Publications

Pt(0.5wt%)-Al-SBA-15 and Pt(0.5wt%)-Al-MCM-41 bifunctional catalysts were prepared by wet impregnation and investigated in the hydrogenation of anthracene and the hydrogenolysis/hydrogenation of a series of synthesized Diels-Alder adducts with anthracene and anthracene derivatives. The mesoporous texture of the investigated catalysts allowed the hydrogenation of these substrates to a large extent. In direct correlation with the size of the Pt particles, Pt-Al-SBA-15 exhibited a higher activity. Both catalysts exhibited a strong Lewis acidity associated with the presence of the Al extra-framework species. The acidity of these catalysts afforded the esterification of the reaction byproduct, that is, succinic anhydride, with methanol or ethanol, and the hydrocracking/decyclization of one hydrogenated ring to lead to 1,2,3,4-tetrahydronaphthalene derivatives. A good correlation with the calculated values of the reaction Gibbs free energy has been evidenced.

A new synthesis method based on the electrochemical reduction of alpha,alpha,alpha',alpha'-tetrabromo-p-xylene in the presence of single-walled carbon nanotubes (SWNTs) is used to obtain composites of carbon nanotubes (CNTs) functionalized with poly(para-phenyl-enevinylene) (PPV). To separate the effects of metallic and semiconducting CNTs on their interaction with PPV, the experiments are carried out with SWNTs enriched in semiconducting (S, 99%) and metallic (M, 98%) tubes. Significant changes in the relative intensity and shift of the radial breathing vibrational mode are reported in the Raman spectra of the as-prepared SWNTs samples, i.e., as mixtures of metallic (33%) and semiconducting (66%) entities and SWNTs enriched in M tubes (98%) that result from the electrofunctionalization with PPV. This different behavior originates in the noncovalent and covalent functionalization of SWNTs enriched in M and S SWNTs tubes with PPV, respectively. A gradual decrease in the absorption of the infrared (IR) bands of PPV situated in the spectral range of 750-1000 cm(-1) as a result of the increase of the polymer weight on the blank Au support is reported. The electrofunctionalization of the as-prepared SWNTs induces position changes of the PPV IR absorption bands. In the presence of S-enriched SWNTs, a significant increase in the absorbance of the two IR bands peaked at 1452 and 1471 cm(-1), which are assigned to the vibrational modes of the phenyl ring stretching and the quinoid structure of the PPV, respectively, is reported. This results from the covalent bonding of the PPV macromolecular chains onto the surface of the SWNTs enriched in S tubes. Our results also demonstrate that the photoluminescence quenching effect reported for the PPV/SWNTs composites is due to the metallic nanotubes.

Triglycine sulphate crystal (TGS) is one of the most studied ferroelectric materials, having a second order transition around 49 degrees C. The complex dielectric constant we have measured on the frequency range 1-10(7) Hz and on a large temperature range, in ferroelectric phase after the para - ferro transition. Temperature was monitored from room temperature to 65 degrees C, were for 30min it was kept constant and then was lowered down at a rate of 0.6 degrees C/min. Both component of permittivity were automatically registered. This study was focused on the dielectric relaxation processes. Three fundamental relaxation mechanisms (LF, MF, and HF) were found and analyzed with the Cole-Cole functions. The activation energy of these relaxation mechanisms have been estimated in the ferroelectric phase

In this work we present the deposition of amorphous SiC thin films by radiofrequency dual magnetron sputtering. The dependence of the deposited films properties over the discharges electrical power and the effect of hydrogenous species (H-2 and/or D-2) addition to main discharge gas (Ar) were investigated. Accurate elemental analysis of the samples, including detection of hydrogen and deuterium, was performed by ion beam analysis (IBA) techniques: RBS (Rutherford Backscattering Spectrometry) and ERDA (Elastic Recoil Detection Analysis). SiCx thin films with thicknesses between 1700 and 4500 angstrom and C/Si ratio between 0.2/1 and 1.25/1 were obtained in different deposition conditions. The results prove that thin films of amorphous SiC with well controlled properties can be produced using radiofrequency dual magnetron sputtering. (C) 2015 Elsevier B.V. All rights reserved.

We investigate partially disordered antiferromagnetism in CoCl2-2SC(NH2)(2), in which ab-plane hexagonal layers are staggered along the c axis rather than stacked. A robust 1/3 state forms in applied magnetic fields in which the spins are locked, varying as a function of neither temperature nor field. By contrast, in zero field and applied fields at higher temperatures, partial antiferromagnetic order occurs, in which free spins are available to create a Curie-like magnetic susceptibility. We report measurements of the crystallographic structure and the specific heat, magnetization, and electric polarization down to T = 50 mK and up to mu H-0 = 60 T. The Co2+ S = 3/2 spins are Ising-like and form distorted hexagonal layers. The Ising energy scale is well separated from the magnetic exchange, and both energy scales are accessible to the measurements, allowing us to cleanly parametrize them. In transverse fields, a quantum Ising phase transition can be observed at 2 T. Finally, we find that magnetic exchange striction induces changes in the electric polarization up to 3 mu C/m(2), and single-ion magnetic anisotropy effects induce a much larger electric polarization change of 300 mu C/m(2).

FePt system attracts currently a great deal of interest for applications as future RE free permanent magnets. Among the key issues to be solved one may count the decreasing of the ordering temperature and improvement of magnetic behavior. For that purpose we have studied the effect of a nitriding post-synthesis procedure on the FePtAgB melt spun ribbons, aimed at refining the microstructure and enhancing the magnetic performances. Deep structural characterization by transmission electron microscopy, electron diffraction, energy dispersive X-ray spectroscopy and X-ray diffraction allowed us to observe the morphology and to correctly assign and identify the nature of the main granular phases observed. Nitriding procedure is shown to strongly enhance the (001) texturing and the degree of ordering of the L1(0) FePt phase, as well as largely increase of coercivity, compared to the as-cast state. These changes are interpreted in terms of Ag segregation towards intergranular region associated to N diffusion and creation of vacancies that favor consistently the process of ordering the FePt grains into the L1(0) tetragonal phase. (C) 2015 Elsevier B.V. All rights reserved.

The strong correlation between morphology and charge storage properties of HfO2/Ge/HfO2/Si trilayer structures was evidenced. The morphology of structures deposited by magnetron sputtering and electron beam evaporation was tailored by rapid thermal annealing and investigated by transmission electron microscopy, Raman and X-ray photoelectron spectroscopies. The best hysteresis loops (capacitance-voltage characteristics) were obtained for trilayers with high density Ge nanocrystals located in the position of as-deposited Ge layer. The decrease of Ge nanocrystals density narrows the memory window, by spreading Ge atoms into HfO2 matrix (sputtered trilayers), or by Ge atoms expulsion toward HfO2 nanocrystals surface (evaporated trilayers). (C) 2015 Elsevier Ltd. All rights reserved.

FePt-based alloys are currently under scrutiny for their possible use as materials for perpendicular magnetic recording. Another possible application is in the field of permanent magnets without rare-earths, magnets that may operate at higher temperatures than the classic Nd-Fe-B magnets. Within this study, FeCoPt alloys prepared by rapid solidification from the melt are structurally and magnetically characterized. In the as-cast FeCoPt ribbons, a three-phase structure comprising well-ordered CoFePt and CoPt L1(0) phases embedded in a disordered fcc FePt matrix was evidenced by XRD, HREM and SAED. Extended transmission electron microscopy analysis demonstrates the incipient formation of ordered L1(0) phases. X-ray diffraction was used to characterize the phase structure and to obtain the structural parameters of interest for L1(0) ordering. In the as-cast state, the co-existence of hard magnetic CoFePt and CoPt L1(0) tetragonal phases with the soft fcc FePt phase is obtained within a refined microstructure made of alternatively disposed grains (grain sizes from 1 to 7 nm). Following a thermal treatment of 1 h at 670 degrees C, the soft magnetic fcc matrix phase transforms to tetragonal L1(0) phases (disorder-order transition). The resulting CoPt and CoFePt L1(0) phases have grains of around 5-20 nm in size. In the as-cast state, magnetic measurements show a quite large remanence (0.75 T), close to the value of the parent L1(0) FePt phase. Coercive fields of about 200 kA/m at 5 K were obtained, comparable with those reported for some FePt-based bulk alloys. Upon annealing both remanence and coercivity are increased and values of up to 254 kA/m at 300 K are obtained. The polycrystalline structure of the annealed FeCoPt samples, as well as the formation of multiple c-axis domains in different CoPt and CoFePt regions (which leads to a reduction of the magneto-crystalline anisotropy) may account for the observed coercive fields that are lower than in the case of very thin FeCoPt films. A Curie temperature of about 820 K (close to 550 degrees C) is reported for the Fe35Co15Pt50 alloy which opens wide possibilities for the use of such magnets in high operating temperature industrial applications. The present results indicate that ternary FeCoPt alloys hold a great potential as a novel class of rare earth free exchange-spring coupled nanocomposite magnets. (C) 2015 Elsevier B.V. All rights reserved.

The possibility to intercalate noble gas atoms below epitaxial graphene monolayers coupled with the instability at high temperature of graphene on the surface of certain metals has been exploited to produce Ar-filled graphene nanosized blisters evenly distributed on the bare Ni(111) surface. We have followed in real time the self-assembling of the nanoblisters during the thermal annealing of the Gr/Ni(111) interface loaded with Ar and characterized their morphology and structure at the atomic scale. The nanoblisters contain Ar aggregates compressed at high pressure arranged below the graphene monolayer skin that is decoupled from the Ni substrate and sealed only at the periphery through stable C-Ni bonds. Their in-plane truncated triangular shapes are driven by the crystallographic directions of the Ni surface. The nonuniform strain revealed along the blister profile is explained by the inhomogeneous expansion of the flexible graphene lattice that adjusts to envelop the Ar atom stacks.