National Institute Of Materials Physics - Romania

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.

We report on the enhancement of critical current density (J(c)) and the unusual behaviour of its dependence on field orientation in YBa2Cu3O7-x (YBCO) nanostructured films by a combination of substrate decoration with Ag nano-dots, of the incorporation of BaZrO3 (BZO) nano-particles and nano-rods, and of multilayer architecture (a thin SrTiO3 layer separating two 1.5 mu m-thick YBCO layers). SrTiO3 insulating layers were 15, 30 or 45 nm thick. The highest improvement of J(c) in applied magnetic fields along the c-axis and smaller than 1 T occurs in the bi-layer with 30 nm-thick STO, but the influence of STO thickness is small. Our thick nanostructured films show significant improvement of J(c) in the magnetic field along the ab-plane direction. The presence of BZO nano-rods, ab-plane defects and nano particles of BZO and Y2O3 was observed in transmission electron microscopy (TEM) images of the film. The peculiarities of artificial pinning centres revealed in the TEM images of the nanostructured films are used to explain an unusual split of the peak in the J(c) dependence on the magnetic field along the ab-plane of YBCO. Effective pinning potentials in high magnetic fields have rather high values for such thick films.

The enhancement of the Raman scattering in Cs3Bi2I9 is evaluated by the ratio I-T/I-300K between the relative intensities of the Raman line peaked at 146cm(-1), when the spectra are recorded in the temperature range of 88-300K, as a signature of exciton-phonon interactions. In the resonant and nonresonant conditions, excitation wavelengths 476, 561, and 660nm, respectively, are used in order to overlap with great accuracy the bands disclosed by diffuse reflection, photoconductivity (PC), photoluminescence (PL), and photoluminescence excitation (PLE) spectra. Based on the experimental analyses, the strength of exciton-phonon interaction is dependent on the defects in the crystal and the type-range interaction of the excitations in an independent Bi2I93- cluster. The noticeable PL band, attributed to excitons trapped on different stacking faults, manifests some defects in crystal that diminish the movement of excitons. This effect significantly decreases the overlaps of excitons with the phonons, resulting in a reduced exciton-phonon coupling.

Fe doped ZnO particles of flower-like shape, hexagonal prisms and hybrid structures flower-prisms have been synthesized by hydrothermal technique, and their luminescence and magnetic properties have been investigated as a function of the morphology changes due to iron dopant (0-0.03 at.% Fe3+). The X-ray diffractograms of Zn1-xFexO powders indicated a hexagonal wurtzite polycrystalline structure. SEM images reveal the change of Zn1-xFexO grains shape from flower-like to hexagonal prisms as the Fe concentration (x) increases from 0 to 3 at.% Fe. Undoped ZnO shown weak room temperatures ferromagnetism, with high coercivity (H-c = 107 Oe) and saturation magnetization M-s of 1.5-10(-3) emu/g. ZnO doped with 1 and 3 at.% Fe presented a significant increase of the magnetization in comparison with the undoped ZnO. For ZnO doped with 3 at.% Fe, Ms = 32.5-10(-3) emu/g and M-rem = 0.78-10(-3) emu/g. Compared with other reports on magnetic properties of undoped and Fe doped ZnO, these results indicated higher coercivity and smaller magnetizations. The drop in the intensity of characteristic green-yellow photoluminescence band of ZnO at about 550-600 nm was attributed to the decrease of the number of oxygen vacancies and interstitial oxygen. By increasing the Fe concentration, the electron paramagnetic resonance (EPR) signal of undoped ZnO decreases due to the decrease of defects concentration. (C) 2017 Elsevier Ltd. All rights reserved.

In this paper, we investigate the influence of Cu, Co, and Al substitutions on the transport properties, and in particular, the magnetoresistive effect in Ni-Fe-Ga ferromagnetic shape memory alloys (FSMAs) prepared as ribbons by melt spinning method and subjected to different thermal treatments. X-ray diffraction, differential scanning calorimetry, magnetometry, and magnetoresistive characterizations were performed. In the range of the martensitic transformation (MT), different FSMA compositions show a rich spectrum of different behaviors. For one of the compositions (Ni52Fe20Co2Ga23Al3), the magnetoresistance (MR) showed a local minimum or, on the contrary, a local maxima of reduced amplitude on cooling, in the range of the MT, depending on the performed thermal treatments. In the same composition, by replacing one Al atom with a Co one, no local extremes are seen, the alloy having a concomitant magneto-structural transition. When the magnetic field was varied, the MR showed a nonmonotonic variation in the martensite phase for some compounds, possibly due to the dynamics of the martensite variants realignment. From the studied compositions, the highest MR found on the MT of -9% for 5 T is for Ni50Fe20Ga27Cu3.