The present study is focused on the development of new VIII group metal on CeO2 – ZrO2 (CZO) catalyst to be used in reforming reaction for syngas production. The catalyst are tested in the oxyreforming process, extensively studied by Barbera [44] in a new multistep process configuration, with intermediate H2 membrane separation, that can be carried out at lower temperature (750°C) with respect the reforming processes (900 – 1000°C). In spite of the milder temperatures, the oxy-reforming conditions (S/C = 0.7; O2/C = 0.21) remain critical regarding the deactivation problems mainly deriving from thermal sintering and carbon formation phenomena. The combination of the high thermal stability characterizing the ZrO2, with the CeO2 redox properties, allows the formation of stable mixed oxide system with high oxygen mobility. This feature can be exploited in order to contrast the carbon deposition on the active metal surface through the oxidation of the carbon by means of the mobile oxygen atoms available at the surface of the CZO support. Ce0.5Zr0.5O2 is the phase claimed to have the highest oxygen mobility but its formation is difficult through classical synthesis (co-precipitation), hence a water-in-oil microemulsion method is, widely studied and characterized. Two methods (IWI and bulk) for the insertion of the active metal (Rh, Ru, Ni) are followed and their effects, mainly related to the metal stability and dispersion on the support, are discussed, correlating the characterization with the catalytic activity. Different parameters (calcination and reduction temperatures) are tuned to obtain the best catalytic system both in terms of activity and stability. Interesting results are obtained with impregnated and bulk catalysts, the latter representing a new class of catalysts. The best catalysts are also tested in a low temperature (350 – 500°C) steam reforming process and preliminary tests with H2 membrane separation have been also carried out.

The work investigates the feasibility of a new process aimed at the production of hydrogen with inherent separation of carbon oxides. The process consists in a cycle in which, in the first step, a mixed metal oxide is reduced by ethanol (obtained from biomasses). The reduced metal is then contacted with steam in order to split the water and sequestrating the oxygen into the looping material’s structure. The oxides used to run this thermochemical cycle, also called “steam-iron process” are mixed ferrites in the spinel structure MeFe2O4 (Me = Fe, Co, Ni or Cu). To understand the reactions involved in the anaerobic reforming of ethanol, diffuse reflectance spectroscopy (DRIFTS) was used, coupled with the mass analysis of the effluent, to study the surface composition of the ferrites during the adsorption of ethanol and its transformations during the temperature program. This study was paired with the tests on a laboratory scale plant and the characterization through various techniques such as XRD, Mössbauer spectroscopy, elemental analysis... on the materials as synthesized and at different reduction degrees In the first step it was found that besides the generation of the expected CO, CO2 and H2O, the products of ethanol anaerobic oxidation, also a large amount of H2 and coke were produced. The latter is highly undesired, since it affects the second step, during which water is fed over the pre-reduced spinel at high temperature. The behavior of the different spinels was affected by the nature of the divalent metal cation; magnetite was the oxide showing the slower rate of reduction by ethanol, but on the other hand it was that one which could perform the entire cycle of the process more efficiently. Still the problem of coke formation remains the greater challenge to solve.

Powder Metallurgy (PM) is a net- shape and cost effective technology used for the production of steel parts having good mechanical properties and geometrical precision. In the conventional press and sinter process, the voids among the powder particles cannot be completely eliminated, and the as sintered microstructure contains a certain amount of residual porosity. Mechanical properties are consequently lower than those of the corresponding wrought steels [1]. In particular, the fatigue resistance is significantly affected by porosity; crack tends to nucleate in correspondence of clusters of pores, and to propagate along the network of interconnected pores [2, 3]. Fatigue resistance can be improved on increasing the density, reducing pore size and pore clustering and enlarging the sintered ligaments between pore, or, similarly to wrought steels, by thermochemical (carburizing and nitriding) or mechanical treatments (shot peening). Carburizing consists in a surface carbon enrichment, which gradually decreases towards the core. After quenching high carbon martensite is formed at the surface, characterized by high hardness and a compressive residual stresses suitable for wear and fatigue resistance. Low pressure carburizing is a variant of the conventional gas carburizing performed under sub-atmospheric pressure with pressurized gas quenching. It is quite attractive for carburized PM sintered steels, for two main reasons. 1. Porosity increases the surface exchange area, enhancing the risk of oxidation mainly in Cr and Cr-Mn steels. Low pressure carburizing uses propane or acetylene, as carburizing gas, which does not contain oxidizing agents. 2. Quenching oil remains entrapped in the open porosity, and has to be eliminated. The possibility to combine low pressure carburizing with gas quenching results in clean parts as well as lower distortion. However, the combination between the very high carburizing potential of LPC and the large surface area of porous steels results in overcarburizing, with the precipitation of grain boundary carbides in Cr steels, and the formation of retained austenite in the case in Cr free ones [4, 5]. This problem can be solved by either increasing density, to close the residual porosity, or rolling and shot peening, to eliminate the surface porosity. Nitriding is based on the nitrogen enrichment of the surface layers of steel. On the base of nitrogen content the surface microstructure can be divided in two zones: the compound and the diffusion layer. The former is in principle a ceramic layer, whilst the latter consists in the base matrix hardened by solid solution and by the precipitation of nitrides. The nitride precipitation induces a compressive residual stress field which offers a resistance to the nucleation and propagation of the fatigue crack, improving the fatigue resistance. In order to obtain a hardened and deep diffusion layer the steel has to contain alloying elements with a high affinity for nitrogen, as chromium and molybdenum. Nickel and manganese have a negligible interaction with nitrogen. Among the different nitriding processes, plasma nitriding is recommended for sintered steel. Plasma nitriding is less sensitive to porosity than gas nitriding due to the particular mechanism of nitrogen diffusion (volume diffusion) which allows a uniform diffusion front on the steel surface and a homogeneous nitrogen distribution [6, 7]. Therefore, a preliminary surface densification is not necessary. Shot peening is a flexible and cost effective solution to improve the fatigue performances of mechanical parts, as gears and springs, thanks to the compressive residual stress generated below the surface and the surface work hardening. The improvement in fatigue resistance is more effective if shot peening is applied on case hardened steels, because of the more stability of the compressive residual stresses. Since the fatigue strength of sintered steels strongly depends on the material density, shot peening is a useful technique to improve such property, owing to the densification of the surface layer [8, 9]. The fatigue cracks nucleates beneath this layer and since it cannot propagate in a compression field, it moves towards the core. This PhD thesis is part of the an international research project, “Höganäs Chair project- fourth round†, financed by Höganäs AB, world leader in the production of ferrous powders, involving four research institutions: Trento University, Technique University of Wien, Carlos III University of Madrid and Slovak Academy of Science, Institute for Materials Research, Kosice. The aim of the project is to carry out a cooperative study to design highly performing structural steels by the conventional Powd

The dramatic impact that vascular diseases have on human life quality and expectancy nowadays is the reason why both medical and scientific communities put great effort in discovering new and effective ways to fight vascular pathologies. Among the many different treatments, endovascular surgery is a minimally-invasive technique that makes use of X-ray fluoroscopy to obtain real-time images of the patient during interventions. In this context radiopaque biomaterials, i.e. materials able to absorb X-ray radiation, play a fundamental role as they are employed both to enhance visibility of devices during interventions and to protect medical staff and patients from X-ray radiations. Organic-inorganic hybrids are materials that combine characteristics of organic polymers with those of inorganic metal oxides. These materials can be synthesized via the sol-gel process and can be easily applied as thin coatings on different kinds of substrates. Good radiopacity of organic-inorganic hybrids has been recently reported suggesting that these materials might find applications in medical fields where X-ray absorption and visibility is required. The present PhD thesis aimed at developing and characterizing new radiopaque organic-inorganic hybrid materials that can find application in the vascular surgery field as coatings for the improvement of medical devices traceability as well as for the production of X-ray shielding objects and garments. Novel organic-inorganic hybrids based on different polyesters (poly-lactic acid and poly-ε-caprolactone) and polycarbonate (poly-trimethylene carbonate) as the polymeric phase and on titanium oxide as the inorganic phase were synthesized. Study of the phase interactions in these materials allowed to demonstrate that Class II hybrids (where covalent bonds exists between the two phases) can be obtained starting from any kind of polyester or polycarbonate, without the need of polymer pre-functionalization, thanks to the occurrence of transesterification reactions operated by inorganic molecules on ester and carbonate moieties. Polyester based hybrids were successfully coated via dip coating on different kinds of textiles. Coated textiles showed improved radiopacity with respect to the plain fabric while remaining soft to the touch. The hybrid was able to coat single fibers of the yarn rather than coating the yarn as a whole. Openings between yarns were maintained and therefore fabric breathability was preserved. Such coatings are promising for the production of light-weight garments for X-ray protection of medical staff during interventional fluoroscopy, which will help preventing pathologies that stem from chronic X-ray exposure. A means to increase the protection capacity of hybrid-coated fabrics was also investigated and implemented in this thesis. By synthesizing the hybrid in the presence of a suspension of radiopaque tantalum nanoparticles, PDMS-titania hybrid materials with tunable radiopacity were developed and were successfully applied as coatings. A solution for enhancing medical device radiopacity was also successfully investigated. High metal radiopacity was associated with good mechanical and protective properties of organic-inorganic hybrids in the form of a double-layer coating. Tantalum was employed as the constituent of the first layer deposited on sample substrates by means of a sputtering technique. The second layer was composed of a hybrid whose constituents are well-known biocompatible organic and inorganic components, such as the two polymers PCL and PDMS, and titanium oxide, respectively. The metallic layer conferred to the substrate good X-ray visibility. A correlation between radiopacity and coating thickness derived during this study allows to tailor radiopacity simply by controlling the metal layer sputtering deposition time. The applied metal deposition technique also permits easy shaping of the radiopaque layer, allowing production of radiopaque markers for medical devices that can be unambiguously identified by surgeons during implantation and in subsequent radiological investigations. Synthesized PCL-titania and PDMS-titania hybrids strongly adhered to substrates and show good biocompatibility as highlighted by cytotoxicity tests. The PDMS-titania hybrid coating was also characterized by high flexibility that allows it to stand large substrate deformations without detaching nor cracking, thus being suitable for application on flexible medical devices.

Tissue engineering is a discipline that aims at regenerating damaged biological tissues by using a cell-construct engineered in vitro made of cells grown into a porous 3D scaffold. The role of the scaffold is to guide cell growth and differentiation by acting as a bioresorbable temporary substrate that will be eventually replaced by new tissue produced by cells. As a matter or fact, the obtainment of a successful engineered tissue requires a multidisciplinary approach that must integrate the basic principles of biology, engineering and material science. The present Ph.D. thesis aimed at developing and characterizing innovative polymeric bioresorbable scaffolds made of hydrolysable polyesters. The potentialities of both commercial polyesters (i.e. poly-e-caprolactone, polylactide and some lactide copolymers) and of non-commercial polyesters (i.e. poly-w-pentadecalactone and some of its copolymers) were explored and discussed. Two techniques were employed to fabricate scaffolds: supercritical carbon dioxide (scCO2) foaming and electrospinning (ES). The former is a powerful technology that enables to produce 3D microporous foams by avoiding the use of solvents that can be toxic to mammalian cells. The scCO2 process, which is commonly applied to amorphous polymers, was successfully modified to foam a highly crystalline poly(w-pentadecalactone-co-e-caprolactone) copolymer and the effect of process parameters on scaffold morphology and thermo-mechanical properties was investigated. In the course of the present research activity, sub-micrometric fibrous non-woven meshes were produced using ES technology. Electrospun materials are considered highly promising scaffolds because they resemble the 3D organization of native extra cellular matrix. A careful control of process parameters allowed to fabricate defect-free fibres with diameters ranging from hundreds of nanometers to several microns, having either smooth or porous surface. Moreover, versatility of ES technology enabled to produce electrospun scaffolds from different polyesters as well as “composite” non-woven meshes by concomitantly electrospinning different fibres in terms of both fibre morphology and polymer material. The 3D-architecture of the electrospun scaffolds fabricated in this research was controlled in terms of mutual fibre orientation by properly modifying the instrumental apparatus. This aspect is particularly interesting since the micro/nano-architecture of the scaffold is known to affect cell behaviour. Since last generation scaffolds are expected to induce specific cell response, the present research activity also explored the possibility to produce electrospun scaffolds bioactive towards cells. Bio-functionalized substrates were obtained by loading polymer fibres with growth factors (i.e. biomolecules that elicit specific cell behaviour) and it was demonstrated that, despite the high voltages applied during electrospinning, the growth factor retains its biological activity once released from the fibres upon contact with cell culture medium. A second fuctionalization approach aiming, at a final stage, at controlling cell adhesion on electrospun scaffolds, consisted in covering fibre surface with highly hydrophilic polymer brushes of glycerol monomethacrylate synthesized by Atom Transfer Radical Polymerization. Future investigations are going to exploit the hydroxyl groups of the polymer brushes for functionalizing the fibre surface with desired biomolecules. Electrospun scaffolds were employed in cell culture experiments performed in collaboration with biochemical laboratories aimed at evaluating the biocompatibility of new electrospun polymers and at investigating the effect of fibre orientation on cell behaviour. Moreover, at a preliminary stage, electrospun scaffolds were also cultured with tumour mammalian cells for developing in vitro tumour models aimed at better understanding the role of natural ECM on tumour malignity in vivo.

This PhD work mainly focus on the synthesis and characterization of calcium phosphate powders for plasma spray coating. The preparation of high temperature phase stabilized βTCP and HA/βTCP powders for plasma spray coating applications has been the topic of investigation. Nowadays plasma sprayed coatings are widely used for biomedical applications especially in the dental and orthopaedic implantation field. Previously Ti based alloys were widely used for the orthopaedic and dental implant applications because of its high corrosion and good biocompatibility. Due to the limited osteoconductivity edges of Ti implants with fibrous tissues delays the healing time. To overcome these limitations different types of surface modification processes are employed on the surface of Ti. The coating of HA is a widely used surface modification technique due to its excellent biological properties. HA is a well employed bone graft material due to its similarity with human hard tissues. The plasma spraying of HA on the Ti surface is the most widely used technique mainly due to its process simplicity, low cost and bulk production. The present research focuses on the modification of HA coatings for the improvement of bio-degradation properties of HA. HA/βTCP composite powders are used to overcome the poor biodegradation properties of HA. The issue related to the use of βTCP is the phase transformation (β to α) at high temperature. To overcome this phase transformation, the βTCP powder was doped with MgO. The high temperature phase stabilized MgO doped βTCP and HA/βTCP powders were synthesized by solid state method and granulated using spray granulation. The properties of the granulated powders (100-150μm) were analysed with XRD, FT-IR, SEM, flowabilty, density etc. and are used in plasma spray coating process. The produced coatings were subjected to the thermal treatment and βTCP and HA/βTCP plasma sprayed coatings are obtained. The successively produced coatings were characterized, and the invitro properties like solubility and bioactivity behaviours were studied.

Hydrothermal carbonization (in acronym, HTC) is a thermochemical conversion process through which it is possible to directly transform wet organic substrates into a carbonaceous material, referred as hydrochar. Hydrochar has chemical and physical characteristics that make it similar to fossil peats and lignite. Depending on the process conditions, mostly temperature and residence time, this material can be enriched in its carbon content, modifying its structure and providing it interesting characteristics that make it possible to be used for several applications, such as for energy production, as a soil conditioner and improver, for carbon dioxide sorption and sequestration, and some others reported in literature. HTC is a different process, if compared to other common thermochemical processes, such as pyrolysis, torrefaction, gasification, etc., because it works in wet conditions (humidity content higher than 60%). As a matter of fact, biomass is transformed into hydrochar because of the properties of hot pressurized water, that acts both as a reactant and as a catalyst. The HTC process has been studied from many years, although at present not all the chemical reactions that occur during the process are completely known. Moreover, the application of this quite new process to different substrates can bring to different results. Even though HTC can be applied to any kind of organic material (of both animal and vegetable derivation), the possible uses of hydrochar can strongly be influenced by the characteristics of the feedstock. This, for example, can be due to legislative constraints. In Chapter 1, an overview of the existing literature is presented. To get insights on this process, a small bench scale batch reactor has been designed and built at the Department of Civil, Environmental and Mechanical engineering of the University of Trento, Italy. This reactor has been tested, prior to be used with real substrates. In Chapter 2 the reactor and the preliminary tests done are described. In this work, the HTC process applied to three different substrates have been studied: grape marc, the EWC 19.05.03 residue and the EWC 19.12.12 residue. In Chapter 3 the three raw substrates are described. Grape marc is produced by the winery industries or by distilleries. This feedstock is composed by woody seeds and holocellulosic skins and it presents an average humidity content of about 60%. At present, it is used for the production of animal food or it is landfilled. In this case, the application of HTC can be an interesting alternative to these end uses because, through this process, grape marc can be recovered, for example, for energy production. The hydrochar produced from this feedstock could be even used as a soil conditioner. In Chapter 4 several analyses on the hydrochar, on the process water and on the gaseous phase obtained during the carbonization tests are presented. The EWC 19.05.03 residue is a by-product of the composting treatment applied to the organic fraction of municipal solid waste (MSW). In collaboration with Contarina S.p.A., a company that collects and treats MSW in the province of Treviso, in the North-East of Italy, this by-product was carbonized and tested both as a soil conditioner and for energy production. Results of the analyses on the solid, liquid and gaseous phases produced by the HTC process are reported in Chapter 5. The EWC 19.12.12 residue is a by-product of the refuse derived fuel (RDF) production, from the residual fraction of the MSW. This substrate was provided by Contarina S.p.A. and preliminary tests on the exploitability of the hydrochar for energy production are reported in Chapter 6, together with analyses on both the liquid and gaseous phases. A rigorous energy balance has been proposed in Chapter 8, based on the experimental data obtained for grape seeds. In this chapter, all the hypotheses and the assumptions taken to evaluate the enthalpy of the HTC reaction at different process conditions (namely, three different temperatures and three residence times) are described. In Chapter 8 a kinetic model is proposed, based on a two-step reaction mechanism. The activation energy and pre-exponential factor of the various degradation reactions were determined by means of least square optimization versus the experimental data of grape marc. A thermo fluid model is even proposed in this chapter. The model integrates mass, momentum and heat equations within the reactor domain by means of the finite volumes method (f.v.m.) approach. Convective and radiative exchange between the reactor and the fluid within the reactor have been implemented in the f.v.m. model. Under two strong assumptions (mono-component and mono-phase fluid, which fulfils the reactor), it was possible to estimate the behaviour of an equivalent fluid (eq_fluid), in terms of thermal properties of the fluid (thermal capacity, thermal conductivity and thermal diffusivity). Moreover, a simplified dynamic analytic model is also presented – based on lumped capacitance method – in order to simulate the thermal behaviour of the system, using the actual temperature profile imposed by the reactor external heater. A resistance-capacitance network was used to describe the system. Finally, the Henry’s law has been applied to assess the amount of gas really produced during the HTC process. In Chapter 9, the main conclusions of this work are reported.