National Institute Of Materials Physics - Romania

Silica-based bioactive glasses (SBG) hold great promise as bio-functional coatings of metallic endo-osseous implants, due to their osteoproductive potential, and, in the case of designed formulations, suitable mechanical properties and antibacterial efficacy. In the framework of this study, the FastOs(R)BG alkali-free SBG system (mol%: SiO2-38.49, CaO-36.07, P2O5-5.61, MgO-19.24, CaF2-0.59), with CuO (2 mol%) and Ga2O3 (3 mol%) antimicrobial agents, partially substituting in the parent system CaO and MgO, respectively, was used as source material for the fabrication of intentionally silica-enriched implant-type thin coatings (similar to 600 nm) onto titanium (Ti) substrates by radio-frequency magnetron sputtering. The physico-chemical and mechanical characteristics, as well as the in vitro preliminary cytocompatibility and antibacterial performance of an alkali-free silica-rich bio-active glass coating designs was further explored. The films were smooth (R-RMS < 1 nm) and hydrophilic (water contact angle of similar to 65 degrees). The SBG coatings deposited from alkali-free copper-gallium co-doped FastOs(R)BG-derived exhibited improved wear performance, with the coatings eliciting a bonding strength value of similar to 53 MPa, Lc3 critical load value of similar to 4.9 N, hardness of similar to 6.1 GPa and an elastic modulus of similar to 127 GPa. The Cu and Ga co-doped SBG layers had excellent cytocompatibility, while reducing after 24 h the Staphylococcus aureus bacterial development with 4 orders of magnitude with respect to the control situations (i.e., nutritive broth and Ti substrate). Thereby, such SBG constructs could pave the road towards high-performance bio-functional coatings with excellent mechanical properties and enhanced biological features (e.g., by coupling cytocompatibility with antimicrobial properties), which are in great demand nowadays.

CuO-ZnO core-shell radial heterojunction nanowire arrays were obtained by a simple route which implies two cost-effective methods: thermal oxidation in air for preparing CuO nanowire arrays, acting as a p-type core and RF magnetron sputtering for coating the surface of the CuO nanowires with a ZnO thin film, acting as a n-type shell. The morphological, structural, optical and compositional properties of the CuO-ZnO core-shell nanowire arrays were investigated. In order to analyse the electrical and photoelectrical properties of the metal oxide nanowires, single CuO and CuO-ZnO core-shell nanowires were contacted by employing electron beam lithography (EBL) and focused ion beam induced deposition (FIBID). The photoelectrical properties emphasize that the p-n radial heterojunction diodes based on single CuO-ZnO core-shell nanowires behave as photodetectors, evidencing a time-depending photoresponse under illumination at 520 nm and 405 nm wavelengths. The performance of the photodetector device was evaluated by assessing its key parameters: responsivity, external quantum efficiency and detectivity. The results highlighted that the obtained CuO-ZnO core-shell nanowires are emerging as potential building blocks for a next generation of photodetector devices.

The present study concerns the in vitro oxidative stress responses of non-malignant murine cells exposed to surfactant-tailored ZnO nanoparticles (NPs) with distinct morphologies and different levels of manganese doping. Two series of Mn-doped ZnO NPs were obtained by coprecipitation synthesis method, in the presence of either polyvinylpyrrolidone (PVP) or sodium hexametaphosphate (SHMTP). The samples were investigated by powder X-ray Diffraction, Transmission Electron Microscopy, Fourier-Transform Infrared and Electron Paramagnetic Resonance spectroscopic methods, and N-2 adsorption-desorption analysis. The observed surfactant-dependent effects concerned: i) particle size and morphology; ii) Mn-doping level; iii) specific surface area and porosity. The relationship between the surfactant dependent characteristics of the Mn-doped ZnO NPs and their in vitro toxicity was assessed by studying the cell viability, intracellular reactive oxygen species (ROS) generation, and DNA fragmentation in NIH3T3 fibroblast cells. The results indicated a positive correlation between the specific surface area and the magnitude of the induced toxicological effects and suggested that Mn-doping exerted a protective effect on cells by diminishing the pro-oxidative action associated with the increase in the specific BET area. The obtained results support the possibility to modulate the in vitro toxicity of ZnO nanomaterials by surfactant-controlled Mn-doping.

The structure of BaLnCo(2)O(6-delta) (Ln =La, Pr, Nd, Sm, Gd, Tb and Dy) was studied by the means of synchrotron radiation powder X-ray diffraction, neutron powder diffraction and Transmission Electron Microscopy (TEM), while water uptake properties were analysed with the use of thermogravimetry (TG) and water adsorption isotherms. The structure refinement revealed that the dominant phase in all compositions was orthorhombic with an ordering of the A-site cations along the c-axis and ordering of oxygen vacancies along the b-axis, which was also directly evidenced by TEM. It was shown that both unit cell volume and average Co-oxidation state at room temperature decrease linearly with decreasing Ln radius. TG water uptake experiments in humidified N-2-O-2 gas mixture at 300 degrees C revealed that among all compositions, only BaLaCo2O6-delta and BaGdCo2O6-delta exhibit significant water uptake. Surface water adsorption studies showed that the alpha, a normalised parameter reflecting the surface hydrophilicity, mostly independently of Ln radius was close to 0.5, which means that the surface is neither hydrophobic nor hydrophilic. The results indicated that water uptake observed at 300 degrees C is a bulk process, which cannot be described by standard hydration/hydrogenation reaction and it is related to the layered structure of the perovskite lattice and characteristic to La or Gd being present in the lattice. (C) 2020 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

Structural and magnetic properties of Fe oxide nanoparticles prepared by laser pyrolysis and annealed in high pressure hydrogen atmosphere were investigated. The annealing treatments were performed at 200 degrees C (sample A200C) and 300 degrees C (sample A300C). The as prepared sample, A, consists of nanoparticles with similar to 4 nm mean particle size and contains C (similar to 11 at.%), Fe and O. The Fe/O ratio is between gamma-Fe2O3 and Fe3O4 stoichiometric ratios. A change in the oxidation state, crystallinity and particle size is evidenced for the nanoparticles in sample A200C. The Fe oxide nanoparticles are completely reduced in sample A300C to alpha-Fe single phase. The blocking temperature increases from 106 K in A to 110 K in A200C and above room temperature in A300C, where strong inter-particle interactions are evidenced. Magnetic parameters, of interest for applications, have been considerably varied by the specific hydrogenation treatments, in direct connection to the induced specific changes of particle size, crystallinity and phase composition. For the A and A200C samples, a field cooling dependent unidirectional anisotropy was observed especially at low temperatures, supporting the presence of nanoparticles with core-shell-like structures. Surprisingly high M-S values, almost 50% higher than for bulk metallic Fe, were evidenced in sample A300C.

The second magnetization peak (SMP) in the fourfold symmetric superconducting single crystals (such as iron pnictides and tetragonal cuprates) has been attributed to the rhombic-to-square transition (RST) of the quasi-ordered vortex solid (the Bragg vortex glass, BVG). This represents an alternative to the pinning-induced BVG disordering as the actual SMP mechanism. The analysis of the magnetic response of BaFe2(As1-xPx)(2) specimens presented here shows that the SMP is not generated by the RST. However, the latter can affect the pinning-dependent SMP onset field if this is close to the (intrinsic) RST line, through the occurrence of a "shoulder" on the magnetic hysteresis curves m(H), and a maximum in the temperature variation of the DC critical current density. These features disappear in AC conditions, where the vortex system is dynamically ordered in the RST domain, emphasizing the essential role of vortex dislocations for an efficient accommodation of the vortex system to the pinning landscape and the SMP development. The m(H) shoulder is associated with a precipitous pinning-induced proliferation of dislocations at the RST, where the BVG elastic "squash" modulus softens. The DC magnetization relaxation indicates that the pinning-induced vortex system disordering continues above the RST domain, as the basic SMP mechanism.

We obtained carbon nanotubes (CNTs) doped polymer dispersed liquid crystal (PDLC) films using the nematic E7 and polymethyl methacrylate, a composite that combines the benefic characteristic of the liquid crystals (LC) and carbon nanoparticles. The clearing temperatures recorded by differential scanning calorimetry for the PDLC blends were found to be lower than the value recorded for pure E7 LC mixture with no significant impact of the CNTs' concentration. Broadband dielectric spectroscopy (DS) measurements were performed in the (10(-1) / 107) Hz frequency range, in the temperature domain (280-350) K. From the DS study, a two order magnitude variation of the conductivity over the entire temperature range was observed. The presence of CNTs results in an increase of electrical conductivity, with increasing concentration. Because the loss tangent spectra have complex shapes, they were fitted using the generalized Havriliak-Negami functions, and the characteristic relaxation times were extracted. The dependency of the characteristic relaxation time on temperature was modeled using the Vogel-Fulcher-Tammann function, and it showed a temperature variation according to the Arrhenius law. The increase of the CNT concentration increases the activation energy of the molecular electric dipoles of the LC. The interface LC-polymer interactions influence the nematic to isotropic phase transition of the LC.

Organic bulk heterojunctions (BHJ) based on zinc phthalocyanine (ZnPc), fullerene compounds (C60 fullerene and [6,6]-phenyl C71 butyric acid methyl ester (PC70BM)), and 5,6,11,12-tetraphenylnaphthacene (rubrene) were fabricated through the matrix-assisted pulsed-laser evaporation (MAPLE) technique. Thus, ZnPc:C60 and ZnPc:PC70BM binary BHJ and ZnPc:rubrene:PC70BM ternary BHJ were deposited as thin films on various substrates. The preservation of the chemical structure of the organic compounds during the MAPLE deposition was confirmed by infrared spectroscopy. The structural, optical, and morphological properties of the deposited layers were investigated by X-ray diffraction (XRD), UV-Vis spectroscopy, photoluminescence (PL), field emission scanning electron microscopy (FESEM), and atomic force microscopy (AFM), respectively. Further, the electrical properties of the developed structures based on ZnPc:C60, ZnPc:PC70BM, and ZnPc:rubrene:PC70BM were evaluated. The J-V characteristics of the organic structures, recorded under illumination, show that an increase in the open-circuit voltage (V-OC) is achieved in the case of the ternary blend in comparison with that obtained for the binary blends. The results evidenced that MAPLE-deposited thin films containing binary and ternary organic bulk heterojunctions can find applications in the field of photovoltaic devices.

xHfO(2)-(1-x)alpha-Fe2O3 (x = 0.1, 0.3, 0.5 and 0.7) nanoparticles system was obtained using mechanochemical activation by high energy ball milling for time periods ranging from 0 to 12 h. X-ray diffraction patterns revealed the presence of two phases, a hafnium-doped hematite and an iron-doped hafnia, which competed with each other to form a solid solution. The trend observed in the lattice parameters using Rietveld refinement was consistent with differences in ionic radii between Hf and Fe. Crystallite sizes for both hematite and hafnia were analyzed as function of milling time using the Scherrer method and found to decrease down to similar to 15 nm for all molar concentrations used. Mossbauer spectroscopy revealed the presence of 1-5 sextets corresponding to different numbers of Hf nearest neighbors of Fe in the hematite structure. The different hyperfine magnetic fields could be resolved in the model of local atomic environment. Substitutions of Fe in hafnia gave rise to a nonmagnetic phase represented by a quadrupole split doublet, whose abundance was found to increase with ball milling time. Hysteresis loops recorded at 5 K showed that the Hf-doped system does not saturate in an applied magnetic field of 5 T. The Morin transition was observed during zero-field-cooling-field cooling (ZFC-FC) in an external magnetic field of 200 Oe. Differential scanning calorimetry with thermal gravimetric analysis (DSC-TGA) evidenced an exothermic peak for the starting oxides and an endothermic peak for the solid solution.