Demand bidding vs. demand response for industrial electrical loads
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If a machine is to perform a given subtask autonomously, it will require an internal model which, combined with operator and environmental inputs, can be used to generate the manipulator functions necessary to complete the task. This paper will advance a technique based on linear transformations by which short, supervised periods of manipulation can be accomplished. To achieve this end a distinction will be made between tasks which can be completely defined during the training period, and tasks which can be only partially defined prior to the moment of execution. A further distinction will be made between tasks which have a fixed relationship to the manipulator base throughout the execution period, and tasks which have a continuously changing task/base relationship during execution. Finally, through a rudimentary analysis of the methods developed in this paper, some of the practical aspects of implementing a supervisory system will be illustrated
With the fast growing popularity of the Internet, many organizations are racing to get onto the on-ramp to the Information Superhighway. However, with frequent headlines such as 'Hackers' break in at General Electric raises questions about the Net's Security', 'Internet Security Imperiled - Hackers steal data that could threaten computers world-wide' and 'Stanford Computer system infiltrated; Security fears grow', organizations find themselves rethinking their approach to the on-ramp. Is the Internet safe? What do I need to do to protect my organization? Will hackers try to break into my systems? These are questions many organizations are asking themselves today. In order to safely travel along the Information Superhighway, organizations need a strong security framework. Developing such a framework for a computer site, whether it be just a few dozen hosts or several thousand hosts is not an easy task. The security infrastructure for a site is often developed piece-by-piece in response to security incidents which have affected that site over time. Or worse yet, no coordinated effort has been dedicated toward security. The end result is that many sites are still poorly prepared to handle the security dangers of the Internet. This paper presents guidelines for building a successful security infrastructure. The problem is addressed in a cookbook style method. First is a discussion on how to identify your assets and evaluate the threats to those assets; next are suggestions and tips for identifying the weak areas in your security armor. Armed with this information we can begin to think about what you really need for your site and what you can afford. In this stage of the process we examine the different categories of security tools and products that are available and then present some tips for deciding what is best for your site.
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A new family of highly uniform, cubic-shaped Cu 3 VS x Se 4−x (CVSSe; 0 ≤ x ≤ 4) nanocrystals based on earth-abundant materials with intermediate bandgaps (IB) in the visible range is reported, synthesized via a hot-injection method. The IB transitions and optical band gap of the novel CVSSe nanocrystals are investigated using ultraviolet-visible spectroscopy, revealing tunable band gaps that span the visible and near-infrared regimes. The composition-dependent relationships among the crystal phase, optical band gap, and photoluminescence properties of the novel IB semiconductors with progressive substitution of Se by S are examined in detail. High-resolution transmission electron microscopy and scanning electron microscopy characterization confirm the high crystallinity and uniform size (~19.7 nm × 17.2 nm for Cu 3 VS 4 ) of the cubic-shaped nanocrystals. Density functional theory (DFT) calculations based on virtual crystal approximation support the experimental findings, showing good agreement in lattice parameters and band gaps across the CVSSe series and lending confidence that the targeted phases and compositions have been successfully realized. A current conversion efficiency, i.e., incident photon-to-current efficiency, of 14.7% was achieved with the p-type IB semiconductor Cu 3 VS 4 . These novel p-type IB semiconductor nanocrystals hold promise for enabling thin film solar cells with efficiencies beyond the Shockley–Queisser limit by allowing sub-band-gap photon absorption through intermediate-band transitions, in addition to the conventional direct-band-gap transition.
Soil microbial communities can play a large role in plant fitness, including plants’ response to drought. How microbes mediate drought response may also differ across the plants’ life stage, but studies rarely study causal effects of microbes on plant fitness at multiple stages. We conducted a greenhouse experiment on switchgrass (Panicum virgatum L.) to investigate how microbial presence (sterile bulk vs. live bulk soils) and microbial source (communities from bulk vs. rhizosphere soil) affect germination and seedling growth (life-stage) during drought. We also investigated how drought and life-stage alter the assembly of the inoculated communities. Both drought conditions and the absence of microbes reduced germination (49% and 50% fewer seedlings, respectively, p < 0.05), but there were few effects of microbial presence on older seedlings. In addition, microbial source had no effect on the evaluated plant traits, but interestingly, the initially similar bulk and rhizosphere communities became compositionally distinct after 34 days with germinating seeds, but not with seedlings. Therefore, it may be that the plants did respond to microbial source through changes in seed or root exudates, and calls for further study. Finally, while sometimes microbes did benefit plants under drought, we did not find evidence that they are especially beneficial in this condition. We suggest that microbes’ effects differ across plant life stage, and may be both positive and negative. Further research should advance understanding of plant stress tolerance within a framework of plant-microbiome co-development.
High-Z plasma facing components redeposit within the sheath through a combination of two distinct mechanisms: prompt (or geometric-driven) and local (or sheath-driven) redeposition. Experimental efforts are needed to determine the leading-order parameters influencing prompt-vs-local trade-off, which sets the fraction of material entering the scrape-off layer. In preparation for such experiments, leading-order parameters are isolated within the PYEAD-RustBCA-GITR coupled net erosion code using Sobol’ sensitivity analysis. Then, experiments resolving prompt-vs-local trade-off under variation of these leading-order parameters are proposed using an isotopic coupon design with multifaceted diagnostic coverage. The measurability of these experiments is evaluated using synthetic diagnostics.
The present investigation is concerned with the factors which might influence the cycle life vs. depth of discharge relationship, taking into account the rate of loss of cell capacity, the amount of excess capacity built into the cells, and the penalty in capacity loss resulting from the use of deep depths of discharge. 'First principles' are used to develop a cell life model for somewhat arbitrary conditions. This model is then used to estimate the cycle life vs. depth of discharge relationships for 'well behaved' cells. The stochastic variations associated with groupings of single cells are then introduced to the battery pack cycle life model. The term 'well behaved' cell is used to describe a single cell which does not suffer any abrupt failure mode during the course of its operation. It gradually loses capacity for any number of the usual reasons at a rate which is the product of the fractional depth of discharge and a factor which is characteristic of the cell under consideration.
Bonding in the low-lying states of ScO, ScS, VO, and VS is theoretically studied. Excellent agreement is obtained with experimental spectroscopic constants for the low-lying states of ScO and VO. The results for VS and ScS show that the bonding in the oxides and sulfides is similar, but that the smaller electronegativity in S leads to a smaller ionic component in the bonding. The computed D0 of the sulfides are about 86 percent of the corresponding oxides, and the low-lying excited states are lower in the sulfides than in the corresponding oxides. The CPF method is shown to be an accurate and cost-effective method for obtaining reliable spectroscopic constants for these systems.
Exploration mission designers and planners have costing models used to assess the affordability of given missions - but very little data exists on the relative science return produced by different ways of exploring a given region. Doing cost-benefit analyses for future missions requires a way to compare the relative field science productivity of spacesuited humans vs. virtual presence/teleoperation from a nearby habitat or orbital station, vs. traditional terrestrial-controlled rover operations. The goal of this study was to define science-return metrics for comparing human and robotic fieldwork, and then obtain quantifiable science-return performance comparisons between teleoperated rovers and spacesuited humans. Test runs with a simulated 2015-class rover and with spacesuited geologists were conducted at Haughton Crater in the Canadian Arctic in July 2002. Early results imply that humans will be 1-2 orders of magnitude more productive per unit time in exploration than future terrestrially-controlled robots.
Phosphoimidazolide activated ribomononucleotides (*pN, see structure) are useful substrates for the non-enzymatic synthesis of oligonucleotides. In the presence of metal ions, aqueous solutions of *pN yield primarily the two internucleotide-linked (pN2' pN and pN3' pN) and the pyrophosphate-linked (N5' ppN) dimers. Small amounts of cyclic dimers and higher oligomers are also produced. In this study the relative reactivity of 2'-OH vs. 3'-OH was determined from the ratio of the yields of pN2' pN vs. pN3' pN. Experiments were performed at 23 degrees C in the range 7.2 < or = pH < or = 8.4 with substrates that differ in nucleobase (guanosine (G), cytidine (C), uridine (U), and adenosine (A)) and leaving group (imidazole (Im), 2-methylimidazole (2-MeIm) and 2,4-dimethylimidazole (2,4-diMeIm)). Two metal ions (Mg2+ or Mn2+) were employed as catalysts. The conditions used here, i.e. a substrate concentration in the range 0.1 M to 1.0 M and metal ion concentration in the range 0.05 M to 0.2 M, favor base-stacking interactions. The ratio pN2' pN: pN3' pN = 2'-5': 3'-5' was found independent of nucleobase and typically varied between 2 to 3 indicating that the 2'-OH is about 2 to 3 times more reactive than the 3'-OH. *pN with Im, compared to 2-MeIm and 2,4-diMeIm leaving group, produce lower yields of internucleotide linked dimers, and a higher pN2' pN: pN3' pN ratio. Trends in the data, observed with all three leaving groups, suggest an increase in pN2' pN: pN3' pN ratio with decreasing substrate concentration (up to 5.47 with 0.051 M ImpG). The observations are in accord with earlier studies reporting a relative reactivity 2'-5': 3'-5' = 6 to 9 obtained with Im as the leaving group, in dilute nucleotide solutions and under conditions that disfavor stacking. It is speculated that the concentration induced change in the relative reactivity is the result of self-association via base-stacking that enhances selectively the proximity of the 3'-OH of one molecule to the reactive P-N bond of an other molecule. The implication of these conclusions for oligomerization/ligation reactions is discussed.
The kinetics and thermodynamics of elementary reaction steps involved in the catalytic reduction of protons to hydrogen define the reaction landscape for catalysis. The mechanisms can differ in the order of the elementary proton transfer, electron transfer, and bond-forming steps and can be further differentiated by the sites at which protons and electrons localize. Access to fully elucidated mechanistic, kinetic, and thermochemical details of molecular catalysts is crucial to facilitate the development of new catalysts that operate with optimal efficiency, selectivity, and durability. The mechanism by which a catalyst operates, as well as the kinetics and thermodynamics associated with the individual steps, can often be accessed through electroanalytical studies. Here, this Account details the application of cyclic voltammetry to interrogate reaction mechanisms and quantify the kinetics and thermodynamics of elementary reaction steps for a series of molecular catalysts that mediate electrochemical proton reduction. I distinguish the limiting scenarios wherein a catalyst operates under kinetic control vs thermodynamic control, with a focus on detecting how cyclic voltammetry features shift with proton source strength and concentration, as well as scan rate. For systems that operate under kinetic control, catalytic currents are observed at, or slightly positive toward, the formal potential for the redox process that triggers catalysis. Under thermodynamic control, catalytic responses shift as a function of the proton source pKa and effective pH of the solution. After drawing this distinction, we introduce the appropriate voltammetry experiments and accompanying analytical expressions for extracting key metrics from the data. To illustrate analytical strategies to quantify elementary reaction steps of catalysts operating under kinetic control, I describe our studies of proton reduction catalysts Co(dmgBF 2 ) 2 (CH 3 CN) 2 (dmgBF 2 = difluoroboryl-dimethylglyoxime) and [Ni(P 2 Ph N 2 Ph ) 2 ] 2+ (P 2 Ph N 2 Ph = 1,5-phenyl-3,7-phenyl-1,5-diaza-3,7-diphosphacyclooctane). Here, peak shift analysis, foot-of-the-wave analysis, and plateau current analysis are applied to data sets wherein voltammetric response are recorded as a function of catalyst concentration, proton source concentration, proton source strength, and scan rate to quantify rate constants for elementary proton transfer and bond-forming steps in a catalytic cycle. Further, the case study of [Ni(P 2 Ph N 2 Ph ) 2 ] 2+ illustrates how complementary spectroscopic methods can bolster the mechanistic assignment. Collectively, these two studies showcase how detailed mechanistic studies inform on rate-limiting elementary steps in catalysis and other key processes underpinning catalysis. Second, I present analytical strategies to interrogate catalysts operating under thermodynamic control, centered on the case study of [Ni II (P 2 Ph N 2 Bn ) 2 ] 2+ (P 2 Ph N 2 Bn = 1,5-dibenzyl-3,7-diphenyl-1,5-diaza-3,7-diphosphacyclooctane). Here, the application of nonaqueous Pourbaix theory to extract thermodynamic information is introduced, and the construction of a coupled Pourbaix diagram is detailed. This study identifies ligand-based protonation as the key process that places catalysis under thermodynamic control and influences the reaction mechanism. Together, the work detailed in this Account showcases the utility of electroanalytical methods to disentangle complex reaction mechanisms and extract key thermochemical and kinetic parameters for elementary steps of catalysis. Through detailed presentation of the key analytical expressions that underpin these analyses, this Account seeks to facilitate the adoption of cyclic voltammetry by the community to fully extract kinetic, thermochemical, and mechanistic information on electrochemical small-molecule activation.
Temporal fluctuations in redox conditions influence the availability of Fe III and greenhouse gas emissions in humid upland soils. However, the impact of fluctuation duration on biogeochemical processes remains unclear. We hypothesized that rates of Fe III reduction and CH 4 production are sensitive to the duration of soil oxygenation. To test this, surface soil from the Luquillo Forest, Puerto Rico, was subjected to fluctuating redox conditions with an anoxic interval of 6 days followed by oxic intervals of either 8, 24, or 72 h. Shorter oxic intervals enhanced Fe reduction, while longer oxic intervals enhanced CH 4 emissions. As O 2 exposure decreased from 72 to 8 h, Fe reduction rates increased from 0.12 ± 0.02 to 0.26 ± 0.05 mmol kg –1 h –1 , whereas cumulative CH 4 decreased from 44.0 ± 4.7 to 12.7 ± 4.6 μmol kg –1 . 13 C-amino acid spikes were preferentially incorporated into the DNA of iron reducers (Anaeromyxobacter sp.) in the shorter oxic treatment (8 h vs 24 h), suggesting that Fe reducers are less inhibited by shorter periods of oxidation. Conversely, longer oxygen pulses appear to suppress Fe reducers more than methanogens, leading to increased CH 4 emissions. These findings highlight the role of the redox oscillation length in modulating biogeochemical processes and greenhouse gas emissions in soils.
Iron(IV)-oxo intermediates found in iron enzymes and artificial catalysts are competent for H atom abstraction in catalytic cycles. For S = 2 intermediates, both axial and equatorial approaches are well-established. The mechanism for S = 1 sites is not as well understood: an equatorial approach is more energetically favorable, and an axial approach requires crossing from the S = 1 to the S = 2 surface. Here, in this study, we use 1s2p resonant inelastic X-ray scattering (RIXS) and Fe L-edge X-ray absorption spectroscopy on the S = 1 [Fe IV O(TMC)(CH3CN)] 2+ and observe both S = 2 and S = 1 final states, which enables the experimental evaluation of the energetics of the axial and equatorial reactivity of an S = 1 Fe IV O center on its S = 2 vs S = 1 surface. The observation of S = 2 final states in the RIXS spectrum demonstrates significant S = 2 character spin–orbit mixed into the S = 1 ground state.
Protonic ceramic electrolysis cells (PCECs) are an attractive green H 2 production technology, given their intermediate-temperature operating range and ability to produce dry H 2 . However, PCECs will benefit from development of more efficient and durable “triple conducting” anodes where steam is split, H incorporated, and oxygen evolved. In this work, we evaluated the kinetics of the steam-splitting/H incorporation reaction on BaPr 0.9 Y 0.1 O 3–δ (BPY) in comparison to the benchmark Ba 1–x Co 0.4 Fe 0.4 Z r0.1 Y 0.1 O 3–δ (BCFZY) composition, replacing most of the transition metal elements (Co, Fe, Zr) with the lanthanide Pr. We prepared geometrically well-defined perovskite BPY and BCFZY thin films by pulsed laser deposition and performed simultaneous optical transmission relaxation and electrical conductivity relaxation measurements at 400–500 °C in 0.21 atm O 2 during switching of the steam partial pressure to isolate and compare their proton surface exchange coefficients (k). The k values of BPY were comparable to those of BCFZY and more stable over time. According to angle-resolved XPS and STEM-EDS mapping of FIB cross-sections, the surface of BPY exhibited Ba enrichment, Pr deficiency, and Si contamination. In contrast, BCFZY exhibited Ba deficiency throughout, no obvious surface segregation, and less Si contamination. The Ba segregation on the BPY film appears to have promoted steam splitting/H incorporation kinetics even though the more basic surface reacted with the acidic environmental SiO x H y . Faster kinetics observed on stoichiometric BCFZY vs. Ba-deficient BCFZY confirmed the benefit of a high A-site Ba concentration. This result contrasts with most work on perovskites applied in solid oxide electrolysis cell anodes, in which A-site segregation is considered deleterious for surface reaction kinetics.
Here, we report the size-controlled synthesis of ultrasmall (3–8 nm), phase-pure, and stoichiometric Cu 3 VS 4 nanocrystals via direct nucleation of the ternary sulvanite phase. An unusual redshift in optical absorption is observed with decreasing size and attributed to the plasmonic-like nature of valence band–intermediate band transitions.
Complex chalcogenides are renowned for their tunable electronic, magnetic, and optical properties under external stimuli. The MPX 3 family (M = Mn, Ni, Co, V; X = S, Se) is a platform for many exciting discoveries—especially under compression—although CdPS3 is thought to be different because the Cd center possesses a filled 4d shell, which precludes Mottness. Here, we combine synchrotron-based infrared absorbance and Raman scattering spectroscopies with diamond anvil cell techniques, complementary lattice dynamics calculations, and an analysis of the energy landscape to reveal a series of structural phase transitions in CdPS 3 . We find four distinct pressure-driven transitions, with low frequency modes detectable over the full 35 GPa range of our investigation. A group–subgroup analysis along with our first-principles calculations allows us to partially unravel the space group sequence. For instance, the first critical pressure is a monoclinic C2/m to trigonal $\overline{R}$3 transition at 10 GPa. Despite the softness and overall sensitivity to pressure, we do not locate an insulator-to-metal transition in this pressure range, indicating that the energy scale for gap closure is significantly higher than expected. We discuss these findings in terms of force-induced color change and Mott vs band character in this system.
Currently, the ICARUS-T600 liquid argon TPC is collecting data exposed to Booster Neutrino and Numi off-axis beams within the SBN program at Fermilab. A light detection system, based on PMTs deployed behind the TPC wire chambers, is in place to detect vacuum ultraviolet photons produced by ionizing particles in LAr. This system is fundamental for the detector operation, providing an efficient trigger and contributing to the 3D reconstruction of events. Moreover, since the TPC is exposed to a huge flux of cosmic rays due to its operations at shallow depths, the light detection system allows for the time reconstruction of events, contributing to the identification and to the selection of neutrino interactions within the beam spill gates. This contribution will primarily focus on the comparative study (data vs. MC) of light signal of cosmic muons to validate the light emulation.