National Institute Of Materials Physics - Romania

Two series of cyclometalated palladium(II) complexes based on Schiff bases and N-benzoylthiourea (BTU) ligands having four alkoxy groups at their periphery, with different number of carbon atoms, have been designed and prepared. The liquid crystalline behavior of these palladium(II) complexes was investigated by a combination of polarized optical microscopy (POM), differential scanning calorimetry (DSC) and powder X-ray diffraction while their thermal stability was studied by thermogravimetric analysis (TGA). The palladium(II) complexes are thermally stable on a broad temperature range up to 230 degrees C showing, depending on the alkoxy chain length, either monotropic or, for longest alkyl chain, enantiotropic smectic A and C phases. The luminescent properties of palladium(II) complexes were reported. These complexes show a yellow-orange solid-state emission at room temperature with two emission maxima at lambda(max) around 580 and 650 nm, respectively, with a shoulder around 710 nm, when the samples are irradiated in the 330-380 nm range. (C) 2017 Elsevier B.V. All rights reserved.

Reduced-activation steels such as Eurofer alloys are candidates for supporting plasma facing components into kamak-like nuclear fusion reactors. In order to investigate the impact of hydrogen/deuterium insertion in their crystalline lattice, annealing treatments in hydrogen atmosphere have been applied on Eurofer slabs. The resulting samples have been analyzed with respect to local structure and atomic configuration both before and after successive annealing treatments, by X-ray diffractometry (XRD), scanning electron microscopy and energy dispersive spectroscopy (SEM-EDS), X-ray photoelectron spectroscopy (XPS) and conversion electron Mossbauer spectroscopy (CEMS). The corroborated data point out for a bcc type structure of the non-hydrogenated alloy, with an average alloy composition approaching Fe0.9Cr0.1 along a depth of about 100 nm. EDS elemental maps do not indicate surface inhomogeneities in concentration whereas the Mossbauer spectra prove significant deviations from a homogeneous alloying. The hydrogenation increases the expulsion of the Cr atoms toward the surface layer and decreases their oxidation, with considerable influence on the surface properties of the steel. The hydrogenation treatment is therefore proposed as a potential alternative for a convenient engineering of the surface of different Fe-Cr based alloys.(C) 2017 Elsevier B.V. All rights reserved.

High performance trilayer memory capacitors with a floating gate of a single layer of Ge quantum dots (QDs) in HfO2 were fabricated using magnetron sputtering followed by rapid thermal annealing (RTA). The layer sequence of the capacitors is gate HfO2/floating gate of single layer of Ge QDs in HfO2/tunnel HfO2/p-Si wafers. Both Ge and HfO2 are nanostructured by RTA at moderate temperatures of 600-700 degrees C. By nanostructuring at 600 degrees C, the formation of a single layer of well separated Ge QDs with diameters of 2-3 nm at a density of 4-5 x 1015 m(-2) is achieved in the floating gate (intermediate layer). The Ge QDs inside the intermediate layer are arranged in a single layer and are separated from each other by HfO2 nanocrystals (NCs) about 8 nm in diameter with a tetragonal/orthorhombic structure. The Ge QDs in the single layer are located at the crossing of the HfO2 NCs boundaries. In the intermediate layer, besides Ge QDs, a part of the Ge atoms is segregated by RTA at the HfO2 NCs boundaries, while another part of the Ge atoms is present inside the HfO2 lattice stabilizing the tetragonal/orthorhombic structure. The fabricated capacitors show a memory window of 3.8. +/-. 0.5 V and a capacitance-time characteristic with 14% capacitance decay in the first 3000-4000 s followed by a very slow capacitance decrease extrapolated to 50% after 10 years. This high performance is mainly due to the floating gate of a single layer of well separated Ge QDs in HfO2, distanced from the Si substrate by the tunnel oxide layer with a precise thickness.

The electronic structure of alpha-Sn (001) thin films strained compressively in-plane was studied both experimentally and theoretically. A new topological surface state (TSS) located entirely within the gapless projected bulk bands is revealed by ab initio-based tight-binding calculations as well as directly accessed by soft x-ray angle-resolved photoemission. The topological character of this state, which is a surface resonance, is confirmed by unravelling the band inversion and by calculating the topological invariants. In agreement with experiment, electronic structure calculations show the maximum density of states in the subsurface region, while the already established TSS near the Fermi level is strongly localized at the surface. Such varied behavior is explained by the differences in orbital composition between the specific TSS and its associated bulk states, i.e., their hybridization, respectively.

TiO2 nanoparticles, undoped and doped with Fe, have been prepared by laser pyrolysis and further investigated with respect to morphological, structural and magnetic aspects by transmission electron microscopy, diffractometry, Mossbauer spectroscopy, and magnetometry. The obtained nanoparticles, consisting of mainly anatase phase, agglomerate in clusters of tenths of units and present a large size distribution in the range from 5 to 40 nm. The anatase to rutile weight ratio (about 9) and the morphology of particles is similar in all analyzed samples (doped by up to 12 0,0 at. % Fe). Only Fe3+ ions in high spin-configuration were observed mainly at the, surface of TiO2 nanoparticles, either distributed or forming fine clusters of Fe oxide.;:Both a paramagnetic phase and a superparamagnetic one with blocking temperature lower than 50 K are superposed over a long-range ferromagnetic phase specific to diluted magnetic oxide systems. The influence of doping Fe ions on the magnetic behavior of each phase is discussed in detail. Evidences for interface exchange couplings (with unidirectional anisotropy in specific conditions) between the long-range ferromagnetic phase and the fine clusters (antiferromagnetic in nature), which become frozen below temperature of 50, K, are provided. The specificity of the processing route and the physical mechanisms responsible observed relevant magnetic features, which can be tailored for suitable applications, are discussed.

N-Containing graphenes obtained either by simultaneous amination and reduction of graphene oxide or by pyrolysis of chitosan under an inert atmosphere have been found to act as catalysts for the selective wet oxidation of glucose to succinic acid. Selectivity values over 60% at complete glucose conversion have been achieved by performing the reaction at 160 degrees C and 18 atm O-2 pressure for 20 h. This activity has been attributed to graphenic-type N atoms on graphene. The active N-containing graphene catalysts were used four times without observing a decrease in conversion and selectivity of the process. A mechanism having tartaric and fumaric acids as key intermediates is proposed.

The purpose of this study was to obtain, characterize and evaluate the cytotoxicity and antimicrobial activity of coatings based on poly(3-hydroxybutyric acid-co-3-hydroxyvaleric acid) -Lysozyme (P(3HB3HV)/ Lys) and P(3HB-3HV) -Polyethylene glycol -Lysozyme (P(3HB-3HV)/PEG/Lys) spheres prepared by Matrix Assisted Pulsed Laser Evaporation (MAPLE) technique, in order to obtain functional and improved Ti-based implants. Morphological investigation of the coatings by Infrared Microscopy (IRM) and SEM revealed that the average diameter of P(3HB-3HV)/Lys spheres is around 2 mm and unlike the drop cast samples, IRM recorded on MAPLE films revealed a good distribution of monitored functional groups on the entire scanned surface. The biological evaluation of MAPLE structured surfaces revealed an improved biocompatibility with respect to osteoblasts and endothelial cells as compared with Ti substrates and an enhanced anti-biofilm effect against Gram positive (Staphylococcus aureus) and Gram negative (Pseudomonas aeruginosa) tested strains. Thus, we propose that the fabricated P(3HB-3HV)/PEG/Lys and P(3HB-3HV)/Lys microspheres may be efficiently used as a matrix for controlled local drug delivery, with practical applications in developing improved medical surfaces for the reduction of implant-associated infections. (C) 2017 Elsevier B. V. All rights reserved.

Pure BT and BT doped with 1 and 2 mol% Zr, with orthorhombic-tetragonal (O-T) phase transitions near room temperature were prepared, with different grain sizes, by conventional ceramic method, at various sintering temperatures. Intrinsic and extrinsic effects of Zr addition on structural, dielectric, piezoelectric and ferroelectric properties of BT ceramics, near O-T phase transition were studied. In coarse grained ceramics, the intrinsic effects manifested in low field measurements (dielectric and piezoelectric constants), were reduced by Zr addition, while the extrinsic effects which control the high field response (remanent polarization and coercive field) were significantly enhanced. Instead, in fine grains ceramics, of either pure or doped BT, the extrinsic effects related to increased domain wall and grain boundaries density were dominant in both low and high field measurements, overlapping Zr effects. The results were explained in terms of crystal anisotropy correlated with grain size effects.

TiSiC-Cr coatings, with Cr and Si as additional elements, were deposited on Si, C 45 and 316 L steel substrates via cathodic arc evaporation. Two series of coatings with thicknesses in the range of 3.6-3.9 mu m were produced, using either CH4 or C2H2 as carbon containing gas. For each series, different coatings were prepared by varying the carbon rich gas flow rate between 90 and 130 sccm, while maintaining constant cathode currents (110 and 100A at TiSi and Cr cathodes, respectively), substrate bias (-200 V) and substrate temperature (similar to 320 degrees C). The coatings were analyzed for their mechanical characteristics (hardness, adhesion) and tribological performance (friction, wear), along with their elemental and phase composition, chemical bonds, crystalline structure and cross-sectional morphology. The coatings were found to be formed with nano-scale composite structures consisting of carbide crystallites (grain size of 3.1-8.2 nm) and amorphous hydrogenated carbon. The experimental results showed significant differences between the two coating series, where the films formed from C2H2 exhibited markedly superior characteristics in terms of microstructure, morphology, hardness, friction behaviour and wear resistance. For the coatings prepared using CH4, the measured values of crystallite size, hardness, friction coefficient and wear rate were in the ranges of 7.2-8.2 nm, 26-30 GPa, 0.3-0.4 and 2.1-4.8 x 10(-6) mm(3) N-1 m(-1), respectively, while for the coatings grown in C2H2, the values of these characteristics were found to be in the ranges of 3.1-3.7 nm, 41-45 GPa, 0.1-0.2 and 1.4-3.0 x 10(-6) mm(3) N-1 m(-1), respectively. Among the investigated coatings, the one produced using C2H2 at the highest flow rate (130 sccm) exhibited the highest hardness (45.1 GPa), the lowest friction coefficient (0.10) and the best wear resistance (wear rate of 1.4 x 10(-6) mm(3) N-1 m(-1)). (C) 2016 Elsevier B.V. All rights reserved.

The present study is focused on the synthesis, characterization and antifungal evaluation of zinc-doped hydroxyapatite (Zn:HAp) coatings. The Zn:HAp coatings were deposited on a pure Si (Zn:HAp_Si) and Ti (Zn:HAp_Ti) substrate by a sol-gel dip coating method using a zinc-doped hydroxyapatite nanogel. The nature of the crystal phase was determined by X-ray diffraction (XRD). The crystalline phase of the prepared Zn:HAp composite was assigned to hexagonal hydroxyapatite in the P6(3/m) space group. The colloidal properties of the resulting Zn:HAp (x(Zn) = 0.1) nanogel were analyzed by Dynamic Light Scattering (DLS) and zeta potential. Scanning Electron Microscopy (SEM) was used to investigate the morphology of the zinc-doped hydroxyapatite (Zn:HAp) nanogel composite and Zn:HAp coatings. The elements Ca, P, O and Zn were found in the Zn:HAp composite. According to the EDX results, the degree of Zn substitution in the structure of Zn:HAp composite was 1.67 wt%. Moreover, the antifungal activity of Zn:HAp_Si and Zn:HAp_Ti against Candida albicans (C. albicans) was evaluated. A decrease in the number of surviving cells was not observed under dark conditions, whereas under daylight and UV light illumination a major decrease in the number of surviving cells was observed.