National Institute Of Materials Physics - Romania

The growth of gold layers on Pb(Zr,Ti)O-3 (PZT) deposited on SrTiO3 is investigated by X-ray photoelectron spectroscopy in the Au thickness range 2-100 angstrom. Two phases are identified, with compositions close to nominal PZT. The 'standard' phase is represented by all binding energies (Pb 4f, Ti 2p, Zr 3d, O 1s) sensibly equal to the nominal values for PZT, whereas the 'charged' phase exhibits all core levels are shifted by similar to 1 eV toward higher binding energies. By taking into account also scanning probe microscopy images together with recent photoemission results, the 'charged' phase belongs to P(+) regions of PZT, whereas the 'normal' phase corresponds to regions with no net ferroelectric polarization perpendicular to the surface. Au deposition proceeds in a band bending of Phi(PZT) - Phi(Au) similar to 0.4-0.5 eV for both phases, identified as similar shifts toward higher binding energies of all Pb, Ti, Zr, O core levels with Au deposition. The Au 4f core level exhibits also an unusually low binding energy component 1 eV below the 'nominal' Au 4f binding energy position (metal Au). This implies the existence of negatively charged gold, or electron transfer from PZT to Au, although the 'normal' PZT phase have a higher work function, as it is derived from the band bending. Most probably this charge transfer occurs toward Au nanoparticles, which have even higher ionization energies. High resolution transmission electron microscopy evidenced the formation of such isolated nanoparticles. (C) 2013 Elsevier B.V. All rights reserved.

We investigated the influence of rare earth (RE) additions on the structural, dielectric, magnetic and magnetostrictive properties of cobalt ferrite bulk materials. Three lanthanide ions with different ionic radii and magnetic properties were used as dopants: Dy, Gd, La. The structural properties of the sintered samples were investigated using X-ray diffraction, Raman spectroscopy and scanning electron microscopy. The room temperature hysteresis loops were obtained using a vibrating sample magnetometer. The frequency dependence of dielectric permittivity and tangent loss was investigated in the 20 Hz-20 kHz range. The variation of the magnetoelectric response with applied dc magnetic field was analyzed. The insertion of rare earth elements influenced the structural characteristics of the samples (density, cell edge, porosity) and the magnetic and electric properties. An increase in coercive field and a decrease in saturation magnetization and magnetostriction coefficient were observed. These results can be partially explained by the weaker nature of the RE3+-Fe3+ interaction compared to Fe3+-Fe3+ interaction and to the antiferromagnetic alignment of the REFeO3 second phase observed in the diffraction patterns after sintering process. (C) 2012 Elsevier BY. All rights reserved.

Postsynthetic modification of [Cu2(mand)2(hmt)] (mand=mandelic acid, hmt=hexamethylenetetramine) with a chiral, dimeric chromium(III)salen complex led to a robust structure. Characterization of this new material showed that it perfectly preserved the textural and structural properties of the parent metalorganic framework (MOF). Although epoxidation of trans-methyl cinnamate with hydrogen peroxide led to copper leaching of 23%, experiments performed with N-methylmorpholine-N-oxide indicated no leaching, even after 72h of exposure. The obtained chiral MOF is an effective catalyst for the enantioselective epoxidation of trans-methyl cinnamate and leads to (2R,3S)-phenylglycidate with a high enantiomeric excess at room temperature.

Cobalt environment and magnetic defects nature in hydrothermal synthesized anatase CoxTi1-xO2 nanopowders (0 <= x <= 0.1) are investigated by x-ray diffraction and a variety of spectroscopic techniques. One shows that cobalt is partially inserted in the anatase lattice, as Co2+ ions located on substitutional and interstitial sites. The fraction of the diluted Co is limited to 3 at.% for x >= 0.05, while the rest of the Co atoms gather into Co3O4 clusters. As found by electron paramagnetic resonance, the Co doping brings about hole-and electron-excess defects. (C) 2013 AIP Publishing LLC [http://dx.doi.org/10.1063/1.4802819]

TiO2-Au aerogels containing different amounts of gold nanoparticles of different sizes (5 and 16 nm) were successfully synthesized using a sol-gel procedure, and were tested for salicylic acid photo-degradation under UV irradiation. The structure and morphology of the obtained materials were investigated using X-ray diffraction, transmission electron microscopy, and N-2 adsorption-desorption measurements. UV-Vis spectroscopy was used to study the optical properties. The effects of the gold nanoparticles on the TiO2 crystallization process were twofold, as follows: (i) the number of crystallized zones was strongly related to the concentration of the gold nanoparticles, and (ii) the smaller gold particles increased the time taken for the crystallization of the samples. It was found that the noble metal-doped samples exhibited higher degradation rates compared with bare titania. It was found that the most active photocatalyst in each studied system was the sample with the highest concentration of gold nanoparticles. Additionally, the highest degradation rate value was obtained with the smallest Au nanoparticles (46.4 x 10(-3) mu mol/(L.s). (C) 2013, Dalian Institute of Chemical Physics, Chinese Academy of Sciences. Published by Elsevier By. All rights reserved.

The cryogenic detectors in the form of bolometers are presently used for different applications, in particular for very rare or hypothetical events associated with new forms of matter, specifically related to searches for dark matter. In the detection of particles with a semiconductor as target and detector, usually two signals are measured: ionization and heat. The amplification of the thermal signal is obtained with the prescriptions from the Luke-Neganov effect. The energy deposited in the semiconductor lattice as stable defects in the form of Frenkel pairs at cryogenic temperatures, following the interaction of a dark matter particle, is evaluated and consequences for measured quantities are discussed. This contribution is included in the energy balance of the Luke effect. Applying the present model to germanium and silicon, we found that for the same incident weakly interacting massive particle the energy deposited in defects in germanium is about twice the value for silicon. (C) 2013 Elsevier B.V. All rights reserved.

The correlation of the lattice disorder with the nanocrystal average size, in ZnO nanocrystals synthesized by several different methods, has been quantitatively monitored by line shape analysis of the multifrequency electron paramagnetic resonance (EPR) spectra of low concentrations of substitutional Mn2+ probing ions. The observed correlation between the line broadening parameter of the spectrum and the average ZnO nanocrystals size, independent of the synthesis procedure of the ZnO nanocrystals, demonstrates the dominance of the size related strain/disorder. On the basis of this result, a new method for determining the average ZnO nanocrystal size from the quantitative analysis of the EPR spectra of the Mn2+ probes was derived. The nanocrystallization of the disordered ZnO formed by the thermal decomposition of hydrozincite was monitored using this procedure. The observed ZnO nanocrystallite growth kinetics at lower temperatures was described by a structural relaxation mechanism consisting of the local ordering by rearrangements of the atoms in the interfaces/grain boundaries, with a growth activation energy of similar to 23 kJ/mol. When the nanostructured ZnO was more than 75% crystallized, another growth mechanism of the nanocrystals was found to occur, driven by the reduction of the total grain boundary energy.

We report on the fabrication of magnetite/salicylic acid/silica shell/antibiotics (Fe3O4/SA/SiO2/ATB) thin films by matrix-assisted pulsed laser evaporation (MAPLE) to inert substrates. Fe3O4-based powder have been synthesized and investigated by XRD and TEM. All thin films were studied by FTIR, SEM and in vitro biological assays using Staphylococcus aureus and Pseudomonas aeruginosa reference strains, as well as eukaryotic HEp-2 cells. The influence of the obtained nanosystems on the microbial biofilm development as well as their biocompatibility has been assessed. For optimum deposition conditions, we obtained uniform adherent films with the composition identical with the raw materials. Fe3O4/SA/SiO2/ATB thin films had an inhibitory activity on the ability of microbial strains to initiate and develop mature biofilms, in a strain-and antibiotic-dependent manner. These magnetite silica thin films are promising candidates for the development of novel materials designed for the inhibition of medical biofilms formed by different pathogenic agents on common substrates, frequently implicated in the etiology of chronic and hard to treat infections.

Highly textured ZnO thin films were implanted with Co ions at fluences of 1 x 10(16) and 1 x 10(17) ions cm(-2). Although their microstructure observed by analytical high-resolution electron microscopy was very different, SQUID magnetometer measurements showed qualitatively similar magnetic properties. In the low-fluence film, only small modifications, such as a slight amorphization, planar defects or very small (<1-1.5 nm) Co clusters, were hardly observable. Implantation at a higher fluence led to important changes in the film structure: heavy amorphization and metallic Co precipitates were identified by electron diffraction, energy dispersive x-ray spectroscopy (EDS), electron energy loss spectroscopy and scanning transmission electron microscopy spectrum imaging. EDS microanalysis additionally revealed the presence of similar to 2 at% Co atoms that were likely dissolved in the ZnO lattice at the atomic level. No Co oxides or other secondary oxide phases were detected. For both implanted samples, the dimensions of Co precipitates were below the superparamagnetic limit at room temperature. Thermo-magnetization curves and magnetic hysteresis loops measured in the temperature range from 5 to 300 K indicated two superimposed magnetic regimes, one predominant above 50 K and the other below 50 K. We analysed the possible mechanisms and quantitative contributions to explain the observed magnetic behaviour at low and room temperature.

The Griess assay has been used to determine the possible changes in the measured NO2- concentrations induced by TiO2 nanoparticles in three types of nitrite-containing samples: aqueous NaNO2 solutions with known concentrations, and two types of cell culture media-Roswell Park Memorial Institute medium (RPMI-1640) and Dulbecco's Modified Eagle Medium (DMEM-F12) used either as delivered or enriched in NO2- by NaNO2 addition. We have used three types of titania with average particle sizes between 10 and 30 nm: Degussa P25 and two other samples (undoped and Fe3+-doped anatase TiO2) synthesised by a hydrothermal route in our laboratory. The structural, morphological, optical and physicochemical characteristics of the used materials have been studied by X-ray diffraction, transmission electron microscopy (EDX), Mossbauer spectroscopy, Brunauer-Emmett-Teller nitrogen adsorption, UV-Vis reflectance spectroscopy, dynamic light scattering and diffuse reflectance infrared Fourier transform spectroscopy. The opacity and sedimentation behaviour of the studied TiO2 suspensions have been investigated by photometric attenuance measurements at 540 nm. To account for the photocatalytic properties of titania in a biologically relevant context, multiple Griess tests have been performed under controlled exposure to laboratory natural daylight illumination. The results show significant variations of light attenuance (associated with NO2- concentrations in the Griess test) depending on the opacity, sedimentation behaviour, NO2- adsorption and photocatalytic properties of the tested TiO2 nanomaterials. These findings identify material characteristics recommended to be considered when analysing the results of Griess tests performed in biological studies involving TiO2 nanoparticles.