National Institute Of Materials Physics - Romania

Low-frequency (X-band) electron spin resonance (ESR) investigations on commercially available large-grained cubic boron nitride (cBN) superabrasive powders of various coloration, combined with high-frequency (W-band) ESR measurements on oriented submillimeter-size single crystallites selected from the same powder samples, resulted in a clear identification of several types of paramagnetic point defects. The resulting spin Hamiltonian parameters describing the ESR spectra observed in the 3-293 K temperature range and the photosensitivity of the paramagnetic defects observed in amber-colored cBN samples are reported. It is shown that the nature of the paramagnetic centers depends on the color of the investigated samples and that, in many cases, uncontrolled impurities seem to be involved in their structure.

Nanocrystalline cubic ZnS doped with 0.2% mol manganese, exhibiting a stable mesoporous structure, was synthesized at room temperature by a non toxic surfactant-assisted liquid liquid reaction. The X-ray diffraction measurements demonstrate the formation of a sponge-like mesoporous material built from cubic ZnS nanocrystals of 1.8 nm average sizes, with a tight distribution of pores of 1.8 nm mean diameter. The transmission electron microscopy images confirm the formation of the mesoporous structure with walls of 3.1 nm mean thickness built from cubic ZnS nanocrystallites of 2.1 nm average size. The resulting tight distribution of crystallites and pores yields a well resolved Electron Paramagnetic Resonance spectrum, with the narrowest reported component lines attributed to three types of isolated Mn2+ centers, called Mn2+ (I), Mn2+ (II) and Mn2+ (III). From the analysis of the spin Hamiltonian parameters it is shown that in the Mn2+ (I) centers the paramagnetic ion is situated at substitutional Zn sites in the ZnS nanocrystals, being also subjected to a small axial distortion. The relative concentration changes under thermal treatment experiments strongly suggest that in both Mn2+ (II) and Mn2+ (III) centers the Mn2+ ion is localized on the surface of the ZnS nanocrystallites, being bond to an oxygen ion in the first case and to an additional water molecule in the second case.

Cobalt-aluminate spinel, CoAl2O4, has been synthesized by two synthesis variants of the complexation method: tartarate and gluconate routes. The complex precursors have been characterized by IR, UV-vis spectroscopy and thermal analysis. The cobalt-aluminate spinet has been investigated by XRD, IR, UV-vis and luminescence spectroscopy and TEM. The results indicated that in both cases the single-phase nanocrystalline CoAl2O4 spinet was formed. The average crystallite size from TEM images was in the range 50-60 nm. The emission spectra of CoAl2O4 in the visible region confirmed the presence of tetrahedral coordinated Co2+ ion. (C) 2010 Elsevier B.V. All rights reserved.

The nonlinear optical (NLO) crystal Y0.6Lu0.4Ca4O(BO3)(3) (starting composition) of good quality has been grown from the melt by the Czochralski pulling method. X-ray diffraction experiments show that the structure of grown crystal belongs to the monoclinic system with space group Cm and its unit cell parameters have been measured to be a = 0.80711(2)nm, b = 1.60132(1)nm, c = 0.35230(8)nm and beta = 101.166(1)degrees. The crystal possesses a wide transmission range from UV to IR, which is advantageous for applications as new NLO material for frequency doubling of solid state lasers operating in the near infrared range.

Macroporous polyacrylonitrile/hydroxyapatite (PAN/HAp) composite bead was studied for cadmium removal in a fixed-bed column. The morphology of PAN/HAp composite bead was measured. The adsorption performance of PAN/HAp composite bead in the column was examined by varying bed height and HAp amount in PAN bead. The maximum adsorption capacity and the exhaustion time were determined from the breakthrough curves. Experimental data was described using the Adams-Bohart model. Bed height did not exert large influence on the maximum adsorption capacity and the exhaustion time. The kinetic rate constant and the adsorption capacity of the bed were found to be affected by the total HAp amount.

In the first part of this study it has shown that the interaction between collagenous polypeptides (collagen type I with native structure of triple helix and collagen hydrolyzates with no significant secondary structure) and ionic surfactants (sodium dodecyl sulfate and hexadecyl trimethylammonium bromide) involves the formation of micelle-like clusters of ionic surfactant adsorbed onto polypeptide backbone (polypeptide-surfactant complexes) at surfactant concentrations much lower than its cmc. The present investigation is focused on the influence of polypeptide-ionic surfactant complexation on thermal denaturation of the collagen type I extracted from calfskin and young horse tendons. On the basis of capillary viscometry, a good correlation between denaturation temperatures and activation energies of viscous flow for the dilute aqueous collagen-ionic surfactant solutions at pH 2.5 and 8.0 has been found. Beginning from that, it has established that the presence of ionic surfactant reduces thermal stability of the two collagens, with a more pronounced effect in the case of sodium dodecyl sulfate. Accordingly, it has been proposed a thermal denaturation mechanism of the collagen triple helix in the presence of ionic surfactants.

Nitrogen doped TiO2 aerogels were obtained by sol gel process followed by supercritical drying with liquid CO2. Urea and NH3 (25% aqueous solution) were used as nitrogen sources. The as-prepared aerogels were submitted to thermal treatments performed under different experimental conditions (temperature and heating time). Increasing the temperature from 450 degrees C to 550 degrees C a decrease about 32% and 15.4% of the particle size and surface OH groups' concentration, respectively and an increase about 21.4% of the incorporated nitrogen in TiO2 lattice were observed. The immersion of the TiO2 aerogels in NH3 solution induced a decreasing by 48.86% and by 80% of the S-BET and the aerogel porosity, respectively. The photocatalytic activity of the obtained N-doped TiO2 was found to depend mainly on the nitrogen incorporation in the TiO2 lattice. (C) 2009 Elsevier Inc. All rights reserved.

Structural and optical properties of (Co0.01Zn0.99)Al2O4 and Zn(Al(1.99)Ln(0.01))O-4 (where Ln(III)=Eu(III), Tb(III)) spinels obtained by a variant of the complexation method-tartarate route were studied. The tartarate precursors have been characterized by IR, UV-vis and luminescence spectroscopy. The doped aluminium based spinets have been investigated by X-ray diffraction (XRD), transsmision electron microscopy (TEM), infrared spectroscopy (IR), ultraviolet visible spectroscopy (UV-vis) and luminescence spectroscopy. Pure spinel nanometer powders were obtained. Under excitation at 380 nm the nanoparticles exhibits strong luminescence corresponding to D-5(0) -> F-7(2) transition of Eu3+ ions and respectively, to D-5(4) -> 7 F-j (j = 3, 4, 5, 6) transition of Tb3+ ions. No blue emission from the D-5(3) state were observed. (C) 2010 Elsevier B.V. All rights reserved.

CuO/Al2O3 and NiO/Al2O3 catalysts prepared by incipient wetness impregnation were used for the oxidation of Reactive Black 5 (RB5) in aqueous solution. Removal of the dye was assessed by High Performance Liquid Chromatography (HPLC) and Total Organic Carbon (TOC) measurements and the generation of the hydroxyl radicals in the process was evaluated by chemiluminescence measurements. To put in evidence the interaction RB5 - catalyst and the surface species formed onto catalysts during the oxidation, Diffuse Reflectance Infrared Fourier Transform (DRIFT) analysis was performed. A different behavior of the two catalytic systems was revealed by the comparative analysis of the data obtained from the adsorption and oxidation tests. Only CuO/Al2O3 was effective in the RB5 degradation, NiO/Al2O3 acted as a simple adsorbent. In the presence of CuO/Al2O3, at H2O2 concentration of 40 mM the azo dye was totally eliminated from both solution and catalyst surface after 4 h, with a mineralization degree higher than 90%. However, a strong inhibition of the catalytic oxidation of RB5 was observed in the presence of phosphate ions. In the conditions of hydrogen peroxide excess, the rate equation in the case of copper catalyst was simply expressed by a pseudo-first order equation and the model was found to fit well the data. The amount of copper leached from catalyst during the oxidation process was only 1.0-1.6% per cycle leading to the conclusion that the decrease of the dye mineralization with the number of cycles has to be explained mostly by the surface covering with the reaction products, at least to a certain extent. (C) 2010 Elsevier B.V. All rights reserved.