Papers by Author: Marco Vittori Antisari

Abstract: Magnesium is one of the most promising materials for hydrogen storage due to its high capacity and low cost. Unfortunately, practical applications are for the moment limited by the slow kinetics and the high operating temperature. Nanostructuring magnesium hydride MgH2, generally by ball milling, introduces plastic deformations and catalysts that highly enhances the H2 absorption and desorption. However a fundamental understanding of the role played by catalysts and interfaces in MgH2 is still lacking. Microscopic characterization of MgH2-Mg system with and without heavy metal catalysts, is achieved by combining accurate SEM observations of samples after partial desorption process and atomic level ab-initio molecular dynamics simulations of MgH2-Mg interfaces. The experimental method is based on low voltage SEM observations of cross sectional powder samples, prepared by a new specific metallographic process. Identification of nucleation sites of the sorption reaction and their correlation with the presence of catalyst particles is achieved by suitable experimental conditions. Moreover ab-initio molecular dynamics clarifies the interplay of interfaces and the deformations induced during desorption by the presence of catalysts that are able to lower binding energies and free hydrogen atoms toward interfaces. Both approaches confirm and characterize the nucleation step in the catalysts driven phase transformation.

Abstract: Carbon nanostructures are under deep investigation due their peculiar properties and possible applications. In particular, development of new methods for the synthesis of these materials and their mechanism of formation represent interesting research fields. Arc discharge allows to produce different forms of carbon nanostructures. The parameters involved in the process, voltage, current density, type and pressure of the surrounding gas can be controlled especially for achieving high quantity of material with enhanced characteristics in terms of purity while the use of transition metal-graphite mixtures has been used to produce single wall structures. Moreover direct current (DC) and alternating current (AC) are suitable for producing carbon nano-materials, but different results can be obtained. In this work the effect of the power frequency in an AC arc discharge technique on the synthesis of carbon nanostructures is reported. Pure graphite electrodes have been arched in air in an homemade apparatus where the material can be collected directly on a cylindrical collector fixed near the arc. In order to avoid the formation of deposits under the arc a symmetrical configuration of the electrodes has been set. The production of carbon soot containing Single Wall Nanohorns (SWNH) and highly convoluted graphene sheets is optimized. The range of power frequencies 32-1000Hz has been investigated and the arcs have been ignited fixing the voltage at 28 V. The materials has been analyzed by field emission scanning electron microscope and high resolution transmission electron microscope. The microstructure of the material synthesized by this apparatus is affected by the power frequency, as the experimental results demonstrate. The samples produced at low frequency presented high amounts of single wall structures, SWNH-type. More compact structures, similar to large onion-like structures, have been found in samples synthesized at high frequency values.

Abstract: One of the factors limiting direct methanol fuel cells (DMFC) performance is the slow kinetics of methanol oxidation at the anode. The importance of the catalyst support for fuel cells has been recognized and different forms of carbon have been suggested. Single wall nanohorns (SWNH) are a new class of carbon with a similar graphitic structure of carbon nanotubes. They are self-assembling materials that produce aggregates of about 100 nm. In the present study, the comparison of the performance of a DMFC equipped with electrocatalysts supported on a commercial carbon black and on SWNH was carried out. The SWNH were synthesized by the arc discharge method in air. The deposition of the Pt and Pt/Ru catalysts on the carbon supports was accomplished by using ethylene glycol as reducing agent. The synthesized catalyst nanoparticles have a very small diameter size (ca. 2.5 nm) and they are uniformly distributed on both carbon supports. The supported electrode catalysts were tested in a DMFC and results indicate that employing SWNH is very promising showing catalytic activities 60 % higher.

Abstract: Hydrogen, being a regenerative and environmentally harmless fuel, can play a crucial role in the energetic scenario of the near future. In recent years several systems for solid-state hydrogen storage have been investigated, among which a few metals and metal alloys show the most promising properties. Mg and Mg-based micro and nanocomposites are widely studied for this application owing to the high gravimetric storage capacity, even if a proper microstructure, mainly at the material surface, has to be setup in order to overtake kinetic constraints often related to the high surface reactivity. In this paper, we present our approach to this problem and report the main findings. We have examined the influence on hydrogenation/dehydrogenation characteristics of different modifications of the bulk and surface microstructure of MgH2 powders processed by ball milling, which appears to be one the most useful methods for preparing powders suitable for hydrogen storage.

Abstract: In order to obtain wear resistant coating as well as thermal barrier on metallic substrates by EPD, the conventional high temperature treatments are inapplicable; so we used an alternative method to densify and make the electrophoretic deposit more adherent. In this work we described a novel method to obtain EPD deposits with good density and adherence to stainless steel substrate. At first, we achieved stabilized alumina and alumina-zirconia based suspensions; to improve the adhesion of ceramic coating on metal, some stainless steel substrates were sandblasted, others were coated with titanium bond layers. Then the substrates were coated by EPD; finally, we used the electron beam to treat the ceramic coating-metallic substrate system on the surface; in this way we obtained adherent and dense EPD coatings. In order to evaluate the quality and the microstructure of the coating sintering, the samples were observed by scanning and transmission electron microscopy; pull tests showed the adhesion of treated EPD coating was about one hundred times higher than that of deposited EPD coating.

Abstract: Carbon nanohorns and multiwalled carbon nanotubes have been synthesized by DC arcdischarge carried out at room pressure in air and Ar-enriched environment, by a specially designed experimental device. The resulting nanostructured material, characterized by electron microscopy and X-ray diffraction, shows different structures according to the condensation channels through which the sublimated carbon atoms are re-condensed in the solid state. Multi-Walled Carbon Nano- Tubes are mainly found in the hard crust formed at the cathode, while nano-horned particles can be recovered from a cylindrical collector surrounding the discharge. Further material, rag-like shaped and with an amorphous structure, can be collected in the reaction area. When the discharge occurs under Ar atmosphere, a larger quantity of this latter phase is synthesized. This suggests that the atmospheric oxygen could play an active role by burning the most reactive among the synthesized phases, like amorphous carbon contributing so to an “in situ” purification of the raw material.

Abstract: The influence of the Co addition and synthesis route on desorption properties of MgH2 were investigated. Ball milling of MgH2-Co blends was performed under Ar using different milling intensities and different weight ratios. Microstructural and morphological characterization, performed by XRD and SEM, show a huge correlation with thermal stability and hydrogen desorption properties investigated by DSC. A complex desorption behaviour is correlated with the dispersion of the catalytic particles that appears to play a main role in desorption performances. The optimum catalyst concentration was found to be around 10 wt.%, while the optimum value of the ball to powder ratio was 10:1.

Abstract: The hydrogen storage performances of Mg-C nanocomposites have been studied on materials synthesized by ball milling with and without addition of an organic additive. The main purpose of this work is to study in more detail the cooperative effect observed when both graphite and benzene are added to the milled blend. In fact, when both components are added to Mg in the ball milling process, good catalyzing properties of the composite surface allow improved sorptiondesorption behavior of the synthesized material. The processed materials have been characterized by XRD to assess the details of the phase structure by Rietveld analysis, while surface features have been studied by XPS, which evidences structural modifications of both the surface Mg oxide and the graphite particles. The hydrogen desorption behavior has been correlated with the surface structure which appears to depend on the carbon to benzene ratio. Thermal stability and hydrogen desorption properties were investigated by DSC. Experimental results on nanocomposites with the same Mg to C weight ratio (70:30) show improved performances for a proper choice of carbon to benzene ratio weight (1/3), even after manipulation of the milled material in air.