Solid State Phenomena Vol. 106

Abstract: Nanopowders of yttrium aluminium garnet Y3Al5O12 (YAG) doped with neodymium ions were obtained by the co-precipitation method from the reaction of aluminium and yttrium nitrate and neodymium oxide with ammonia. After washing and drying the hydroxide precursors were calcined at 500, 700, 800 and 900 °C for 1 hour and at 1000 °C for 3 hours. This product was treated by ball milling in a zirconia vial for 0.5, 1.5 and 10 h in order to achieve smaller nanoparticles. The structure, microstructure, morphology and optical properties were investigated by means of diffractometric, microscopic and spectroscopic techniques. The course of the amorphous-to-crystalline transformation was complete after calcining the powder for 1 hour at 900 °C. In the sample calcined for 3 hours at 1000 °C, the mean size of crystallite microdomains was reduced from 600 Å to 300, 250 and 160 Å after 0.5, 1.5 and 10 h of mechanical treatment respectively. The treated product was found to be contaminated with ZrO2. This contamination, from the vial and hardened ZrO2 balls reaches ca. 30 wt % after 10 h of mechanical treatment but causes only a slight reduction of the neodymium luminescence life-time, thus maintaining significant applicative properties.

Abstract: The preparation of transparent nanoceramics from nanocrystalline Y3Al5O12 (YAG) powders doped with rare-earth ions has been described and the results of investigation of the structure and morphology have been presented. Decomposition of YAG nanocrystals into YAlO3 (YAP) was observed. The temperature and pressure for the decomposition was much lower than that reported for larger crystals. The transformation was connected with grain coarsening. The influence of the method of preparation of the YAG nanopowders on the final transparency of the nanoceramic produced was determined. Preliminary results of the dependence of luminescence properties on the structural transformation of the nanograins are presented.

Abstract: Experimental results are presented on the ablation of copper and brass targets in a liquid environment: ethanol, acetone, or water by irradiation with either a pulsed copper vapour laser (0.51 μm) or a pulsed Nd:YAG laser (1.06 μm). The ablated material was ejected into the surrounding liquid as nanoparticles of average size 20 nm. The nanoparticle composition depends on the nature of the liquid. Ablation of 60%Cu, 40%Zn brass in ethanol results in formation of core-shell nanoparticles. Brass nanoparticles were characterized by a well-defined plasmon peak at 510-520 nm.

Abstract: In this paper studies of the changes of the morphology of silver colloidal nanoparticles under laser irradiation at different fluences and wavelengths have been presented. Silver nanoparticles of size 10-30 nm were prepared in a gelatin stabilized AgNO3 solution under reduction with K-Na-tartrate. They were then exposed to pulsed laser radiation at 532 nm, 400 nm and 266 nm. In addition to the fragmented particles, relatively larger-size (1400-1500 nm) rightangled structures were found to be formed in the solution. The experimental conditions favouring laser-induced transformation of the morphology of nanoparticles have been determined.

Abstract: 4-mercaptoaniline functionalised platinum particles of 2 nm diameter were synthesised and over-grafted with 2-thiophenecarbonyl chloride. The derivative particles were dispersed in DMSO and gave long term stable suspensions. The Langmuir-Blodgett technique was then used to build up stable Langmuir-Blodgett films and the electrochemical behaviour of these ultra-thin films towards oxygen reduction was investigated in an acidic medium. It revealed direct activity without any previous activation treatments despite of the presence of the organic shell at the particle surface. Furthermore, XPS experiments revealed that the organic crown was not significantly destroyed on prolonged cycling. The results open a way to study original and versatile platinum-based nanocomposites.

Abstract: Classical precipitation techniques applied to a nickel di-dodecylsulphate Ni(DS)2 precursor were developed. In the range of concentrations studied this precursor forms direct micelles in water. In pH-controlled double jet precipitation with soda at 60°C, the pure a, poorly crystallised bbc and well crystallised b phases are successively obtained by pH shifts from 8 to 11, whereas the platelet morphology remains similar. In the same conditions, classical salts never lead to a phase and the particle size and morphology is pH dependent. Hydroxide precipitation by ammonia decomplexation, via heating at 60°C, Ni(DS)2 leads to well-calibrated stacks of b- Ni(OH)2 nanopancakes (300 nm in diameter and 200 nm stacking length) whereas classical salts lead to micrometric particles characterised by thin interconnected walls.

Abstract: BaTiO3 (BT) nanoparticles were prepared by the hydrothermal technique using different starting materials and the microstructure examined by XRD, SEM, TEM and HRTEM. X-ray diffraction and electron diffraction patterns showed that the nanoparticles were the cubic BaTiO3 phase. The BT nanoparticles prepared from the starting materials of as-prepared titanium hydroxide and barium hydroxide have spherical grain morphology, an average size of 65 nm and a fairly narrow size distribution. A uniform diffraction contrast across each single grain is observed in the TEM images, and the clear lattice fringes (with d110 = 0.28 nm) observed in HRTEM images reveal that well-crystallized BT nanoparticles are synthesized by the hydrothermal method. The edges of the particles are very smooth, with no surface steps. BT nanoparticles with average grain size of 90 nm, synthesized using barium hydroxide and titanium dioxide as the starting materials, show surface facets. In this case a bimodal size distribution of large faceted and smaller particles is observed. Diffraction contrast variation across the particles caused by high strains within the particles is clearly observed. The high strains obviously stem from structural defects formed during hydrothermal synthesis, presumable in the form of lattice OH− ions and their compensation by cation vacancies. HRTEM images demonstrate that surface facets parallel to the (100) and (110) planes and small islands with 3 ~ 4 atomic layer thickness are frequently observed around the edge of the particles.

Abstract: The aim of the work is to establish if maleic anhydride copolymer acts as a grain growth modulator and/or as a biocompatible functionalisation agent for hydroxyapatite. Experimental work was developed in three directions: nanocomposites synthesis, nanocomposites characterization and citotoxicity tests on nanocomposites. Maleic anhydride copolymer – HAp nanocomposites were prepared by in situ functionalisation in hydrothermal conditions and were characterized by chemical quantitative analysis, XRD, FT-IR, SEM, specific surface area and picnometric densities. Chemical bonding between the copolymer carboxyl groups and calcium ions of HAp induced a peak of 1577 cm-1 on the FT-IR analysis. Following the evolution of this characteristic peak with the hydrothermal synthesis conditions (different temperatures and pressures) and corroborates the results with XRD and SEM analysis it was pointed out the copolymer grain growth modulator behaviour. Citotoxicity studies in vitro on mice fibroblast cultures were performed. The results proved the biocompatibility of new hybrid –polymer nanocomposites.

Abstract: Tin dioxide is a wide band semiconductor, with interesting chemical physical and mechanical properties, used in a variety of industrial, domestic, medical and agricultural applications, including gas detectors, transparent conductors, solar cells, anti-static films, nanoelectronic devices etc. The variety of nanosized SnO2 production methods in the form of powders or layers (e.g. solid state, sol-gel, sputtering, laser ablation, template, solution precipitation, precursor oxidation, CVD, PVD, etc) are discussed.

Abstract: Zirconia can be considered to be one of the most important ceramic materials because of its large range of industrial applications (catalysis, coatings, spacecraft shielding, paint additives, oxygen sensors, fuel cells, nuclear fuel matrices, an alternative high permittivity material to replace silicon oxide as a gate dielectric in MOS devices). Many of these applications require the use of zirconia in a nanocrystalline form. It is now well established that a monoclinc to tetragonal phase transition is trigged by the grain size of zirconia. The mechanism of this phase transition in zirconia is not yet clearly understood. Several experiments point out that the thermodynamic properties of nanocrystalline solids are particle-size dependent. Size-related effects like the reduction of the melting temperature and displacement of the phase boundaries can be predicted. Zirconia can be considered a textbook example for describing these effects. In this ceramic several polymorphic transformations occur with the change of external parameters (Temperature, pressure, …). In this paper, the behaviour of the tetragonal to monoclinic martensitic phase transition within Landau theory framework in particular will be discussed, pointing out the peculiar effects related the small grain size of the nanoparticles. Neutron diffraction experiments will illustrate the of these arguments and provide some insight to the understanding of the behaviour of nanocrystals in severe environments, such as in nuclear reactors or in space applications.