National Institute Of Materials Physics - Romania

Amination of bromobenzene with aniline was carried out on heterogeneous Au-TiO2 catalysts prepared using the deposition-precipitation method. The deposition of gold in loadings in the range 0.1-0.9 wt.% on titania occurred with the formation of gold particles with controlled size and oxidation state as demonstrated from TEM and XPS measurements. In addition, Raman and DR-UV-Vis investigation of these catalysts showed that the interaction of Au particles with the support stabilized the metallic state of gold. Catalytic results demonstrated that the conversion and selectivity depended on the gold-particle size and dispersion, while the mechanism of reaction was in direct relation with the reaction medium. Working in DMC, the solvent was playing the role of base. The advantage of working in DMC was avoiding the formation of KBr which is very difficult to be separated from the reaction products. HBr resulted as a by-product formed adducts with the coupling product, which was separated as crystals at room temperature by a simple filtration. However, in DMC, the reaction occurred with low selectivities. In dioxane, the presence of potassium ethoxide as base was mandatory. The reaction occurred with very high selectivities for moderate conversions. The conversion was limited by KBr released from the reaction. However, the use of the heterogeneous catalyst has the advantage of scavenger, since KBr becomes chemisorbed on the surface and could be simple removed by percolation and the catalyst can be reused. (C) 2012 Elsevier Inc. All rights reserved.

Samarium is deposited on Si(001) at various temperatures (room temperature to 400 A degrees C), and the surface structure, interface reactivity, electron configuration, and magnetic properties are investigated by low-energy electron diffraction (LEED), X-ray photoelectron spectroscopy (XPS), and magneto-optical Kerr effect (MOKE), respectively. It is found that metal Sm is present on samples prepared at room temperature with an interface layer containing mostly Sm2+ and a lower amount of Sm3+. When samples are prepared at high temperature, much less Sm-0 is found with an increasing amount of Sm2+. Freshly prepared Sm-0 and SmSi2 layers react strongly with oxygen from the residual gas, promoting formation of Sm2O3 at the expense of both metal Sm and SmSi2. Room temperature ferromagnetism is observed for all prepared layers with a decrease of the saturation magnetisation when samples are prepared at high temperature. It is found that ferromagnetism implies mostly Sm3+ and Sm metal. In addition to these findings, this work proposes a new assignment of the Sm 3d chemically shifted components. Also, a noticeable variation of the XPS Sm 3d spin-orbit splitting is found as a function of the Sm ionization state.

Novel complexes of type M2L(CH3COO)(4)center dot nH(2)O (M:Ni, n = 4; M:Cu, n = 2 and M:Zn, n = 0; L: ligand resulted in 1,2-phenylenediamine, 3,6-diazaoctane-1,8-diamine and formaldehyde template condensation) were synthesised and characterised. The features of complexes have been assigned from microanalytical, IR, UV-Vis, H-1 NMR, EPR as well as magnetic data at room temperature. Processes as water elimination as well as oxidative degradation of both organic components (bismacrocycle and acetate) were observed. The final product of decomposition was metal (II) oxide as powder X-ray diffraction indicates.

Effect of an antibacterial drug, sulfacetamide, IUPAC name N-[(4-aminophenyl) sulfonyl] acetamide (APSA), on the corrosion products formed on carbon steel surface in 1.0 mol L-1 HCl solution has been investigated using mass loss, X-ray photoelectron spectroscopy (XPS), and simultaneous thermal and differential scanning calorimetry/differential thermal analysis (TG/DSC/DTA). Mass loss measurements reveal that the corrosion rate of carbon steel is retarded by APSA and that the inhibition efficiency of this inhibitor increases with increasing the concentration. XPS analysis shows that, at this stage, the main product of corrosion is a non-stoichiometric Fe3+ oxyhydroxide, consisting of a mixture of FeO(OH) in anhydrous or hydrated forms, containing Cl- inclusions and adsorbed APSA molecules. The mechanism of inhibition was discussed in light of the chemical structure of the investigated inhibitor. The corrosion products were analyzed using TG/DSC/DTA technique.

Single molecule magnets are of great interest due to a multitude of potential applications for some of which thin films are required. Traditional physical vapor deposition techniques are not suitable for the deposition of these fragile materials with low decomposition temperatures. Matrix Assisted Pulsed Laser Evaporation technique has been employed for the growth of thin films of the single molecule magnet Mn-12(Propionate) on Si and glass substrates. In this paper we report on the appropriate growth conditions and also the morphology, chemical composition and magnetic behavior of the films. Continuous Mn-12(Propionate) films with properties similar to bulk materials have been obtained. (c) 2011 Elsevier B.V. All rights reserved.

Amorphous titania thin films with increasing Fe content have been prepared by RF magnetron sputtering. X-ray absorption spectroscopy revealed modifications of both local structures/environment of the Ti and Fe atoms, with formation of phases containing amorphous material and a magnetite-like phase. The temperature dependence of the electrical conductivity of the films was investigated for temperatures higher than half of the Debye temperature (T > 391 K). It was found that the electrical conductivity in the amorphous Fe/TiO2 films obeys the Meyer-Neldel rule. The origin of this behavior is explained on the basis of the multiphonon-assisted hopping model.

The effects of the self-assembled 4,4'-thio-bis-benzenethiolate protected gold nanoclusters onto a p-GaAs (1 0 0) electrode were examined by AFM, XPS, SHG and EIS investigations. The AFM and XPS results revealed a well-ordered overlayer exhibiting a bi-modal highly correlated fractal behavior which, however, cannot fully protect the semiconducting surface against the oxidation in air. The EIS data pointed out the influence exerted by the gold-monolayer protected clusters (Au-MPCs) over the charging/discharging processes observed at p-GaAs (1 0 0) electrode. Although the applied potential is varied linearly, the potential drop within the semiconductor space charge region as well as that across the Au-MPCs layer undergoes stepped changes supposed to result in the discrete charging of the Au-MPCs. These effects point to an electronic equilibrium between the Au-MPCs and the semiconducting substrate. Fermi level pinning and enhancement of the SHG response in the potential range where the surface/interface states in the semiconductor band gap become electrically active bring further proof in this respect. (c) 2012 Elsevier Ltd. All rights reserved.

High quality pulsed laser deposited lead zirconate titanate (PZT) films are obtained by pulsed laser deposition on SrRuO3(111) single crystal layers and characterized by X-ray photoelectron spectroscopy (XPS), to determine the surface composition. It is found that a minor amount of Pb forms PbO2 at the surface and also some Pb is included into the contamination layer, in form of a Pb(CO3)2 layer of about 1?nm thickness, occupying about one quarter of the PZT surface. The stoichiometry of the outermost 45?nm layers yielded as PbZr0.25Ti0.80O2.5, which suggest the formation of an oxygen depleted, Brownmillerite-like layer at the surface, of at least 5?nm thickness.

Epitaxial growth of Bi1.5-xZn0.92-yNb1.5O6.92-1.5x-y (BZN) thin films was achieved on (100)(pc) LaAlO3 substrate by pulsed laser deposition (PLD) and by chemical solution deposition based on Pechini process. Effect of bismuth and zinc deficiency on the BZN thin films obtained by PLD was discussed, in relation with the starting target composition. Dielectric permittivity and bandgap values were determined from electrical and spectroscopic ellipsometry measurements performed on randomly oriented films grown on Pt/Si substrate. BZN thin films obtained by PLD exhibit, at 100 kHz, a dielectric constant of epsilon(r) = 203 and quite low dielectric losses of tan delta = 5 x 10(-2). Epitaxial ferroelectric - dielectric KTa0.65Nb0.35O3 (KTN) -Bi1.5-xZn0.92-yNb1.5O6.92-1.5x-y (KTN on BZN and BZN on KIN) bilayers were obtained by PLD on (100)(pc) LaAlO3 with the insertion of a suitable buffer layer of KNbO3 in the case of KTN on BZN. Such multilayer heterostructures with an epitaxial growth control of each layer are promising candidates for potential integration in microwave devices. (C) 2011 Elsevier B.V. All rights reserved.

Different hybrid structures were obtained by coating magnetic nanoparticles of perovskite type manganite at optimal doping (La0.67Sr0.33MnO3, LSMO) with different quantities of polypyrrole (PPy). The amorphous layer of polypyrrole surrounding the crystalline magnetic core was observed by high resolution transmission electron microscopy (HRTEM) and analyzed by using X-ray photoelectron spectroscopy (XPS) and X-ray absorption spectroscopy (XAS) measurements in near edge structure (XANES) techniques. By analyzing the magnetic behavior of the samples one can observe that the surface modification of magnetic nanoparticles by PPy results in an increase in the saturation magnetization of the composites. The process is ascribed to paired electrons transferred from the delocalized p states of the PPy into the outer disordered layers of the manganite. The analysis of pre-edge peak of the Mn K-edge XANES spectra in the case of PPy coated LSMO nanoparticles indicates that the charge transfer between polymer and nanoparticles is (directed) going to missing or distorted oxygen positions, hence increasing the 3d electrons' mobility and orbital hybridization between the neighboring manganese ion. As a consequence, within the surface layers of LSMO nanoparticles, both energy bands disrupted the structure, and the double exchange process between Mn ions was reestablished determining the saturation magnetizations and pre-edge features increase, respectively. (C) 2012 American Institute of Physics. [doi:10.1063/1.3686662]