Oxidation of PCEA nuclear graphite by low water concentrations in helium
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Concentrated Solar Power (CSP) is considered as a viable large-scale renewable energy source to produce electricity. However, current costs to produce electricity from CSP are not cost competitive as compared to the traditional energy generation technologies based on fossil fuels and nuclear. It is envisioned that development of high efficiency and high heat capacity thermal storage fluids will increase system efficiency, reduce structural storage volume, and hence, contribute to reducing costs. Particularly, with respect to CSP, current high temperature energy storage fluids, such as molten salts, are relatively limited in terms of their thermal energy storage capacity and thermal conductivity. The current work explores possibility of boosting the thermal storage capacity of molten salts through latent heat of added phase change materials. We studied the advantage Of adding coated Zn micron-sized particles to alkali chloride salt eutectic for enhanced thermal energy storage. Zinc particles (0.6 mu m and 5 mu m) obtained from commercial source were coated with an organo-phosphorus shell to improve chemical stability and to prevent individual particles from coalescing with one another during melt/freeze cycles. Thermal cycling tests (200 melt/freeze cycles) showed that coated Zn particles have good thermal stability and are chemically inert to alkali chloride salt eutectic in both N-2 and in air atmospheres. Elemental mapping of the cross-sectional view of coated Zn particles from the composite after thermal cycles showed no signs of oxidation, agglomeration or other type of particle degradation. The measured enhancement in volumetric thermal storage capacity of the composite with just similar to 10 vol% of coated Zn particles over the base chloride salt eutectic varies from 15% to 34% depending on cycling temperature range (Delta T = 50 degrees C -100 degrees C. (C) 2015 Elsevier Ltd. All rights reserved.
Concentrated solar power (CSP) plants have the potential to provide 24 h, renewable electricity. Current CSP systems have high capital and operational costs which makes the levelized cost of electricity uncompetitive with conventional techniques. Recent experimental research has shown the potential of small unit cells (up to 2 × 2 cm) containing micropin arrays (D H < 1 mm) to operate efficiently at high incident flux (>140 W cm -2 ) using supercritical carbon dioxide as the working fluid. Applying this technology to CSP systems would result in a smaller central receiver, which would reduce thermal losses, increase receiver efficiency and reduce the capital cost of the receiver component. This study investigates and addresses the practical thermal and hydraulic issues in numbering up these small unit cells into numerous parallel cells within an integrated module design. A thermal hydraulic network model is developed to quantify the distribution and the overall receiver efficiency of an integrated module. This model is used to specify maximum allowable unit cell size and header dimensions to maintain acceptable thermal performance and pressure loss. Once a module design was finalized, parametric studies were performed to study the effects of varying incident flux on flow distribution and thermal performance of the module. Finally, the results show that an integrated module design can be achieved with less than 5% flow maldistribution and a pressure drop acceptable to the remainder of the system.
High-nickel layered-oxide cathodes (LiNi x Mn y Co 1-x-y O 2 , x ≥ 0.8) exhibit high capacities, but also experience rapid capacity fade during cycling, and are susceptible to heat generation and gas release. Advanced electrolytes, such as localized high-concentration electrolytes (LHCE), substantially stabilize the cathode during cycling and have lower flammability than conventional electrolytes, but gas generation with these electrolytes is yet to be assessed. We demonstrate here that gas generation from a high-nickel cathode in an LHCE is half as much as in a conventional electrolyte at 4.4 V. The gas generation in LHCE is further reduced at 4.3 V, but the LHCE generates a similar amount of gas as the conventional electrolyte at 4.6 V. Neither electrolyte can prevent gas generation after cycling; cathodes after 200 cycles generate similar amounts of gas as pristine cathodes during high-voltage hold. Finally, it is shown that in both electrolytes, oxygen from the cathode lattice plays a critical role in gas generation.
Unconventional methods to exploit monocrystalline silicon and other established materials in photovoltaic (PV) systems can create new engineering opportunities, device capabilities and cost structures. Here we show a type of composite luminescent concentrator PV system that embeds large scale, interconnected arrays of microscale silicon solar cells in thin matrix layers doped with luminophores. Photons that strike cells directly generate power in the usual manner; those incident on the matrix launch wavelength-downconverted photons that reflect and waveguide into the sides and bottom surfaces of the cells to increase further their power output, by more than 300% in examples reported here. Unlike conventional luminescent photovoltaics, this unusual design can be implemented in ultrathin, mechanically bendable formats. Furthermore, detailed studies of design considerations and fabrication aspects for such devices, using both experimental and computational approaches, provide quantitative descriptions of the underlying materials science and optics.
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Luminescent solar concentrators (LSCs) can serve as large-area sunlight collectors for terrestrial and space-based photovoltaics. Due to their high emission efficiencies and readily tunable emission and absorption spectra, colloidal quantum dots have emerged as a new and promising type of LSC fluorophore. Spectral tunability of the quantum dots also facilitates the realization of stacked multilayered LSCs, where enhanced performance is obtained through spectral splitting of incident sunlight, as in multijunction photovoltaics. Here, we demonstrate a large-area (>230 cm 2 ) tandem LSC based on two types of nearly reabsorption-free quantum dots spectrally tuned for optimal solar-spectrum splitting. This prototype device exhibits a high optical quantum efficiency of 6.4% for sunlight illumination and solar-to-electrical power conversion efficiency of 3.1%. In conclusion, the efficiency gains due to the tandem architecture over single-layer devices quickly increase with increasing LSC size and can reach more than 100% in structures with window sizes of more than 2,500 cm 2 .
Lead chalcogenides have exhibited their irreplaceable role as thermoelectric materials at the medium temperature range, owing to highly degenerate electronic bands and intrinsically low thermal conductivities. PbTe-PbS pseudo-binary has been paid extensive attentions due to the even lower thermal conductivity which originates largely from the coexistence of both alloying and phase-separated precipitations. To investigate the competition between alloying and phase separation and its pronounced effect on the thermoelectric performance in PbTe-PbS, we systematically studied Spark Plasma Sintered (SPSed), 3 at% Na- doped (PbTe) 1-x (PbS)x samples with x=10%, 15%, 20%, 25%, 30% and 35% by means of transmission electron microscopy (TEM) observations and theoretical calculations. Corresponding to the lowest lattice thermal conductivity as a result of the balance between point defect- and precipitates- scattering, the highest figure of merit ZT~2.3 was obtained at 923 K when PbS phase fraction x is at 20%. The consistently lower lattice thermal conductivities in SPSed samples compared with corresponding ingots, resulting from the powdering and follow-up consolidation processes, also contribute to the observed superior ZT. Notably, the onset of carrier concentration modulation ~600 K due to excessive Na’s diffusion and re-dissolution leads to the observed saturations of electrical transport properties, which is believed equally crucial to the outstanding thermoelectric performance of SPSed PbTe-PbS samples.
Caustic conditions are often employed for dissolution of a wide variety of minerals, where ion sorption, surface diffusion, and interfacial organization impact surface reactivity. In the case of gibbsite, gamma-Al(OH)3, the chemistry at the NaOH(aq) interface is deeply intertwined with industrial processing of aluminum, including metal production and the disposition of Al-containing wastes. To date, little is known about the structure, speciation, and dynamic behavior of gibbsite interfaces (and that of many other minerals) with NaOH(aq)—particularly as a function of ionic strength. Yet concentration-dependent interfacial organization and dynamics are a critical starting point to develop a fundamental understanding of the factors that influence dissolution. This work reports equilibrium molecular dynamics simulations of the gamma-Al(OH)3:NaOH(aq) interface, revealing the sorption behavior and speciation of ions from 0.5–10 M [NaOH]. As inner-sphere complexes, Na+ primarily coordinates to the side of the gibbsite hexagonal cavities, while OH accepts hydrogen-bonding from the surface-OH groups. The mobility of inner-sphere Na+ and OH ions is significantly reduced due to a strong surface affinity in comparison to previous reports of NaCl, CaCl2, or BaCl2 electrolytes. At high [NaOH], contact ion pairing that is observed in the bulk solution is partially disrupted upon sorption to the gibbsite surface by the individual ion–surface interactions. The molecular-scale changes to surface speciation and competition between ion–surface vs. ion–ion interactions influence surface characterization of gibbsite and potential dissolution processes, providing a valuable baseline for starting conditions needed within future reactive molecular simulations.
The local structures of six perovskite compounds containing equal amounts of manganese and ruthenium on the B-site have been investigated by neutron and x-ray pair distribution function analysis. The compounds SrMn{sub 0.5}Ru{sub 0.5}O{sub 3}, Sr{sub 0.5}Ca{sub 0.5}Mn{sub 0.5}Ru{sub 0.5}O{sub 3}, and CaMn{sub 0.5}Ru{sub 0.5}O{sub 3} were studied to investigate the effects of pure chemical pressure on the local structure and valency ratio between Mn{sup 3+}/Ru{sup 5+} and Mn{sup 4+}/Ru{sup 4+}. Reverse Monte Carlo simulations confirm that there is a shift in the B-site cation charge distribution from nearly equal amounts of Mn{sup 3+}, Ru{sup 5+}, Mn{sup 4+}, and Ru{sup 4+} for SrMn{sub 0.5}Ru{sub 0.5}O{sub 3} to primarily Mn{sup 4+} and Ru{sup 4+} for CaMn{sub 0.5}Ru{sub 0.5}O{sub 3}. The compounds Ba{sub 0.5}La{sub 0.5}Mn{sub 0.5}Ru{sub 0.5}O{sub 3}, Ca{sub 0.5}La{sub 0.5}Mn{sub 0.5}Ru{sub 0.5}O{sub 3}, and Sr{sub 0.5}Ca{sub 0.25}La{sub 0.25}Mn{sub 0.5}Ru{sub 0.5}O{sub 3} were also investigated to study the effects of changing the charge of the A-site cation. Although substitution of La{sup 3+} for a divalent alkaline earth ion increases the Mn{sup 3+} content, this series of compounds also shows a relative increase in the concentration of Mn{sup 4+} as the average size of the A-site cation is decreased. In all compounds the octahedra containing Mn{sup 3+} are found to be Jahn-Teller distorted regardless of whether or not long-range orbital ordering is observed, while the Ru-centered octahedra are symmetric. No evidence for short-range cation ordering at either the A- or B-sites was found for any of the compositions. This study also reports that locally the A-site cations lie closer to the Mn ions than to the Ru ions and this asymmetry appears to be correlated to the degree of octahedral tilting.
This work is motivated by the need for large-scale simulations to extract physical information on the iron-chromium system that is a binary model alloy for ferritic steels used or proposed in many nuclear applications. From first-principles calculations and the experimental critical temperature we build a new energetic rigid lattice model based on pair interactions with concentration and temperature dependence. Density functional theory calculations in both norm-conserving and projector augmented-wave approaches have been performed. A thorough comparison of these two different ab initio techniques leads to a robust parametrization of the Fe-Cr Hamiltonian. Mean-field approximations and Monte Carlo calculations are then used to account for temperature effects. The predictions of the model are in agreement with the most recent phase diagram at all temperatures and compositions. The solubility of Cr in Fe below 700 K remains in the range of about 6 to 12%. It reproduces the transition between the ordering and demixing tendency and the spinodal decomposition limits are also in agreement with the values given in the literature.
The electron-phonon interaction is well known to create major resistance to electron transport in metals and semiconductors, whereas fewer studies are directed to its effect on phonon transport, especially in semiconductors. Herein we calculate the phonon lifetimes due to scattering with electrons (or holes), combine them with the intrinsic lifetimes due to the anharmonic phonon-phonon interaction, all from first principles, and evaluate the effect of the electron-phonon interaction on the lattice thermal conductivity of silicon. Unexpectedly, we find a significant reduction of the lattice thermal conductivity at room temperature as the carrier concentration goes above 1019 cm –3 (the reduction reaches up to 45% in p-type silicon at around 1021 cm –3 ), a range of great technological relevance to thermoelectric materials.
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Recent studies have shown the potential for nanocrystalline metals to possess excellent fatigue resistance compared to their coarse-grained counterparts. Although the mechanical properties of nanocrystalline metals are believed to be particularly susceptible to material defects, a systematic study of the effects of geometric discontinuities on their fatigue performance has not yet been performed. In the present work, nanocrystalline Ni–40 wt%Fe containing both intrinsic and extrinsic defects were tested in tension–tension fatigue. The defects were found to dramatically reduce the fatigue resistance, which was attributed to the relatively high notch sensitivity in the nanocrystalline material. Microstructural analysis within the crack-initiation zones underneath the defects revealed cyclically-induced abnormal grain growth (AGG) as a predominant deformation and crack initiation mechanism during high-cycle fatigue. Furthermore, the onset of AGG and the ensuing fracture is likely accelerated by the stress concentrations, resulting in the reduced fatigue resistance compared to the relatively defect-free counterparts.
This continuation is a synthesis of the first three tasks of the first year of the project. Hence, we try to follow as much as possible the outline of the SOPO instead of a purely chronological order. For each task, we remind the SOPO objective. We then present our approaches and our results. We start by discussing the objectives and results of the Task 1.1 that mainly consisted in investigating the unit cell of the metasurface concentrators. We then discuss the Task 1.2 that describes the strategies that can be used to design broad angle metasurfaces. Finally, we present the fabrication details and the experimental setups in the last part of the report that mainly corresponds to the Task 1.3.
The invention provides a cathode active material having a discrete change in concentrations of a first base region and a second pulse region. Also provided is a method for preparing a cathode active material, the method having the steps: supplying chelating agent, aqueous basic solution and a first aqueous metal salt solution to a reactor to create a base region; supplying a second aqueous metal-salt solution to a reactor to form a pulse region, wherein the second aqueous metal-salt solution is intermittently or continuously added during or after the creation of the base region; thermally treating the base region and the pulse region to create active metal precursors; mixing the precursors with lithium salt to produce a mixture; and thermally treating the mixture.
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