write printing. Another AM technique, digital light process (DLP) 3D printing, has generated significant interest as it affords LCE free-forms with high fidelity and resolution. However, one challenge of printing LCEs using vat polymerization methods such as DLP is enforcing alignment. Here, we document the preparation of aligned, main-chain LCEs via DLP 3D printing using a 100 mT magnetic field. Systematic examination isolates the contribution of magnetic field strength, alignment time, and build layer thickness on the degree of orientation in 3D printed LCEs. Informed by this fundamental understanding, DLP is used to print complex LCE free-forms with through-thickness variation in both spatial orientations. Further, the hierarchical variation in spatial orientation within LCE free-forms is used to produce objects that exhibit mechanical instabilities upon heating. DLP printing of aligned LCEs opens new opportunities to fabricate stimuli-responsive materials in form factors optimized for functional use in soft robotics and energy absorption.

36 MATERIALS SCIENCE↗

Structural relaxation of water during rapid cooling from ambient temperatures

Experiments investigating the properties of deeply supercooled liquid water are needed to develop a comprehensive understanding of water’s anomalous properties. One approach involves transiently heating nanoscale water films into the supercooled region for several nanoseconds at a time and then interrogating the water films after they have quenched to cryogenic temperatures. To relate the results obtained with this approach to other experiments and simulations on supercooled water, it is important to understand how closely the quenched structure tracks the (metastable) equilibrium structure of water as a function of the transient heating temperature. A key step involves quantifying the extent to which water that is transiently heated to ambient temperatures [hyperquenched water (HQW)] subsequently relaxes toward the structure of low-density amorphous (LDA) ice as it cools. We analyzed the infrared reflection–absorption spectra of LDA, HQW, and crystalline ice films to determine their complex indices of refraction. With this information, we estimate that HQW retains ~50%–60% of a structural motif characteristic of water at high temperatures with the balance comprised of a low-temperature motif. This result, along with results from x-ray diffraction experiments on water and amorphous ices, allows one to quantify the fraction of the high-temperature motif at approximately zero pressure as a function of temperature from 150 to 350 K.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Recent advances of two-dimensional material additives in hybrid perovskite solar cells

Perovskite solar cells (PSCs) have become one of the state-of-the-art photovoltaic technologies due to their facile solution-based fabrication processes combined with extremely high photovoltaic performance originating from excellent optoelectronic properties such as strong light absorption, high charge mobility, long free charge carrier diffusion length, and tunable direct bandgap. However, the poor intrinsic stability of hybrid perovskites under environmental stresses including light, heat, and moisture, which is often associated with high defect density in the perovskite, has limited the large-scale commercialization and deployment of PSCs. The use of process additives, which can be included in various subcomponent layers in the PSC, has been identified as one of the effective approaches that can address these issues and improve the photovoltaic performance. Among various additives that have been explored, two-dimensional (2D) materials have emerged recently due to their unique structures and properties that can enhance the photovoltaic performance and device stability by improving perovskite crystallization, defect passivation, and charge transport. In this work, we provide a review of the recent progresses in 2D material additives for improving the PSC performance based on key representative 2D material systems, including graphene and its derivatives, transitional metal dichalcogenides, and black phosphorous, providing a useful guideline for further exploiting unique nanomaterial additives for more efficient and stable PSCs in the near future.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

Photoemission Induced Plasma Breakdown (Update)

Laser-induced photoemission of electrons offers opportunities to trigger and control plasmas and discharges. However, the underlying mechanisms are not sufficiently characterized to be fully utilized. Photoemission is highly nonlinear, achieved through multiphoton absorption, above threshold ionization, photo-assisted tunneling, etc., where the dominant process depends on the work function of the material, photon energy and associated fields, surface heating, background fields, etc. To characterize the effects of photoemission on breakdown, breakdown experiments were performed and interpreted using a 0D plasma discharge circuit model and quantum model of photoemission.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗