National Institute Of Materials Physics - Romania

We report on thin film deposition by matrix-assisted pulsed laser evaporation of simple hydroxyapatite (HA) or silver (Ag) doped HA combined with the natural biopolymer organosolv lignin (Lig) (Ag:HA-Lig). Solid cryogenic target of aqueous dispersions of Ag:HA-Lig composite and its counterpart without silver (HA-Lig) were prepared for evaporation using a KrF* excimer laser source. The expulsed material was assembled onto TiO2/Ti substrata or silicon wafers and subjected to physical-chemical investigations. Smooth, uniform films adherent to substratum were observed. The chemical analyses confirmed the presence of the HA components, but also evidenced traces of Ag and Lig. Deposited HA was Ca deficient, which is indicative of a film with increased solubility. Recorded X-ray Diffraction patterns were characteristic for amorphous films. Lig presence in thin films was undoubtedly proved by both X-ray Photoelectron and Fourier Transform Infra-Red Spectroscopy analyses. The microbiological evaluation showed that the newly assembled surfaces exhibited an inhibitory activity both on the initial steps of biofilm forming, and on mature bacterial and fungal biofilm development. The intensity of the antibiofilm activity was positively influenced by the presence of the Lig and/or Ag, in the case of Staphylococcus aureus, Pseudomonas aeruginosa and Candida famata biofilms. The obtained surfaces exhibited a low cytotoxicity toward human mesenchymal stem cells, being therefore promising candidates for fabricating implantable biomaterials with increased biocompatibility and resistance to microbial colonization and further biofilm development.

Although Raman spectra reveal, as a signature of double-walled carbon nanotubes (DWCNTs), two radial breathing mode (RBM) lines associated with the inner and outer tubes, the specification of their nature as metallic or semiconducting remains a topic for debate. Investigating the spectral range of the RBM lines, we present a new procedure of the indexing of the semiconducting or metallic nature of the inner and outer shell that forms the DWCNT. The procedure exploits the difference between the intensities of recorded anti-Stokes Raman spectrum and the anti-Stokes spectrum calculated by applying the Boltzmann formulae to the recorded Stokes spectrum. The results indicate that the two spectra do not coincide with what should happen in a normal Raman process, namely, that there are RBM lines of the same intensity in both spectra, as well as RBM lines of higher intensity that are observed in the calculated spectrum. This discrepancy results from the surface-enhanced Raman scattering mechanism that operates differently on metallic or semiconducting nanotubes. In this context, the analysis of the RBM spectrum can reveal pairs of lines associated with the inner/outer shell structure of DWCNT, and when the intensities between the recorded and calculated spectra coincide, the nanotube is metallic; otherwise, the nanotube is semiconducting. Copyright (c) 2014 John Wiley & Sons, Ltd.

xEu(2)O(3)-(1-x)alpha-Fe2O3 (x=0.1, 0.3, 0.5, and 0.7) nanoparticle system was successfully synthesized by mechanochemical activation of Eu2O3 and alpha-Fe2O3 mixtures for 0-12 h of ball milling time. The investigations aimed at exploring the formation of magnetic ceramic nanostructures, which are of crucial importance for catalysis and sensing applications. X-ray powder diffraction (XRD),as well as Fe-57 and Eu-151 Mossbauer spectroscopy and thermal analysis by differential scanning calorimetry (DSC) and thermal gravimetric analysis (TGA) was used to study the phase evolution of xEu(2)O(3)-(1-x)alpha-Fe2O3 nanoparticle system under the mechanochemical activation process. Rietveld refinement of the XRD patterns yielded the values of the particle size as a function of composition and milling times and indicated the formation of the EuFeO3 perovskite for large x values and long milling times. The Fe-57 Mossbauer studies showed that the spectrum of the mechanochemically activated composites evolved from a sextet for hematite to sextets and a doublet upon duration of the milling process with europium oxide. The Eu-151 Mossbauer investigations showed that the isomer shift decreased with increasing milling time for all molar concentrations employed. These results correlate well with the DSC/TGA analysis, which shows the consumption of hematite and the formation of EuFeO3 in the system under investigation. (C) 2014 Elsevier Ltd and Techna Group S.r.l. All rights reserved.

xIrO(2)-(1-x)alpha-Fe2O3(x=0.1, 0.3 and 0.5) nanoparticle systems were successfully synthesized by mechanochemical activation of IrO2 and alpha-Fe2O3 mixtures for 0-12 h of ball milling time. The study aims at exploring the formation of magnetic oxide semiconductors at the nanoscale, which is of crucial importance for catalysis, sensing and electrochemical applications. X-ray powder diffraction (XRD), Mossbauer spectroscopy, magnetic measurements and simultaneous differential scanning calorimetry (DSC) and thermal gravirnetric analysis (TGA) were used to study the phase evolution of xIrO(2)-(1-x)alpha-Fe2O3 nanoparticle systems under the mechanochemical activation process. Rietveld refinement of the XRD patterns yielded the values of the particle size and lattice parameters as function of composition and milling times and indicated the presence of Ir-substituted hematite and Fe-doped iridium oxide for large x values and long milling times. The Mossbauer studies showed that the spectrum of the mechanochemically activated composites evolved from a sextet for hematite to sextets and a doublet upon duration of the milling process with iridium oxide. Magnetic measurements recorded at 5 K in an applied magnetic field of 40,000 Oe showed that the saturation magnetization of the milled samples increased with ball milling time while preserving a multidomain magnetic structure. The unmilled sample at 5 K showed a spinflop type metarnagnetic transition around 30,000 Oe. The Morin transformation was evidenced by zero-field cooling field cooling (ZFC-FC) measurements in 200 Oe and 1 T and the transformation characteristic temperatures were shifted to lower values. (C) 2014 Elsevier Ltd and Techna Group S.r.l. All rights reserved.

Ribbons of Fe-Pd ferromagnetic shape memory alloys were prepared by rapid solidification via the melt-spinning technique. The effect of moderate and high temperature heat treatments on the martensitic transformation and the related changes of the magnetic behavior was analyzed by X-ray diffraction, differential scanning calorimetry and temperature, and field-dependent magnetometry. In addition, information about magnetic easy axis and magnetically field-induced strains (MFIS) were achieved from linear thermal expansion measurements performed under cooling at different applied fields. The observed low values of MFIS in the as-prepared ribbons are due, besides to the small size and random orientation of the grains, to the high atomic disorder inside the crystalline grains. The anisotropy field is enhanced by the reduced atomic disorder, as reflected by the increased MFIS values after thermal treatments.

The charge storage properties of Ge nanocrystals-based MOS-like capacitors with tunnel and gate HfO2 are studied. HfO2/Ge/HfO2/Si trilayer structures were prepared by magnetron sputtering (in Ar) and subsequent rapid thermal annealing (650 degrees C). HfO2/Si structures were also prepared, some under similar conditions, while others were deposited in Ar:O-2. TEM investigations and C-V measurements were performed. TEM on annealed trilayers evidences the formation of ordered and precisely positioned array of Ge nanocrystals embedded in crystalline HfO2. The annealed Al/HfO2/Ge/HfO2/p-Si/Al capacitors present counterclockwise C-V hysteresis (0.8 V memory window) mainly given by Ge nanocrystals, with negligible contribution from crystallized-HfO2 traps.

ZnO complex microstructures were deposited onto interdigitated metallic electrodes by electrospraying. Simple methods, such as wet chemical precipitation and optical lithography, were used for the synthesis of flower-like and snowflake-like ZnO structures and for the preparation of interdigitated metallic electrodes, respectively. The electrosprayed ZnO particles preserve the structural, optical and morphological properties of the chemically synthesized ZnO powders. During the electrospraying process, the ZnO microstructures form bridges between the interdigitated metallic electrodes leading to electrical contacting. Changes in the electron transport through the ZnO microstructures are evidenced by their exposure to ammonia or their passivation with poly(methyl methacrylate). Merging such easy-scalable and low-cost techniques, devices based on electrosprayed complex ZnO structures can be designed.

The main purpose of this study was to evaluate the inhibitory effect of glycerol- iron oxide thin films on Methicillin-Resistant Staphylococcus aureus (MRSA). Our results suggest that glycerol-iron oxide thin films could be used in the future for various biomedical and pharmaceutical applications. The glycerol-iron oxide thin films have been deposited by spin coating method on a silicon (111) substrate. The structural properties have been studied by X-ray diffraction (XRD) and scanning electron spectroscopy (SEM). The XRD investigations of the prepared thin films demonstrate that the crystal structure of glycerol-iron oxide nanoparticles was not changed after spin coating deposition. On the other hand, the SEM micrographs suggest that the size of the glycerol-iron oxide microspheres increased with the increase of glycerol exhibiting narrow size distributions. The qualitative depth profile of glycerol-iron oxide thin films was identified by glow discharge optical emission spectroscopy (GDOES). The GDOES spectra revealed the presence of the main elements: Fe, O, C, H, and Si. The antimicrobial activity of glycerol-iron oxide thin films was evaluated by measuring the zone of inhibition. After 18 hours of incubation at 37 degrees C, the diameters of the zones of complete inhibition have been measured obtaining values around 25 mm.

One of the most fundamental aspects of the heterogeneous catalysis field is the manipulation of the catalysts' activity. In photocatalysis this is carried out by maximizing the right crystal plane of a semiconductor oxide. Until now, most of the papers have achieved this by a combination of different oxides, with noble metals and sometimes with carbon nanomaterials. In this work MWCNTs (multiwalled carbon nanotubes) were applied as "crystallization promoters" in a very simple, safe, one-step hydrothermal method. By this method TiO2 nano/micro crystals with exposed {001} facets were obtained in the first step. The next episode in the crystal manipulation "saga" was the modification of the (001) crystallographic plane's structure by creating ordered/own faceted "crystallographic holes". These elements are capable of further enhancing the obtained activity of titania microcrystals to a higher extent, as shown by the UV driven photocatalytic phenol degradation experiments. The appearance of the holes was "provoked" by simple calcination and their presence and influence were demonstrated by XPS and HRTEM.

Titanium films sputtered on FTO glass were used for obtaining highly oriented titania nanotubes via anodization technique. Then, pulsed laser deposition of CdS was carried out for sensitizing of similar to 60 nm wide titania nanotubes by applying 50, 100, 150 or 200 subsequent laser pulses. Scanning electron microscopy was used to indicate which samples had the open nanotubular structure of titania preserved after the deposition of CdS. Energy dispersive spectroscopy showed that a higher number of applied laser pulses results in the increase of Cd and S quantity within samples. Pulsed laser deposition technique was also employed for the fabrication of PbS counter electrode. I-V characteristics of the photovoltaic cells consisting the obtained electrodes were measured and compared under one-sun illumination. The photovoltaic cell with photoanode sensitized with CdS by applying 150 laser pulses showed the highest current density and voltage among the investigated cell.