National Institute Of Materials Physics - Romania

The work demonstrates growth by the Verneuil method of SrTiO3 single crystals of 30 mm in diameter. Experiments are performed under an industrial environment. Growth was for 4.75 h, i.e., within one production shift. The optimum growth conditions for which the length of the region with bubbles D is zero and the effective length EL (i.e., the crystal length of commercial value) is maximized are for the amount of SrCO3 additive of similar to 3 wt % and for H-2 outer flow rate of similar to 35 L/min. These two parameters show the strongest influence on the bubble-free growth, but other growth parameters (H-2 inner flow rate, O-2 flow rate increase, rotation speed) were also optimized. Selected crystals are characterized from the structural, microstructural, optical, and THz spectroscopy viewpoints, and they are compared with a commercial substrate and with crystals reported in the literature. This work opens the possibility for the industrial growth of large SrTiO3 single crystals and commercialization of large area substrates.

This is the first report on synthesis and photocatalytic activity for trichloroethylene (TCE) degradation under simulated solar light over RbLaTa2O7 layered perovskites with predominant nanowire or platelet morphologies. SEM images witnessed that the one step thermal treatment at 1200 degrees C lead to formation of RbLaTa2O7 nanowires with diameter of 80-320 nm and several microns in length associated in bundles and sharp-edged, merged platelets (minor phase). The two-step annealing at 950 degrees C and 1200 degrees C resulted in decrease of wires bundle population and increase in that of platelets merged in facetted particles. The RbLaTa2O7 nanowires are made of by well-aligned atomic rows with preferred orientation toward the c-axis, relatively free of defect. High density of hydroxyl groups on the sample calcined in mild conditions (RbLaTa_01) favors the photo mineralization of TCE. In contrast, the activity of RbLaTa_02 annealed in harsh conditions (950 and 1200 degrees C), poor in surface hydroxyl groups, remained modest. The weak surface basicity directed the reaction mainly to generation of intermediate chlorinated compounds. Pd and Au were supported on RbLaTa2O7 perovskites as an alternative strategy to boost the removal of chlorinated pollutants by combining photocatalytic (mineralization) and catalytic (hydrodechlorination, HDC) processes. The mineralization of TCE to Cl- was drastically hindered in presence of methanol due to quenching of -OH radicals by alcohol. The results suggested that the density of RbLaTa2O7 surface hydroxyl groups is essential for photo mineralization of TCE whereas the surface carbonate is beneficial for the formation of intermediate chlorinated product.

This research work is dedicated to study structural, morphological, optical and photoluminescence properties of samarium doped calcium sulfate (CaSO4) thin films after exposure to high gamma radiations. Polycrystalline doped CaSO4 thin films have been grown on glass substrates by spray pyrolysis technique and irradiated at different high gamma doses 3, 7, 15 and 40 kGy. Physical characterization of irradiated thin films has been made by X-ray diffraction, Spectrophotometer, Scanning Electron Microscope, Energy Dispersive Spectroscopy, Fluorescence Spectrometer and Thermoluminescence. The most remarkable result, as shown by structural analysis, is the increase of grain size from 52 to a maximum value of 93 nm for 15 kGy gamma dose which indicates a clear enhancement in crystal structure by gamma irradiation. Moreover, the preferred orientation has been immediately changed from (102) plan to (100) just after the first 3 kGy gamma dose. SEM micrographs of irradiated thin layers show deep modifications in surface morphology. Optical transmission spectra have shown a sharp and intense peak at 350 nm wavelength. Band gap energy has been slightly decreased from 3.9 eV before irradiation to 3.6 eV for 40 kGy. A new and strong energy level noted E r , has been emerged and created due to high gamma irradiations in addition to the principal one relative to band gap energy. Other parameters like absorption and extinction coefficients and refractive index have been determined. Thermoluminescence data show a high sensibility to gamma radiations doses which offer opportunities for dosimetry applications. These experimental results suggest the use of irradiated samarium doped calcium sulfate as optical window for space photovoltaic devices where gamma rays are abundant. These results are also helpful for researchers using CaSO4 thin films near nuclear apparatus (nuclear reactors and particle accelerators) or those interested in studying interaction between radiations and condensed matter.

Topological and thermal disorder complicate the mobility characterization in poly(3,4-ethylenedioxythiophene) systems and presently leaves the exact transport mechanisms not fully understood. Here we show that ac-Hall measured by lock-in amplifier is able to resolve the Hall voltage in semimetallic polymers between room temperature and 32 K. These results are evaluated using an organic random phase model. This accounts for the role of tail states and, particularly, for thermal disorder of molecular semiconductors. We report band mobilities up to 3.7 cm(2) V-1 s(-1) in semimetallic polymers occurring in delocalized bands that originate from significant electron coherence across the polymer chains.

The results of experimental and theoretical ab initio study of structural and piezoelectric properties of (Ba,Sr)TiO3 perovskite solid solutions are discussed and compared. Experimentally, plate-like (Ba,Sr)TiO3 particles were synthesized by the topochemical conversion in the molten salt from Bi4Ti3O12 template plates. All dimensions (side length approximate to 1 mu m, thickness approximate to 200-400 nm) were well above the critical size necessary for observation of piezo- and ferroelectricity. The first-principles computations of the structural and electromechanical properties of solid solutions were performed with the CRYSTAL14 computer code within the linear combination of atomic orbitals approximation, using three advanced hybrid functionals of density functional theory. Different chemical compositions are considered for the ferroelectric and paraelectric phases. The calculated structural properties of solid solutions in tetragonal and cubic phases are in very good agreement with experimental data. Experimentally obtained and calculated band gaps are compared for cubic SrTiO3 and tetragonal BaTiO3. BaTiO3/SrTiO3 heterostructures were considered theoretically for different chemical compositions. The calculated piezoelectric properties of solid solutions and heterostructures in the ferroelectric phase are compared. It is predicted that both solid solutions and heterostructures improve the piezoelectric properties of bulk BaTiO3, but solid solutions are more preferable for equal Sr concentrations.

Temperature dependent interfacial coupling mechanisms in SRO/BFO/Fe layered structures were investigated. The BFO/Fe heterostructures were prepared by PLD and sputtering, respectively, on the STO(0 0 1) substrate with a 20 nm SRO buffer layer. An annealing treatment in external magnetic field was further applied. Complex characterizations with X-ray diffraction, atomic force microscopy, Transmission Electron Microscopy, Mossbauer spectroscopy, magneto-optic Kerr effect and SQUID magnetometry were performed. Before annealing, the films show good crystallization and epitaxy of the SRO and BFO layers with smooth interfaces. Two coupling mechanisms of the ferromagnetic layers (top Fe and bottom SRO, respectively) to the epitaxial BFO film with mainly antiferromagnetic structure were evidenced in the as deposited samples at low temperatures. Negative exchange bias fields of up to 67(10) Oe and 37(5) Oe at low temperatures were observed for the two ferromagnetic components, respectively, depending on the thickness of the Fe layer. The field annealing treatments induce a specific morphology and magnetic spin structure at both interfaces of the BFO spacer layer, giving rise to a long range magnetostatic coupling between the two ferromagnetic films, in addition to the interfacial couplings. Moreover, the experimentally evidenced Fe clusters penetrating the BFO/Fe interface toward the BFO layer give support for this interaction. As an additional consequence, a considerable enhancement of both uniaxial and unidirectional anisotropies as well as an increased blocking temperature of exchange bias were obtained. The involved exchange coupling mechanisms were discussed in detail. (C) 2018 Elsevier B.V. All rights reserved.

The present work proposes the simultaneous removal of these classes of pollutants by a catalytic hydrotreatment processes. For this purpose, bimetallic Pd-Cu catalysts (with mass ratio Pd:Cu of 4:1) supported on macroporous strong base anion resin were prepared by different methods. The catalysts were characterized (by XRD, SEMEDX, XPS, AAS and H-2 chemisorption) and tested in a continuous flow system. The selected catalyst preparation protocol consists in a two-step method, which implies the deposition of palladium by ion exchange and the subsequent deposition of copper by controlled reaction on the surface of the pre-reduced palladium. The effectiveness of the catalyst in the simultaneous reduction of nitrate and hydrodechlorination of 4-chlorophenol was demonstrated. By adjusting the initial pH and the flow rate of the aqueous solution, nearly complete hydrodechlorination of 4-chlorophenol can occur together with selective nitrate reduction at a conversion of 95% and a selectivity to N-2 of 92% (this value contains the contribution of all gaseous products, including the eventually formed NOx). The bimetallic catalyst was found to remains relatively stable after 100 h of test time.

The properties of ferroelectric materials, which were discovered almost a century ago(1), have led to a huge range of applications, such as digital information storage(2), pyroelectric energy conversion(3) and neuromorphic computing(4,5). Recently, it was shown that ferroelectrics can have negative capacitance(6-11), which could improve the energy efficiency of conventional electronics beyond fundamental limits(12-14). In Landau-Ginzburg-Devonshire theory(15-17), this negative capacitance is directly related to the double-well shape of the ferroelectric polarization-energy landscape, which was thought for more than 70 years to be inaccessible to experiments(18). Here we report electrical measurements of the intrinsic double-well energy landscape in a thin layer of ferroelectric Hf0.5Zr0.5O2. To achieve this, we integrated the ferroelectric into a heterostructure capacitor with a second dielectric layer to prevent immediate screening of polarization charges during switching. These results show that negative capacitance has its origin in the energy barrier in a double-well landscape. Furthermore, we demonstrate that ferroelectric negative capacitance can be fast and hysteresis-free, which is important for prospective applications(19). In addition, the Hf0.5Zr0.5O2 used in this work is currently the most industry-relevant ferroelectric material, because both HfO2 and ZrO2 thin films are already used in everyday electronics(20). This could lead to fast adoption of negative capacitance effects in future products with markedly improved energy efficiency.

The aim of the present paper is to develop ceramic thin films by laser ablation in order to improve the biological behaviour of metallic implants dedicated to hard tissue restoration. The composition of the coatings was selected within SiO2-P2O5-CaO-MgO-ZnO-CaF2 system, while their processing has gone through two stages: target preparation via a wet chemistry approach and films deposition through a physical deposition method, on titanium substrates. The characteristics of the final layered structures were evaluated by X-ray diffraction, Fourier-transform infrared spectroscopy, scanning and transmission electron microscopy, energy-dispersive X-ray spectroscopy and selected area electron diffraction. In vitro investigation techniques were employed for the bioactivity and biocompatibility assessment. The results indicated the growth of nanostructured akermanite-based thin films with an excellent bioactivity and a good effect on stem-type cells, which validates the suitability of such structures for medical implant applications.

Spirobifluorene-based porous organic polymers (POP) were synthesized following two different protocols; the acetylenic coupling reaction conditions and the Sonogashira cross-coupling reaction. These were utilized as support for the hydrogenation of a series of species containing unsaturated C=C and C=O bonds (4-nitrostyrene, 4-bromobenzophenone, acetophenone, 7-nitro-1-tetralone and 1,2-naphtoquinone confirmed their efficiency). POP1 prepared via a copper-catalysis protocol was completely inactive, while POP2-4 containing residual Pd exhibited different activities in accordance to the accessibility of the substrates to the metal. Further deposition of 0.5wt% Pd led to active and stable catalysts. They were easily separated by filtration, and after re-dispersion, afforded the same performances for ten successive cycles. This study also evidenced the specific role of the support in these reactions by comparing the behavior of Pd/POP with that of a Pd/C catalyst with the same loading of palladium. The deposition of Pt on these supports led to sub-nanometric particles and, in accordance, to a different catalytic behavior reflected merely by differences in the selectivity.