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We have successfully prepared La0.5Sr0.5MnO3nanowires using a novel hydrothermal synthesis process and studied their magnetic and magnetocaloric properties. The system exhibits an inverse magnetocaloric effect (IMCE) around 175 K indicating presence of significant AFM correlation. The MCE study reveals a clear paramagnetic (PM) to ferromagnetic (FM) transition near room temperature (T ~ 325K) which is followed by onset of AFM at lower temperatures. The development of the FM-like magnetic state at low temperature is attributed to the enhanced double exchange (DE) driven ferromagnetism in AFM state as predicted by recent theoretical studies.
The commercial viability of solar power will depend on a careful balance of reliability, efficiency, and overall cost. A systematic approach to the optimization of the latter two for the case of organic solar cells is outlined. This relies among other on the development of a detailed understanding of the charge generation process and the systematic application of analytical tools such as UV-vis, photoluminescence, lifetime measurements, and current-voltage (I-V) curves.
We have developed a QCM (Quartz Crystal Microbalance) based method for direct gravimetric determination of water adsorption on PuO2 surrogate surfaces, especially CeO2, under conditions representative of those in a typical PuO2 storage can. In this application, the method of transduction of the QCM relies upon the linear relationship between the resonant frequency of piezoelectrically active quartz crystals and the mass adsorbed on the crystal surface. The spurious effect of high temperatures on the resonant frequency of coated QCM crystals has been compensated for by modeling the temperature dependence of the frequency response of the surrogate coated-QCM crystal in the absence of water. Preliminary results indicate that water is readily adsorbed from the vapor phase into porous metal oxide structures by capillary condensation, an observation that may have important ramifications for water uptake within the packed powder beds that may obtain in PuO2 storage cans.
The theory of the interaction of elastic waves with dislocations is reviewed, as is the extent to which it has been tested by experiment. There are two essential ingredients to the wave-dislocation interaction: one is that, when a wave hits a dislocation, the latter will respond by moving in some fashion. The other is that, when a dislocation moves, it generates (“radiates”) elastic waves. For a linearly elastic solid continuum, both phenomena can be described by equations that are linear outside the dislocation core. One is a linear elastic wave equation with a right-hand-side term that is localized at the dislocation position. The other is a linear equation for the vibrations of a string (that is coincident with the dislocation), with an external loading provided by the wave. This provides the basic mechanism for the scattering of elastic waves by dislocations, and it can be worked out in considerable detail for pinned dislocation segments and prismatic dislocation loops in infinite media, as well as for the scattering of surface (Rayleigh) elastic waves by subsurface dislocation segments.
The results for the scattering by a single dislocation can be used as input in a multiple scattering formalism to study the properties of a coherent wave propagating in a solid with many dislocations present. Expressions for the effective velocity of propagation, and for the disorder-induced (as distinct from the internal losses) attenuation can be found. They test successfully with Resonant Ultrasound Spectroscopy (RUS) experimental measurements.
Open problems, possible further applications and current efforts are discussed.
Glass-Ceramic monoliths of the SiO2-CaO-MgO-Al2O3 system are obtained in this research. Due to its potential dual role as a flux and as a nucleating agent, two CaF2 levels (X = 3 and X = 6 mol.%) are investigated in the parent glass composition. Due to its good mechanical properties, we intend to obtain Diopside-type pyroxene [(Ca)(Mg,Al)(Al,Si)2O6] as the main crystalline phase in the synthesized glass-ceramics. Vickers microhardness (HV), density and type of crystallization are determined in the latter materials. The morphology and size of the Diopside crystals, as well as the crystallized fraction, are determined with the help of Scanning Electron Microscopy (SEM) and X-Ray Diffraction (XRD). Both materials exhibit surface crystallization with Diopside-type pyroxene phase with acicular morphology homogeneously distributed in the glassy matrix. The specimen with the least amount of added fluorine shows the highest microhardness value, as well as the largest and thickest acicular crystals of Diopside-type pyroxene, the lowest apparent density and the largest crystallized fraction. Our results indicate that CaF2 added in the amounts used by us does not act as nucleating agent, but it does affect the growth of the acicular crystals of the Diopside-type pyroxene phase. This is attributed mainly to the effect of fluorine on the glass structure and properties. The materials developed in this study may be considered as viable alternatives for applications in abrasive and corrosive environments, as well as for substrates for metallic coatings, and for abrasion-resistant floor tiles and other structural applications.
In the framework of long term prediction of corrosion in French geological repository systems, the modelling of the time evolution of the corrosion rate of iron over centuries is of high matter. The DPCM (Diffusion Poisson Coupled Model), implemented with the fully implicit CALIPSO numerical code can give access to the evolution of the oxide thickness grown on iron and the resulting corrosion rate. DPCM parameters for outer interfacial reactions have been set to fit to XANES experimental data provided by literature, and then the parameters for inner reaction rates have been evaluated from fitting to ellipsometry results taken from literature. The result is a good average fitting of the model to the experimental data.
Our previous studies proved the occurrence of the shape memory effect (SME) in a biocompatible porous nitinol (inter-metallic phase NiTi), obtained by the selective laser sintering (SLS) method. In this report we propose to use the SME peculiar to the nitinol, for a functional design of the drug delivery system and to discuss the process flow pattern. In living tissues (flesh) the elevated temperature at the disease origination leads to the nitinol pores size reduction caused by the austenite phase transformation, and to the pharmaceutical composition extrusion from the pores. And vice versa, during the cooling stage when the tissue temperature reverts to normal level, the drug intake will stop. Depending on the type of the three dimensional structure of a porous matrix (scaffold) identified at the stage of a computer-aid-design, the velocity of penetration can be controllable.
Bismuth is an element obtained as a sub-product in lead production; Mexico occupies the second position in the world in production of this element. Bismuth is used as iron, aluminum and copper alloying, in the pharmaceutical industry, in the cosmetics industry, etc. Bismuth is separated from lead by the Kroll-Betterton Process in which a Ca-Mg alloy is added to the melting lead to form the intermetallic compounds Ca3Bi2, Mg3Bi2 and Ca2MgBi2 which float to the surface of the bath. Unfortunately, there is little thermodynamical information of the compounds of the system Ca-Mg-Bi which can be used to study and optimize the Kroll-Betterton process in a theoretical way. In this work there were synthesized the compounds Ca3Bi2, Mg3Bi2 and CaMg2Bi2 using powders of pure elements (Ca, Mg and Bi) in the required amounts and melted under an inert atmosphere. After synthesis, the samples were characterized by X-Ray Diffraction to ensure the formation of the desire compounds. Later, calorimetric technique was used to determine the thermodynamical properties of the compounds. The results obtained by X-Ray Diffraction show the formation of Mg3Bi2 and Mg2CaBi2 species; however, there is no crystallographic information of the compound Ca3Bi2. The heating curves obtained by calorimetry show endothermic peaks, due to the presence of phases changes as is indicated in the Ca-Bi, Mg-Bi and Ca-Mg-Bi phases diagrams.
In the present work, a comparison study of the Ni catalysts supported on SBA-15 silica support prepared with and without the addition of organic ligands (citric acid and ethylenediaminetetraacetic acid (EDTA) was undertaken. The aim of this study was to inquire on the effect of the addition of organic ligands on the characteristics of the supported NiO and Ni nanoparticles and on their activity and selectivity in hydrogenation (HYD) of aromatics. Catalysts with different metal loadings (5, 10 and 20 wt. % of Ni) were prepared, characterized by nitrogen physisorption, small-angle and powder XRD, TPR, UV-vis DRS, and HRTEM, and tested in HYD of naphthalene (NP). It was found that Ni(II)-Ligand complexes were formed in aqueous solutions of Ni(NO3)2 containing citric acid (CA) or EDTA. Catalysts prepared from impregnation solutions with and without ligands had different textural characteristics and dispersion of NiO particles after calcination at 500 °C for 4 h. As it was shown by XRD, DRS and TPR, dispersion of NiO particles significantly increased when EDTA was used, whereas it noticeably decreased after the addition of CA. Similar trends were observed in the dispersion of metallic Ni particles after reduction of the NiO/SBA-15 precursors (HRTEM). In line with the characterization results, catalytic activity tests revealed strong differences in the activity of the prepared Ni/SBA-15 catalysts in hydrogenation of naphthalene. Catalysts prepared with the addition of EDTA were more active than those prepared without ligands. On the contrary, the HYD activity of a series of the Ni catalysts prepared with citric acid was lower than of other corresponding samples. The reasons of such a different behavior of the catalysts prepared with two organic ligands used are discussed on the basis of the obtained characterization results.
GaP, GaAs, and InP nanowires were grown on graphitic layers by the vapor-liquid-solid method in a metalorganic vapor phase epitaxy chamber. On graphene/SiC(0001), Au particles as catalyst were formed at the steps by controlling the Au deposition rate and the annealing temperature in a low-energy electron microscopy system. GaP nanowires were grown on this substrate, and it was found that vertical nanowires were formed at the steps of the surface. We also performed GaP, GaAs, and InP nanowire growth on graphite substrates. Free-standing nanowires were obtained for all three materials, although they were vertically, diagonally, and laterally-oriented at the same time. The results suggested that the growth at the steps is the key to growing nanowires vertically on graphene surface.
Over the course of use, both in-service and during storage, fuel claddings for nuclear reactors undergo complex changes that can drastically change their material properties. Exposures to irradiation, temperature changes, and stresses, as well as contact with coolant, storage pool, and dry storage environments, may induce microstructural changes, such as formation of radiation defects, precipitate dissolution, and chemical segregation, that can ultimately result in failure of the cladding if pushed beyond its limit. In order to predict the performance of cladding in-service and during storage, understanding of the dominant processes related to these changes and their consequences is essential. In situ transmission electron microscopy (TEM) allows dynamic observation, at the nanoscale, of microstructural changes under a range of stimuli, making it an excellent tool for deepening our understanding of microstructural evolution in claddings. This proceeding presents details of the new in situ ion irradiation TEM and in situ gas cell TEM capabilities developed at Sandia National Laboratories. In addition, it will present the initial results from both systems investigating radiation tolerance of potential Generation IV cladding materials and understanding degradation mechanisms in Zr-based claddings of importance for dry storage.
Besides the importance of the actinide dioxide series as a nuclear fuel, the magnetic properties of these compounds at low temperatures are particularly interesting. Their surprisingly varied physical properties at low temperatures stimulate continuing interest for both theory and experiment. Recently, we have performed 17O-NMR studies for the first time on Pu and Amcontaining dioxide systems, (Pu1-xAmx)O2. For the x=0.09 sample, a temperature-dependent NMR line broadening has been observed at low temperatures. By comparing the experimental data with the results of NMR line simulations, we have estimated the effective moment of Am ions to be Peff=1.38 μB. The value suggests the 5f5 (Am4+) state of the Am ion in PuO2. For the x=1 (=AmO2) sample, on the other hand, our 17O-NMR data provide the first microscopic evidence for a phase transition at 8.5 K as a bulk property in this system. A spectrum with a triangular line shape indicates that the internal field is distributed very nearly randomly in the ordered state.
In this paper, we combine the use of Drop-on-Demand (DOD) ink-jet printing with completely water- based inks as a novel approach to the CSD process for coated conductors. This method holds the promise of improved scalability due to lower ink losses, continuous processing and a drastically increased precursor lifetime due to the prevention of solvent evaporation and dust incorporation. Moreover, ink-jet printing has the potential to switch quite easily from continuous coatings to a multi-filamentary pattern, which is particularly important for alternating current (AC) or field applications of coated conductors. The fluid properties, often expressed with dimensionless constants, like the Reynolds and Weber numbers, for printable liquids were determined. For proof-of-concept, single crystals of SrTiO3 with a low mismatch towards YBCO, were used as substrates.
A multisite lattice-gas (msLG) model with realistic and precise surface diffusion kinetics is applied to provide a reliable description of the initial stages of non-equilibrium self-growth of a NiAl alloy by simultaneous stoichiometric codeposition of Ni and Al on the NiAl(110) surface. Deposition at 300 K produces intermixing but poor alloy ordering. Increasing temperature enhances alloy ordering to near perfection at 600 K, but island shapes remain un-equilibrated.
We have investigated the nonthermal bioplasma sources and their characteristics as well as their interactions with biological cells. The electron temperature and plasma density are measured to be about 1.5 eV and 3×1012 cm-3 , respectively, for the direct palsma jet under Ar gas flow. The hydroxyl radical density has also been investigated and measured to be maximum value of about 3 ×1015 cm-3 and 8 ×1014 cm-3 in the direct plasma jet and dielectric barrier discharge bioplasma, respectively, by the ultraviolet optical absorption spectroscopy. Herein, we have investigated the basic interactions of these nonthermal bioplasma with the living organisms in morphological and biomolecular aspects. We found that the secondary electron emision coefficient of the biological surface has been drastically increased by atmospheric bioplasma, which indicates the biological surface to be oxidized especially by the hydroxyl (OH) radical species. In order to elucidate the basic mechanisms for the cell shrinking and apoptosis leading to a cell death by the nonthermal bioplasma, the cell membrane potential has been estimated based on the ROS density as well as cell capacitances. It is also found that the molecular electron energy band structure in the biological cells have been shifted closer toward the vacuum surface and accordingly their central energy of molecular band becomes small by the nonthermal bioplasma due to cell oxidation caused by OH radicals.
In this paper we present a microfabricated SiC based alternative to glass-fiber optogenetic stimulation. The glass fiber system currently used for stimulation has numerous drawbacks. First, the very presence of glass can evoke an immune response in cortical tissue that can impede the light-to-neuron optical interface. This glial scarring of brain tissue effectively lowers the spatial resolution and power output of the system. Second, the fragility of an implanted glass fiber is a problem that has yet to be fully addressed. Using SiC the proposed optical structure will address these problems by significantly lowering the amount glial scarring and astrocytic activity expressed as a result of the implant. In addition, single crystal SiC allows for a flexible device that can move with the surrounding tissue without fracturing. Finally, the current glass fibers tend be single channel devices with a single ended emitter. The proposed microfabricated device will allow for multiple channels, multiple wavelengths of stimulation, and electrical feedback on each channel improving upon the current standard.
By systematically altering the number and position of phenylalanine andcarboxylate groups on a series of hydrogelators containing a naphthalenemotif, we evaluated the correlation of molecular structures, self-assembly,and the rheological properties of the hydrogels. The storage moduli of thehydrogels decrease with the increase of the number of phenylalanine or withthe insertion of a cysteine residue, and the effect of the carboxylic groupon the rheological properties depends on the backbone of the hydrogelators.Transmission electron microscopy shows that these hydrogelatorsself-assemble in water to form nanofibers and result in threedimensionalnetworks. Circular dichroism experiment indicates the hydrogelatorsself-assemble to form β-sheet-like structure within the nanofibers. Thiswork suggests that control of the synergy of hydrogen bonding andaromatic-aromatic interactions may offer a feasible way to modulate therheological properties of molecular hydrogels consisting of smallmolecules.
Degradation of cementitious materials produces leachates of high pH. Such an alkaline plume, if reaching the bentonite buffer, is likely to induce mineralogical and chemical changes in bentonite over long times and may jeopardise the set safety function of the buffer.The objective of this ongoing research is to study the possible alterations of two bentonites, MX-80 and Deponit CA-N, in alkaline leachates at two different temperatures. Also the buffering capacity of the bentonites against high pH will be evaluated.
The ongoing batch experiments are carried out in an anaerobic glove-box (Ar atmosphere, low CO2) at two temperatures (25/60 °C) with three types of simulated cement waters (pH 9.7/9,3, 11.3/10.2 and 12.0/10.9) at 25/0 °C) and one saline groundwater simulate (pH 8.3/7.9) as reference. The solid to liquid ratio used is 1/10. For each set of experiments there are three parallels so that bentonite alteration can be analysed after three different time periods. In the experiment each bentonite sample is leached with several batches of leaching solution. For each renewal of the leaching solution the phases are separated by centrifugation, the reacted solution withdrawn and the chemical composition analysed.
The high-pH experiments (11.3 and 12.0, at 25°C) have continuously shown an initial decrease in the pH-values after each leachate renewal, albeit less dramatic than in the beginning, indicating remaining buffering capacity of the bentonites. The other two experiments (pH 8.3 and 9.7 at 25°C) have shown rather unaltered pH-values. In general, slightly lower pH-values were observed in the Deponit CA-N samples than in those of MX-80. The main cations (Na and Ca) analysed in the leachates have shown a rather expected trends as a result of ion-exchange occurring in the bentonites. The analysed Si concentrations indicate possible dissolution of smectite. More conclusions are possible after the bentonites have been characterized. One experimental set of the 25 °C experiments has been finished and the bentonite phases are being characterized. Other experiment sets are still continued.
The development of accurate constitutive equations is important for the success of computer simulations of high temperature forming operations. Often, these simulations must be made on alloys that have not been completely characterized. For that reason physically-based constitutive equations taking the chemical composition into consideration, involving deformation mechanisms and characteristic properties of the material are necessary. The influence that exerts the solute elements to an alloy on the mechanisms of diffusion on deformation processes at high temperatures is not an easy subject and the available information in literature is scarce.
This study examines that influence working on the basis of eight structural plain carbon steels with the chemical composition ranging between 0.15-0.45%C, 0.2-0.4%Si and 0.6-1.6%Mn produced by Electro-Slag Remelting ESR process and tested by isothermal uniaxial compression technique. The studied deformation conditions include strain rates ranging between 5·10−4 to 1·10−1 s−1 and temperatures between 0.6-0.75Tm, with Tm the melting temperature.
A constitutive expression for the hot working behavior is proposed, it includes the variation of the diffusion parameters with the chemical composition. To such aim the effect of the chemical composition of the alloy on the pre-exponential factor D0 of the gamma iron self-diffusion coefficient Dsd is included. Finally, a comparison of the experimental and predicted results shows the good agreement of the model with experimental flow data.
We present the results of our systematic investigation of the RE dependency of superconductivity in the parent compounds T’-RE2CuO4 (RE = Pr, Nd, Sm, Eu, Gd, and Tb). Superconducting samples were prepared by metal organic decomposition (MOD). A stringent control of synthesis- and post-annealing-conditions is required to obtain superconducting samples. Superconductivity with a transition temperature (Tconset) ≥ 30 K is achieved for RE = Pr and Nd. By contrast, Tconset is at highest 20 K for RE = Gd. Our results indicate that the induction of superconductivity into T’-RE2CuO4 cuprates strongly depends on the RE3+ ionic size. This trend is discussed from the viewpoint of RE-dependent thermodynamic stability of T’-RE2CuO4. For smaller RE3+ ions, the thermodynamic boundary conditions become tighter.