Laboratoire Procédés, Matériaux et Energie Solaire

Abstract This article presents an XPS study of Ce 3d emission spectra dominated by atomic multiplet effects in core level spectroscopy of rare earth compounds (Ce oxides). Core level spectroscopy has been used to study the electronic states of Ce 3d 5/2 and Ce 3d 3/2 levels in Ce 4+ and Ce 3+ states. The well‐resolved components of Ce 3d 5/2 and Ce 3d 3/2 spin‐orbit components, due to various final states (4f 0 , 4f 1 , 4f 2 configurations), were determined on 3d XPS spectra from commercial powders (CeO 2 , CePO 4 ). These results were used to study the 3d spin‐orbit component of mixed cerium‐titanium oxide. This compound was prepared by co‐melting commercial powders of CeO 2 and TiO 2 at 1800 K under air using a solar furnace with a flux density of 16 MW.m −2 at the focal point of the parabolic concentrator. The mixed oxide Ce 2 Ti 2 O 7 was produced and contained Ce(III) species which may be reactive with water to give back the initial metal oxides and generate hydrogen, a valuable product considered as a promising energy carrier in the future in replacement of oil. The 3d photoemission spectra revealed the presence of mixed components attributed to mainly Ce(III) and Ce(IV) species. Copyright © 2008 John Wiley & Sons, Ltd.

The aim of this paper is to confirm the existence of atmospheric pressure dielectric controlled glow discharge and to describe its main behavior. Electrical measurements, short time exposure photographs, and numerical modeling were used to achieve this task. Experimental observations and numerical simulation are in good agreement. Therefore, the analysis of the calculated space and time variations of the electric field together with the ion and electron densities helps to explain the discharge mechanisms involved, showing the main role played by the electron as well as helium metastable density just before the discharge is turned on.

The Solar Wind Electrons Alphas and Protons (SWEAP) Investigation on Solar Probe Plus is a four sensor instrument suite that provides complete measurements of the electrons and ionized helium and hydrogen that constitute the bulk of solar wind and coronal plasma. SWEAP consists of the Solar Probe Cup (SPC) and the Solar Probe Analyzers (SPAN). SPC is a Faraday Cup that looks directly at the Sun and measures ion and electron fluxes and flow angles as a function of energy. SPAN consists of an ion and electron electrostatic analyzer (ESA) on the ram side of SPP (SPAN-A) and an electron ESA on the anti-ram side (SPAN-B). The SPAN-A ion ESA has a time of flight section that enables it to sort particles by their mass/charge ratio, permitting differentiation of ion species. SPAN-A and -B are rotated relative to one another so their broad fields of view combine like the seams on a baseball to view the entire sky except for the region obscured by the heat shield and covered by SPC. Observations by SPC and SPAN produce the combined field of view and measurement capabilities required to fulfill the science objectives of SWEAP and Solar Probe Plus. SWEAP measurements, in concert with magnetic and electric fields, energetic particles, and white light contextual imaging will enable discovery and understanding of solar wind acceleration and formation, coronal and solar wind heating, and particle acceleration in the inner heliosphere of the solar system. SPC and SPAN are managed by the SWEAP Electronics Module (SWEM), which distributes power, formats onboard data products, and serves as a single electrical interface to the spacecraft. SWEAP data products include ion and electron velocity distribution functions with high energy and angular resolution. Full resolution data are stored within the SWEM, enabling high resolution observations of structures such as shocks, reconnection events, and other transient structures to be selected for download after the fact. This paper describes the implementation of the SWEAP Investigation, the driving requirements for the suite, expected performance of the instruments, and planned data products, as of mission preliminary design review.

Abstract Over the last ten years, expansion of atmospheric pressure plasma solutions for surface treatment of materials has been remarkable, however direct plasma technology for thin film deposition needs still great effort. The objective of this paper is to establish the state of the art on scientific and technologic locks, which have to be opened to consider direct atmospheric pressure plasma‐enhanced chemical vapor deposition (AP‐PECVD) a viable option for industrial application. Basic scientific principles to understand and optimize an AP‐PECVD process are summarized. Laboratory reactor configurations are reviewed. Reference points for the design and use of AP‐PECVD reactors according to the desired thin film properties are given. Finally, solutions to avoid powder formation and to increase the thin film growth rate are discussed. magnified image

This paper is a state of the art of the understanding on the physics of homogeneous dielectric barrier discharges at atmospheric pressure. It is based on the analysis of present and previous work about the behavior of these discharges and the conditions to get them. Mechanisms controlling the homogeneity during gas breakdown and discharge development are successively discussed. The breakdown has to be a Townsend one, the ionization has to be slow enough to avoid a large avalanche development. During the breakdown, the discharge homogeneity is related to the ratio of the secondary emission at the cathode (γ coefficient) on the ionization in the gas bulk (α coefficient). Higher is this ratio, higher is the pressure × gas gap product (Pd) value for which a Townsend breakdown is obtained. Among the phenomena enhancing the secondary emission there is the negative charge of the dielectric on the cathode surface, the trapping of ions in the gas and the existence of excited state having a long lifetime compared to the time between two consecutive discharges. The first phenomenon is always present when the electrodes are covered by a solid dielectric, the second one is related to the formation of a positive column and the third one is specific of the gas. During the discharge development, the homogeneity is mainly controlled by the voltage or the current imposed by the electrical circuit/electrode configuration and by the gas ability to be slowly ionized. Larger is the contribution of a multiple step ionization process like Penning ionization, higher will be the working domain of the discharge. A decrease of the gas voltage during the discharge development is a solution to enhance the contribution of this process. After 20 years of research a lot of mechanisms have been understood however there is still open questions like the nature of the Inhibited homogeneous DBD, surface energy transfers, role of attachment and detachment...

Currently, hydrogen is mainly generated by steam methane reforming, with significant CO2 emissions, thus exacerbating the greenhouse effect. This environmental concern promotes methane cracking, which represents one of the most promising alternatives for hydrogen production with theoretical zero CO/CO2 emissions. Methane cracking has been intensively investigated using metallic and carbonaceous catalysts. Recently, research has focused on methane pyrolysis in molten metals/salts to prevent both reactor coking and rapid catalyst deactivation frequently encountered in conventional pyrolysis. Another expected advantage is the heat transfer improvement due to the high heat capacity of molten media. Apart from the reaction itself that produces hydrogen and solid carbon, the energy source used in this endothermic process can also contribute to reducing environmental impacts. While most researchers used nonrenewable sources based on fossil fuel combustion or electrical heating, concentrated solar energy has not been thoroughly investigated, to date, for pyrolysis in molten media. However, it could be a promising innovative pathway to further improve hydrogen production sustainability from methane cracking. After recalling the basics of conventional catalytic methane cracking and the developed solar cracking reactors, this review delves into the most significant results of the state-of-the-art methane pyrolysis in melts (molten metals and salts) to show the advantages and the perspectives of this new path, as well as the carbon products’ characteristics and the main factors governing methane conversion.

The solar thermochemical splitting of CO2 and H2O with ceria and Zr-doped ceria for CO and H2 production is considered. The two-step process is composed of the thermal reduction of the ceria-based compound followed by the oxidation of the nonstoichiometric ceria with CO2/H2O to generate CO/H2, respectively. As a reference, the reactivity of pure undoped ceria was first characterized during successive thermochemical cycles using a thermobalance. Then, Zr0.25Ce0.75O2 was synthesized using different soft chemical synthesis routes to evaluate the influence of the powder morphology on the reactivity during the reduction and the oxidation steps. The reduction yield of ceria was significantly improved by doping with Zr as well as the CO/H2 production yields, but the kinetic rates of the oxidation step for doped ceria were lower than for pure ceria. CO and H2 production of 241 and 432 μmol/g, respectively, have been measured. A kinetic analysis of the CO2-splitting step allowed one to estimate the activation energy that ranged between 83 and 103 kJ/mol depending on the synthesis route of Zr0.25Ce0.75O2. The powder morphology played an important role on the materials cyclability. In contrast to pure ceria, Zr-doped ceria showed possible deactivation when cycling at 1400 °C, and the influence of the synthesis route on the thermal stability was evidenced. The thermally resistant powders with porous morphology ensured stable reactivity during cycling. The Zr-doped ceria synthesized via pechini process produced the largest amounts of CO/H2 during successive cycles.

Ceria has emerged as an attractive candidate for solar thermochemical hydrogen production; however, the necessary temperatures for CeO2 reduction to Ce2O3 are too high for conventional solar concentrating systems, while the reduction to nonstoichiometric CeO2−δ below 1500 °C shows restricted chemical yield. Doping ceria with another metal can improve the reactivity at lower temperatures. This study focuses on the doping of ceria with different metals such as tantalum or trivalent lanthanides (La, Sm, and Gd) to form binary oxides and on the doping of ceria–zirconia solid solutions to form ternary oxides. Ceria materials doped with tantalum show a high reducibility, but the structural evolution during thermal treatment leads to the formation of a secondary phase that hinders the water dissociation reaction. Besides, the doping with trivalent lanthanides results in an improved thermal stability during consecutive cycles, while the hydrogen production is unchanged compared to ceria. Concerning ternary oxides, the addition of 1% gadolinium to ceria–zirconia solid solutions results in the production of 338.2 μmol (7.58 mL) of hydrogen per gram during one cycle with the O2-releasing step at 1400 °C and the H2-generation step at 1050 °C. This production is higher than the one observed for undoped ceria–zirconia. The addition of lanthanum enhances the thermal stability of ceria–zirconia solid solution, thus leading to stable reactivity during repeated cycles.

This study addresses the synthesis, characterization, and thermochemical redox performance evaluation of perovskites and parent structures (Ruddlesden–Popper phases) as a class of oxygen-exchange materials for hydrogen generation via solar two-step water splitting. The investigated materials are LaxSr1–xMO3 (M = Mn, Co, Fe), BaxSr1–x(Co,Fe)O3, LaSrCoO4, and LaSrFeO4, also used as mixed ionic-electronic conductors in fuel cells. Temperature-programmed reduction, powder X-ray diffraction, and thermogravimetric analysis were used to obtain a preliminary assessment of these materials performances. Most of the perovskites studied here stand out by larger thermal reduction capabilities and oxygen vacancies formation at modest temperatures in the range 1000–1400 °C when compared with reference nonstoichiometric compounds such as spinel ferrites or fluorite-structured ceria-based materials. In addition, these materials offer noticeable access to metallic valence transitions during reoxidation in steam atmosphere that are not available in stoichiometric oxides. The promising behaviors characterized here are discussed in regard to the crystal chemistry of the perovskite and parent phases.

Abstract The Fe‐MgO core‐shell morphology is proposed within the single‐domain nanoparticle regime as an enhanced magnetically driven hyperthermia carrier. The combinatory use of metallic iron as a core material together with the increased particle size (37–65 nm) triggers the tuning of dipolar interactions between particles and allows for further enhancement of their collective heating efficiency via concentration control. A theoretical universal estimation of hysteresis losses reveals the role of dipolar interactions on heating efficiency and outlines the strong influence of coupling effects on hyperthermia opening a novel roadmap towards multifunctional heat‐triggered theranostics particles.

This paper presents a stochastic framework for the optimization of microgrids that has the functionality of providing flexibility services to System Operators (SOs) considering uncertainties in the energy forecast. The methodology is developed with the aim of being applied to complex microgrids composed of different distributed energy resources and hybrid energy storage systems (ESS). The associated optimization problem is operated in two stages: the first one performs a stochastic optimization of the microgrid in order to reserve an up/down regulation capacity with which to deal with the energy forecast uncertainties of the microgrid. The different microgrid devices are optimized by considering their operational costs in order to achieve their optimal operation in the Day-Ahead Market (DM). The second stage is used to re-schedule the initial planning according to the signal request and an economic offer from the SO. The control problem is developed using Stochastic Model Predictive Control (SMPC) techniques and Mixed-Integer Quadratic Programming (MIQP), owing to the presence of logic, integer, mixed and probabilistic variables. The simulation results show that the proposed methodology reduces the risk of undergoing up/down-penalty deviations in the Regulation Service Market (RM), also being able to provide flexibility services to the SOs, despite being subject to uncertainties in the energy forecast carried out for the microgrid.

Ceria-type materials were investigated as reactive chemical intermediates, in view of solar thermochemical hydrogen production via two-step water-splitting. Ceria/zirconia mixed oxides and ceria doped with yttrium, lanthanum, praseodymium, or gadolinium were studied using a thermobalance to evaluate their thermal reduction capacity in inert atmosphere and their subsequent reactivity with water steam to generate hydrogen. Ceria/zirconia materials present the highest reduction yields with a noticeable linear increase as a function of the zirconium content (in the range 0–54% Zr), while the gravimetric amount of O2 released during reduction tends to level off for Zr atomic contents above 25%. Temperature-programmed reduction experiments demonstrate that the zirconium insertion favors the bulk reduction. The addition of different dopants (among Y, La, Pr, and Gd) did not affect the global materials reducibility, although it should favor the material thermal stability during repeated cycles. The marked effect of the synthesis method of the material and of the temperature of the reduction reaction on the reactivity of ceria/zirconia was highlighted. In addition, the beneficial influence of decreasing the system total pressure for improving the thermal reduction of ceria/zirconia was experimentally evidenced, offering new prospects for operating a solar thermochemical reactor.

Solar thermal energy storage is used in many applications, from building to concentrating solar power plants and industry. The temperature levels encountered range from ambient temperature to more than 1000 °C, and operating times range from a few hours to several months. This paper reviews different types of solar thermal energy storage (sensible heat, latent heat, and thermochemical storage) for low- (40–120 °C) and medium-to-high-temperature (120–1000 °C) applications.

We have investigated by (27)Al nuclear magnetic resonance spectroscopy some compositions in the Ln(2)O(3)-Al(2)O(3)-SiO2 (Ln = Y or La) ternary phase diagram containing more than 60 mol % of SiO2. One- and two-dimensional high-field (17.6 T) high-speed (30 kHz) magic angle spinning experiments have been performed along with simulations of the spectra to quantify the amount of penta-coordinated aluminum present in those glasses as a function of composition. Very high-temperature experiments have allowed to follow selected samples from 2200 degrees C down to 1700 degrees C and hence to characterize the aluminum coordination state and dynamics in those liquids. The present study re-enforces the current view that "minor" species such as penta-coordinated aluminum are actually present in a considerable amount in aluminosilicate glasses, and high-temperature liquids at and above the charge compensation join. The high-field strength of Y3+ and La3+ reveal, for the first time in glasses, a different mean electric field gradient perceived by the tetra- and penta-coordinated aluminum environments. The movements responsible for the NMR relaxation of aluminum in the high-temperature liquid are shown to be uncorrelated with the movements responsible for the macroscopic shear viscosity. Results obtained both on glasses and in situ at high-temperature suggest a preferential localization of Ln3+ nearby tetra-coordinated aluminum species, with possible formation of tricluster and/or Ln3+ coordination changes.

Solar thermochemical processes have the potential to efficiently convert high-temperature solar heat into storable and transportable chemical fuels such as hydrogen. In such processes, the thermal energy required for the endothermic reaction is supplied by concentrated solar energy and the hydrogen production routes differ as a function of the feedstock resource. While hydrogen production should still rely on carbonaceous feedstocks in a transition period, thermochemical water-splitting using metal oxide redox reactions is considered to date as one of the most attractive methods in the long-term to produce renewable H2 for direct use in fuel cells or further conversion to synthetic liquid hydrocarbon fuels. The two-step redox cycles generally consist of the endothermic solar thermal reduction of a metal oxide releasing oxygen with concentrated solar energy used as the high-temperature heat source for providing reaction enthalpy; and the exothermic oxidation of the reduced oxide with H2O to generate H2. This approach requires the development of redox-active and thermally-stable oxide materials able to split water with both high fuel productivities and chemical conversion rates. The main relevant two-step metal oxide systems are commonly based on volatile (ZnO/Zn, SnO2/SnO) and non-volatile redox pairs (Fe3O4/FeO, ferrites, CeO2/CeO2−δ, perovskites). These promising hydrogen production cycles are described by providing an overview of the best performing redox systems, with special focus on their capabilities to produce solar hydrogen with high yields, rapid reaction rates, and thermochemical performance stability, and on the solar reactor technologies developed to operate the solid–gas reaction systems.

Enhancement of Gilbert damping in polycrystalline cobalt thin-film multilayers of various thicknesses, overlayered with copper or iridium, was studied in order to understand the role of local interface structure in spin pumping. X-ray diffraction indicates that cobalt films less than 6 nm thick have strong fcc(111) texture while thicker films are dominated by hcp(0001) structure. The intrinsic damping for cobalt thicknesses above 6 nm is weakly dependent on cobalt thickness for both overlayer materials, and below 6 nm the iridium overlayers show higher damping enhancement compared to copper overlayers, as expected due to spin pumping. The interfacial spin mixing conductance is significantly enhanced in structures where both cobalt and iridium have fcc(111) structure in comparison to those where the cobalt layer has subtly different hcp(0001) texture at the interface.

Current technologies of concentrated solar power plants (CSP) are under extensive industrial development but still suffer from lack of adapted thermal energy storage (TES) materials and systems. In the case of extended storage (some hours), thousands of tonnes of materials are concerned leading to high investment cost, high energy and GHG contents and major conflicts of use. In this paper, recycled industrial ceramics made by vitrification of asbestos containing wastes (ACW) are studied as candidates to be used as sensible TES material. The material presents no hazard, no environmental impact, good thermophysical properties (λ= 1.4 W m−1 K−1; Cp = 1025 J kg−1 K−1; ρ= 3100 kg m−3) and at very low investment cost. Thanks to the vitrification process of the wastes, the obtained ceramics is very stable up to 1200 °C and can be directly manufactured with the desired shape. The vitrified ACW can be used as TES material for all kinds of the CSP processes (from medium up to high concentration levels) with properties in the same range than other available materials but with lower cost and without conflict of use. The proposed approach leads also to sustainable TES allowing a pay back of the energy needed for the initial waste treatment. Furthermore, this new use of the matter can enhance the waste treatment industry instead of land fill disposal.

In the framework of the EU-project SOLZINC, a 300-kW solar chemical pilot plant for the production of zinc by carbothermic reduction of ZnO was experimentally demonstrated in a beam-down solar tower concentrating facility of Cassegrain optical configuration. The solar chemical reactor, featuring two cavities, of which the upper one is functioning as the solar absorber and the lower one as the reaction chamber containing a ZnO/C packed bed, was batch-operated in the 1300–1500 K range and yielded 50 kg/h of 95%-purity Zn. The measured energy conversion efficiency, i.e., the ratio of the reaction enthalpy change to the solar power input, was 30%. Zinc finds application as a fuel for Zn/air batteries and fuel cells, and can also react with water to form high-purity hydrogen. In either case, the chemical product is ZnO, which in turn is solar-recycled to Zn. The SOLZINC process provides an efficient thermochemical route for the storage and transportation of solar energy in the form of solar fuels.

The solar wind has been measured directly from 0.3 AU outward, and the Sun's atmosphere has been imaged from the photosphere out through the corona. These observations have significantly advanced our understanding of the influence of the Sun's varying magnetic field on the structure and dynamics of the corona and the solar wind. However, how the corona is heated and accelerated to produce the solar wind remains a mystery. Answering these fundamental questions requires in situ observations near the Sun, from a few solar radii ( R S ) out to ∼20 R S , where the internal, magnetic, and turbulent energy in the coronal plasma is channeled into the bulk energy of the supersonic solar wind. A mission to make such observations has long been a top priority of the solar and space physics community. The recent Solar Probe study has proven that such a mission is technically feasible and can be accomplished within reasonable resources.

A-site and B-site substituted lanthanum manganite perovskites were synthesized and characterized for application in two-step metal oxide redox cycles for thermochemical splitting of CO₂.