Babikov, Yurii L.; Mikhailenko, Semen N.; Barbe, Alain; Tyuterev, Vladimir G.
Spectroscopy and Molecular Properties of Ozone ("S&MPO") is an Internet accessible information system devoted to high resolution spectroscopy of the ozone molecule, related properties and data sources. S&MPO contains information on original spectroscopic data (line positions, line intensities, energies, transition moments, spectroscopic parameters) recovered from comprehensive analyses and modeling of experimental spectra as well as associated software for data representation written in PHP Java Script, C++ and FORTRAN. The line-by-line list of vibration-rotation transitions and other information is organized as a relational database under control of MySQL database tools. The main S&MPO goal is to provide access to all available information on vibration-rotation molecular states and transitions under extended conditions based on extrapolations of laboratory measurements using validated theoretical models. Applications for the S&MPO may include: education/training in molecular physics, radiative processes, laser physics; spectroscopic applications (analysis, Fourier transform spectroscopy, atmospheric optics, optical standards, spectroscopic atlases); applications to environment studies and atmospheric physics (remote sensing); data supply for specific databases; and to photochemistry (laser excitation, multiphoton processes). The system is accessible via Internet on two sites: http://smpo.iao.ru and http://smpo.univ-reims.fr.
Huotari, Simo; Suljoti, Edlira; Sahle, Christoph J.; Raedel, Stephanie; Monaco, Giulio; de Groot, Frank M. F.
We report high-resolution x-ray Raman scattering studies of high-order multipole spectra of rare earth 4d -> 4f excitations (the N-4,N-5 absorption edge) in nanoparticles of the phosphates LaPO4, CePO4, PrPO4, and NdPO4. We also present corresponding data for La 5p -> 5d excitations (the O-2,O-3
Znamierowska, T.; Mizer, D.
The system Nd(PO 3 ) 3 - KPO 3 has been investigated by differential thermal analysis (during heating), thermogravimetric analysis, mass spectrometry, Raman spectroscopy and X-ray powder diffraction and its phase diagram was proposed. It was discovered that initial metaphosphates react at a 1:1 molar ratio forming intermediate compound KNd(PO 3 ) 4 . It was found that it melts incongruently at 854 o C giving Nd(po)3) 3 and a liquid rich in KPO 3 . Phosphate KNd(PO 3 ) 4 is stable down to room temperature and does not show any polymorphic transitions. (author)
Anfimova, Tatiana; Bjerrum, Niels J.; Li, Qingfeng
The goal of the present study was to obtain a comprehensive knowledge about synthesis conditions, structure, thermal behavior and conductivity properties of neodymiumorthophosphates in order to analyze of use this material in intermediate temperature fuel cells due to their thermal and chemical...... stability properties.The impedance spectroscopy technique (IS) was used to measure the conductivity. The conductivity of composites observed to be lower than conductivity of pure CsH2PO4 but had improved sufficiently conductivity of pure NdPO4·nH2O...
Taghavi, Reza; Seifi, Ali Reza; Samet, Haidar
Environmental concerns besides fuel costs are the predominant reasons for unprecedented escalating integration of wind turbine on power systems. Operation and planning of power systems are affected by this type of energy due to the intermittent nature of wind speed inputs with high uncertainty in the optimization output variables. Consequently, in order to model this high inherent uncertainty, a PRPO (probabilistic reactive power optimization) framework should be devised. Although MC (Monte-Carlo) techniques can solve the PRPO with high precision, PEMs (point estimate methods) can preserve the accuracy to attain reasonable results when diminishing the computational effort. Also, this paper introduces a methodology for optimally dispatching the reactive power in the transmission system, while minimizing the active power losses. The optimization problem is formulated as a LFP (linear fuzzy programing). The core of the problem lay on generation of 2m + 1 point estimates for solving PRPO, where n is the number of input stochastic variables. The proposed methodology is investigated using the IEEE-14 bus test system equipped with HVDC (high voltage direct current), UPFC (unified power flow controller) and DFIG (doubly fed induction generator) devices. The accuracy of the method is demonstrated in the case study. - Highlights: • This paper uses stochastic loads in optimization process. • AC–DC load flow is modified to use some advantages of DC part in optimization process. • UPFC and DFIG are simulated in a way that could be effective in optimization process. • Fuzzy set has been used as an uncertainty analysis tool in the optimization
Li, Jia; Lam, Edmund Y.
Mask topography effects need to be taken into consideration for more advanced resolution enhancement techniques in optical lithography. However, rigorous 3D mask model achieves high accuracy at a large computational cost. This work develops a combined source, mask and pupil optimization (SMPO) approach by taking advantage of the fact that pupil phase manipulation is capable of partially compensating for mask topography effects. We first design the pupil wavefront function by incorporating primary and secondary spherical aberration through the coefficients of the Zernike polynomials, and achieve optimal source-mask pair under the condition of aberrated pupil. Evaluations against conventional source mask optimization (SMO) without incorporating pupil aberrations show that SMPO provides improved performance in terms of pattern fidelity and process window sizes.
Rare earth based materials have recently attracted considerable attention as potential eco-friendly colourants for low temperature as well as high temperature applications. In the present study, we have synthesized a series of Ca-doped PrPO4 compounds with the general formula, Pr1–CaPO4 ( = 0–0.4 in steps of 0.1) ...
Babikov, Yurii L.; Mikhailenko, Semen N.; Barbe, Alain; Tyuterev, Vladimir G.
Spectroscopy and Molecular Properties of Ozone (“S and MPO”) is an Internet accessible information system devoted to high resolution spectroscopy of the ozone molecule, related properties and data sources. S and MPO contains information on original spectroscopic data (line positions, line intensities, energies, transition moments, spectroscopic parameters) recovered from comprehensive analyses and modeling of experimental spectra as well as associated software for data representation written in PHP Java Script, C++ and FORTRAN. The line-by-line list of vibration–rotation transitions and other information is organized as a relational database under control of MySQL database tools. The main S and MPO goal is to provide access to all available information on vibration–rotation molecular states and transitions under extended conditions based on extrapolations of laboratory measurements using validated theoretical models. Applications for the S and MPO may include: education/training in molecular physics, radiative processes, laser physics; spectroscopic applications (analysis, Fourier transform spectroscopy, atmospheric optics, optical standards, spectroscopic atlases); applications to environment studies and atmospheric physics (remote sensing); data supply for specific databases; and to photochemistry (laser excitation, multiphoton processes). The system is accessible via Internet on two sites: (http://smpo.iao.ru) and (http://smpo.univ-reims.fr). - Highlights: • S and MPO – spectroscopic databank and information system. • S and MPO – useful tools for ozone spectroscopy. • Description of an Internet accessible information system
Babikov, Yurii L. [V.E. Zuev Institute of Atmospheric Optics SB RAS, 1, Academician Zuev Square, Tomsk 634021 (Russian Federation); Tomsk State University, Tomsk 634050 (Russian Federation); Mikhailenko, Semen N., E-mail: email@example.com [V.E. Zuev Institute of Atmospheric Optics SB RAS, 1, Academician Zuev Square, Tomsk 634021 (Russian Federation); Barbe, Alain; Tyuterev, Vladimir G. [Groupe de Spectrométrie Moléculaire et Atmosphérique, UMR CNRS 7331, UFR Sciences Exactes et Naturelles, BP 1039, 51687 Reims Cedex 2 (France)
Spectroscopy and Molecular Properties of Ozone (“S and MPO”) is an Internet accessible information system devoted to high resolution spectroscopy of the ozone molecule, related properties and data sources. S and MPO contains information on original spectroscopic data (line positions, line intensities, energies, transition moments, spectroscopic parameters) recovered from comprehensive analyses and modeling of experimental spectra as well as associated software for data representation written in PHP Java Script, C++ and FORTRAN. The line-by-line list of vibration–rotation transitions and other information is organized as a relational database under control of MySQL database tools. The main S and MPO goal is to provide access to all available information on vibration–rotation molecular states and transitions under extended conditions based on extrapolations of laboratory measurements using validated theoretical models. Applications for the S and MPO may include: education/training in molecular physics, radiative processes, laser physics; spectroscopic applications (analysis, Fourier transform spectroscopy, atmospheric optics, optical standards, spectroscopic atlases); applications to environment studies and atmospheric physics (remote sensing); data supply for specific databases; and to photochemistry (laser excitation, multiphoton processes). The system is accessible via Internet on two sites: (http://smpo.iao.ru) and (http://smpo.univ-reims.fr). - Highlights: • S and MPO – spectroscopic databank and information system. • S and MPO – useful tools for ozone spectroscopy. • Description of an Internet accessible information system.
Heuser, Julia Maria
The safe disposal of radioactive waste in deep geological formations is a challenging task of present and future generations. Innovative strategies as the conditioning of radionuclides in ceramic matrices can make a contribution here. This work points out monazite-type ceramics as potential waste forms for minor actinides and Pu. Several aspects concerning nuclear disposal as well as fundamental structural information were investigated. Lanthanide phosphate endmembers (LnPO 4 ) within the stability field of monazite (Ln = La-Gd) were synthesised within the scope of this work. To extend the knowledge of monazite phases, monoclinic TbPO 4 - and DyPO 4 -phases were prepared and characterised. Tb- and Dy-phosphates are situated in the xenotime stability field close to that of monazite. They can exist as metastable monazite phases. Structural characterisations of long- and short-range order were performed by X-ray diffraction, infrared (IR) and Raman spectroscopy. Structural data could be complemented, enhanced and gaps of knowledge could be filled by the first systematic consideration of the complete Ln-monazite-series (Ln = La-Dy). Furthermore, this work focuses on Sm-monazite phases. Samarium with an atomic number of 62 is located in the middle part of the lanthanides showing the monazite structure. Accordingly, it has a mean cationic radius within the Ln-monazite-series and hence shows a relative high flexibility regarding the incorporation of radionuclides with different radii. Sintering densities of SmPO 4 ceramics were optimised by varying process parameters like pressure and number of pressing steps. An irregular texture as well as densities of 94% of the theoretical value could be achieved. The resistance of Sm-monazite against ionising radiation were examined. Radiation damages caused by the α-decay of radionuclides incorporated in a ceramic matrix were simulated by computer calculations and experimentally by heavy ion bombardment of SmPO 4 . Thin layers of
Anfimova, Tatiana; Li, Qingfeng; Jensen, Jens Oluf
as the rhabdophane structure is preserved. The bound hydrate water is accommodated in the rhabdophane structure and is stable at temperatures of up to 650 oC. The thermal stability of the hydrate water and the phosphate structure are of significance for the proton conductivity. The LaPO4·0.6H2O and NdPO4•0.5H2O......Hydrated orthophosphate powders of three rare earth metals, lanthanum, neodymium and gadolinium, were prepared and studied as potential proton conducting materials for intermediate temperature electrochemical applications. The phosphates undergo a transformation from the rhabdophane structure...... to the monazite structure upon dehydration. The thermal stability of the hydrate is studied and found to contain water of two types, physically adsorbed and structurally bound hydrate water. The adsorbed water is correlated to the specific surface area and can be reversibly recovered when dehydrated as long...
Sole, Jose Garcia; Ramirez O, Maria de la; Rodenas, Airan; Jaque, Daniel; Bausa, Luisa; Bettinelli, Marco; Speghini, Adolfo; Cavalli, Enrico; Ivleva, Lioudmila
In this work, we have examined three new bistable systems based on the luminescence of three different crystals activated with trivalent rare earth ions. We have focussed our attention on Yb 3+ ions activators, for which the most relevant results are obtained. The first crystal, Sr 0.6 Ba 0.4 Nb 2 O 6 , is a ferroelectric material with a relatively low phase transition temperature (∼370 K), which provides bistability in the luminescence of Yb 3+ ions due to the thermal hysteresis associated with phase transition. The second crystal, LiNbO 3 , provides an intrinsic bistability in the luminescence of Yb 3+ ions, which is driven by changes in the excitation intensity. In the third crystal, NdPO 4 , a new mechanism of excitation intensity driven bistability is obtained when activated with Yb 3+ ions, due to a interplay between the Nd 3+ ↔Yb 3+ energy transfer and back transfer processes
Galerkin, Y.; Rekstin, A.; Soldatova, K.
Gas dynamic design of the pipe line compressor 32 MW was made for PAO SMPO (Sumy, Ukraine). The technical specification requires compressor efficiency of 90%. The customer offered favorable scheme - single-stage design with console impeller and axial inlet. The authors used the standard optimization methodology of 2D impellers. The original methodology of internal scroll profiling was used to minimize efficiency losses. Radically improved 5th version of the Universal modeling method computer programs was used for precise calculation of expected performances. The customer fulfilled model tests in a 1:2 scale. Tests confirmed the calculated parameters at the design point (maximum efficiency of 90%) and in the whole range of flow rates. As far as the authors know none of compressors have achieved such efficiency. The principles and methods of gas-dynamic design are presented below. The data of the 32 MW compressor presented by the customer in their report at the 16th International Compressor conference (September 2014, Saint- Petersburg) and later transferred to the authors.
Two phosphate-based materials were investigated for cesium immobilization after its partitioning from spent nuclear fuel: apatites and rhabdophanes. The incorporation of cesium into the apatitic lattice creates steric stresses. These stresses induce the formation of secondary phases which are rapidly leached. The effectiveness of the cesium immobilization in this material is not therefore validated. A second phosphate CsCaNd(PO 4 ) 2 was consistently found at the end of the leach test and its properties were further characterized. The structure of CsCaNd(PO 4 ) 2 , which is rhabdophane-like, is made of large channels which enable the incorporation of the largest alkaline cations. The synthesis involves two intermediates: the monazite, NdPO 4 , and a soluble phosphate, CsCaPO 4 . The study of a rhabdophane with 10 wt.% of cesium reveals satisfactory intrinsic properties: a thermal stability up to 1100 C and a leach rate of 10 -2 g/(m 2 .d). The next step will be to improve the reaction yield. (author)
Standard thermodynamic properties (STP) of lanthanides (Ln 3+ ) are necessary to predict their transport in hydrothermal fluids. New STP (apparent molal volumes and heat capacities) of Ln 3+ are determined with dilute (La 3+ , Nd 3+ , Gd 3+ , Yb 3+ ) triflates solutions, up to 300 deg. C and 300 bars, using a vibrating tube flow densimeter and a differential heat flow calorimeter. The triflate anion (CF 3 SO 3 ), stable at high temperature, does not form complexes with Ln 3+ . The STP of HCF 3 SO 3 and NaCF 3 SO 3 are measured in order to get the STP of CF 3 SO 3 . The solubility of the Nd-pure pole of monazite (NdPO 4 ) studied between 300 and 800 deg. C at 2 kbars in H 2 O and H 2 O+NaCl using weight loss and isotope dilution methods, is prograde for neutral pH. The study of Nd 3+ speciation at 650 deg. C and 300 deg. C, 2 kbars, shows that only hydroxylated species are present. These data allow the revision of Ln 3+ parameters in the HKF model. (author)
Du Fou De Kerdaniel, E.
In the field of the radwaste storage in underground repository, several matrices were considered as promising ceramics for the specific immobilization of actinides. Two of them, britholites and monazite/ brabantite solid solution, have been considered during this work. In order to examine the dissolution mechanisms occurring at the solid liquid interface, several leaching experiments have been conducted on (Ln III PO 4 ), brabantite (Ca II An IV (PO 4 ) 2 : An = Th, U) and britholites (Ca 9 Nd 0.5 An 0.5 IV (PO 4 ) 4.5 (SiO 4 ) 1.5 F 2 : An = Th, U). Some steady experiments, performed in under saturation conditions for various pH and temperature conditions allowed to evaluate the long term behaviour of such matrices through their chemical durability. On the contrary, the thermodynamic equilibria were examined through the leaching experiments performed near the saturation conditions. By the way, various secondary phases, precipitated onto the surface of altered samples have been identified and characterized. Among them, the (Nd, Ca, Th) - rhabdophane, novelly prepared in over- saturation experiments for a thorium weight loading lower than 11 % appeared to be metastable. Indeed, it turns into TPHPH (Th 2 (PO 4 ) 2 HPO 4 .H 2 O) and Nd - rhabdophane (NdPO 4 .1/2H 2 O) when increasing leaching time. (author)
Li, Qinghua; Yuan, Yongbiao; Chen, Zihan; Jin, Xiao; Wei, Tai-huei; Li, Yue; Qin, Yuancheng; Sun, Weifu
In this work, a core-shell nanostructure of samarium phosphates encapsulated into a Eu(3+)-doped silica shell has been successfully fabricated, which has been confirmed by X-ray diffraction, transmission electron microscopy (TEM), and high-resolution TEM. Moreover, we report the energy transfer process from the Sm(3+) to emitters Eu(3+) that widens the light absorption range of the hybrid solar cells (HSCs) and the strong enhancement of the electron-transport of TiO2/poly(3-hexylthiophene) (P3HT) bulk heterojunction (BHJ) HSCs by introducing the unique core-shell nanoarchitecture. Furthermore, by applying femtosecond transient absorption spectroscopy, we successfully obtain the electron transport lifetimes of BHJ systems with or without incorporating the core-shell nanophosphors (NPs). Concrete evidence has been provided that the doping of core-shell NPs improves the efficiency of electron transfers from donor to acceptor, but the hole transport almost remains unchanged. In particular, the hot electron transfer lifetime was shortened from 30.2 to 16.7 ps, i.e., more than 44% faster than pure TiO2 acceptor. Consequently, a notable power conversion efficiency of 3.30% for SmPO4@Eu(3+):SiO2 blended TiO2/P3HT HSCs is achieved at 5 wt % as compared to 1.98% of pure TiO2/P3HT HSCs. This work indicates that the core-shell NPs can efficiently broaden the absorption region, facilitate electron-transport of BHJ, and enhance photovoltaic performance of inorganic/organic HSCs.
Proper knowledge of the diffusion rates of lead in monazite is necessary to understand the U-Th-Pb age anomalies of this mineral, which is one of the most used in geochronology after zircon. Diffusion experiments were performed in NdPO 4 monocrystals and in Nd 0.66 Ca 0.17 Th 0.17 PO 4 polycrystals from Nd 0.66 Pb 0.17 Th 0.17 PO 4 thin films to investigate Pb 2+ + Th 4+ ↔ 2 Nd 3+ and Pb 2+ ↔ Ca 2+ exchanges. Diffusion annealings were run between 1200 and 1500 Celsius degrees, at room pressure, for durations ranging from one hour to one month. The diffusion profiles were analysed using TEM (transmission electronic microscopy) and RBS (Rutherford backscattering spectroscopy). The diffusivities extracted for Pb 2+ + Th 4+ ↔ 2 Nd 3+ exchange follow an Arrhenius law with parameters E equals 509 ± 24 kJ mol -1 and log(D 0 (m 2 s -1 )) equals -3.41 ± 0.77. Preliminary data for Pb 2+ ↔ Ca 2+ exchange are in agreement with this result. The extrapolation of our data to crustal temperatures yields very slow diffusivities. For instance, the time necessary for a 50 μm grain to lose all of its lead at 800 Celsius degrees is greater than the age of the Earth. From these results and other evidence from the literature, we conclude that most of the perturbations in U-Th-Pb ages of monazite cannot be attributed to lead diffusion, but rather to interactions with fluids. (author)
Dutta, Dimple P.; Ningthoujam, R. S.; Tyagi, A. K.
Sm"3"+ doped YPO_4 spherical nanoparticles are prepared by wet chemical route. Pure YPO_4 shows the tetragonal phase, which is stable up to 900 °C, whereas pure SmPO_4 shows the phase transition from hexagonal to monoclinic when heated above 800 °C. The (2-10 at.%) Sm"3"+ doped YPO_4 shows the mixture of phases of tetragonal and hexagonal, which transform to the tetragonal phase above 800 °C. Infra-red study could distinguish confined water in the pore of hexagonal phase from water present on the surface of particles. Luminescence intensities of Sm"3"+ at 564, 601 and 645 nm are weak in case of as-prepared samples because of high non-radiative rate arising from the H_2O molecules present in pores of hexagonal lattice. The intensities increase for samples heated up to 900 °C because of increase of extent of radiative rate. Luminescence lifetime increases with increase of heat-treatment up to 900 °C. When solvent of as-prepared sample was changed from the H_2O to D_2O, 5 times enhancement in luminescence intensity is observed, which can be ascribed to the lower vibration energy of D-O over H-O, which is near to Sm"3"+. When Y"3"+ and P"5"+ ions are substituted by Ca"3"+ and W"3"+ up to 3 at.%, there is an enhancement of luminescence. In order to use them as bio-labeling in drug delivery for hyperthermia applications, hybrid of Fe_3O_4@YPO_4:7Sm is prepared and heating up to 45 °C is observed under AC magnetic field.
Studies of natural and synthetic apatites allow to propose such crystals as matrix for nuclear waste storage. The neodymium substituted britholite, Ca 9 Nd(PO 4 ) 5 (SiO 4 )F 2 . is a model for the trivalent actinide storage Neodymium can be substituted in two types of sites. The aim of this thesis is to compare the chemical nature of this two sites in fluoro-apatite Ca 9 (PO 4 ) 6 F 2 and then in britholite, using ab initio atomistic modeling. Two approaches are used: one considers the infinite crystals and the second considers clusters. The calculations of the electronic structure for both were performed using Kohn and Sham density functional theory in the local approximation. For solids, pseudopotentials were used, and wave functions are expanded in plane waves. For clusters, a frozen core approximation was used, and the wave functions are expanded in a linear combination of Slater type atomic orbitals. The pseudopotential is semi-relativistic for neodymium, and the Hamiltonian is scalar relativistic for the clusters. The validation of the solid approach is performed using two test cases: YPO 4 and ScPO 4 . Two numerical tools were developed to compute electronic deformation density map, and calculate partial density of stases. A full optimisation of the lattice parameters with a relaxation of the atomic coordinates leads to correct structural and thermodynamic properties for the fluoro-apatite, compared to experience. The electronic deformation density maps do not show any significant differences. between the two calcium sites. but Mulliken analysis on the solid and on the clusters point out the more ionic behavior of the calcium in site 2. A neodymium substituted britholite is then studied. Neodymium location only induces local modifications in; the crystalline structure and few changes in the formation enthalpy. The electronic study points out an increase of the covalent character the bonding involving neodymium compared with the one related to calcium
This work is devoted to the study of radiation damage produced by swift heavy ions in rare earth phosphates, materials that are considered as perspective for radioactive waste storage. Single crystals of rare earth phosphates were exposed to 2.1 GeV gold (Au) and 1.5 GeV xenon (Xe) ions of and analyzed mainly by Raman spectroscopy. All phosphates were found almost completely amorphous after the irradiation by 2.1 GeV Au ions at a fluence of 1 x 10 13 ions/cm 2 . Radiation-induced changes in the Raman spectra include the intensity decrease of all Raman bands accompanied by the appearance of broad humps and a reduction of the pronounced luminescence present in virgin samples. Analyzing the Raman peak intensities as a function of irradiation fluence allowed the calculation of the track radii for 2.1 GeV Au ions in several rare earth phosphates, which appear to be about 5.0 nm for all studied samples. Series of samples were studied to search for a trend of the track radius depending on the rare earth element (REE) cation. Among the monoclinic phosphates both Raman and small-angle X-ray scattering (SAXS) suggest no significant change of the track radius with increasing REE mass. In contrast, within the tetragonal phosphates Raman spectroscopy data suggests a possible slight decreasing trend of the track radius with the increase of REE atomic number. That finding, however, requires further investigation due to the low reliability of the qualitative Raman analysis. Detailed analysis of Raman spectra in HoPO 4 showed the increase of peak width at the initial stage of the irradiation and subsequent decrease to a steady value at higher fluences. This observation suggested the existence of a defect halo around the amorphous tracks in HoPO 4 . Raman peaks were found to initially shift to lower wavenumbers with reversing this trend at the fluence of 5 x 10 11 for NdPO 4 and 1 x 10 12 ions/cm 2 for HoPO 4 . At the next fluence steps peaks moved in the other direction, passed