Wear is an ubiquitous phenomenon affecting an extremely wide number of technological system, often determining their premature failure. In this regard, wear and friction behavior of friction materials and the characterization of wear debris from brake disc system is an important step to understand the dominant wear mechanisms active in a given tribological system, in order to improve its performances and to increase the expected lifetime. In the thesis, four tribological task has been performed, under the code name Case I, II, III & IV. This thesis present the work on the development of a characterization methodology of a wear debris from brake pad-disc system, M1 and M2 friction materials at elevated temperatures and study of the wear and frictional behavior of a heat treated cast iron disc. In Case I, the dry sliding behavior of two friction materials (M1 & M2) have been investigated. The sliding tests were carried out on a pin-on-disc test rig, using a cast iron disc as a counterface, under mild conditions (the applied nominal pressure was 2 MPa and the sliding speed was 3.14 m/s). The results shows that friction material M2 is characterized by a lower friction coefficient than friction material M1, and the friction coefficient is stable during the test. In addition, friction material M2 shows a lower wear rate than M1. The results were explained by considering the characteristics of the friction layer that is established during the test. On the bases of the experimental observations, the lower friction and wear of friction material M2 was attributed to the formation a quite uniform and well compacted friction layer, due to the presence of ingredients, such as Zr oxides, able to form small particles during sliding that are compacted and held together by the presence of metallic ingredients, such as copper. The absence of Zr-oxides in the formulation of M1friction material and the presence, in their place, of hard and abrasives Mg, Zn and Al-oxides, impeded the formation of wide covering friction layer, increasing friction and wear. The different frictional properties of the brake pads determine their driving performances, and the different wear behavior determine their in-service deterioration and also their attitude to emit particulate matter in the environment, which is nowadays a concern of increasing importance. Under the Case II, a streamline characterization protocol for wear debris emitted under wear testing conditions (Case I - M1 friction material) used for disc brake assemblies is presented. An important aspect of the experimental test methodology concerns the powder collection methodology on different substrates: aluminum foil, for a gravitational integral collection, and polycarbonate filters of an ELPI+ impactor equipment, on which particles are selectively trapped, according to their average size. The protocol is based on the application of different materials characterization tools, like scanning electron microscopy (SEM), energy dispersive X-ray spectroscopy (EDXS), X-ray diffraction (XRD), transmission electron microscopy (TEM) and selected area electron diffraction (SAED). The deliberate aim of the study was to identify suitable selection parameters, like specimen availability and average particle size, for an effective and smart application of the mentioned experimental techniques so to optimize testing times and obtain statistical reliable results. The proposed characterization approach could be profitably employed also in other contexts, like environmental and health monitoring, as far as particulate matter, even from other sources than brake systems, is concerned. We extended the work in Case I by investigating further wear mechanisms of M1 & M2 pins at elevated temperatures i.e., 170°C, 200°C, 250°C, 300°C and 350°C, under Case III. The results showed a clear evolution of frictional parameters with temperature. For M1, the working temperature were 155°C, 200°C, 250°C and 300°C, the absence of frictional parameters with temperature and wear behavior of M1 is higher than M2 with one degree higher order of magnitude. Wear tracks on the discs form from the piling up of wear fragments produced both by the tribo-oxidation of the disc itself and from the wearing out of the pin materials. This accumulation of wear debris on the disc surface nearly compensate for the weight loss associated with disc wear. The observed tribological behaviour is very much influenced by the thermal degradation of the phenolic binder of the friction material. The thermal decomposition kinetics was confirmed by thermogravimetric analyses, conducted on purpose on the pin material, and by Raman spectroscopy results, that confirmed the presence of carbonaceous products on the worn out pin surface. For M2, the working temperature were 170°C, 200°C, 250°C, 300°C and 350°C, above 170°C a transition from mild to severe wear was observed. Correspondingly, the friction layers, in particular, the secondary plateaus, which develop on the pins and disc surface during sliding displayed quite different features, as proved by electron microscopy observations and X-ray spectroscopy analyses. As concerns the pins, at 25°C and 170°C, the friction layer consists of primary and well compacted secondary plateaus. At 200°C and above, a progressive reduction of the pin surface coverage by the secondary component of the friction layer and a corresponding thinning of this component are observed. Secondary plateaus are barely present on the samples tested at 350°C. Although referring to rather extreme conditions and simplified sliding conditions, the results obtained in this study provide useful indications on the role that the thermal stability of the organic component may have in determining wear rate in brake systems in which the temperature rise may be induced by actual operational conditions. The Case IV work aims at illustrating the role of conventional heat-treatments on the friction and wear behavior of the above system. Wear rates of both disc and M2 friction material were reduced by almost one order of magnitude when the disc is preliminarily heat-treated and then grinded to remove the surface decarburized layer that forms during the adopted treatment cycle. Heat-treatment and heat-treatment plus ground results in the reduction of the friction coefficient, which was comparatively low for the grounded samples (grinded to remove the surface decarburized layer). The friction and wear behavior along with the contact temperature evolutions were rationalized according to the materials characteristics and the observed wear mechanisms.

This work reviews, expands upon, tests, and utilizes reciprocal space models of diffraction. In Chapter 2, reciprocal space models are reviewed, moving from strict assumptions of spatial unboundedness and three-dimensional periodicity to more relaxed assumptions of partial periodicity and finite crystals. Throughout the chapter, concepts are illustrated practically through examples of metallic nickel. New expressions are presented and a new approach is shown for approximating the diffraction effect of finite crystal size for a powder ensemble of one-dimensionally disordered crystals. A generalized shape function approach is demonstrated for the first time for the case of a spatially finite one-dimensionally disordered average crystal, without introducing any new definition to the layer electron density. It is explicitly pointed out that care must be taken in choosing models: there is a trade-off between computational expense, accuracy, and physicality. It is essential that the limitations (assumptions) of the models are kept in mind when adopting any specific approach. In Chapter 3, reciprocal space models are tested on synthetic powder diffraction data computed by applying the Debye scattering equation to several atomistic powder specimens. A process for creating atomistic powder ensembles is outlined, and a novel method is proposed for accurately approximating the ensemble-averaged powder diffraction pattern. The minimum library size is determined and compared for each ensemble considered, and it is found that libraries of less than 620 domains are generally sufficient to approximate the ensemble average. The ensemble-averaged powder diffraction data is fit where possible using several different models, and it is found that only the new model for finite, linearly disordered-crystals is successful both at reproducing the powder diffraction data and accurately retrieving the physical characteristics of the samples. It is seen that while a failure to satisfy model assumptions does not necessarily imply that the data fitting fails, it can necessitate that the fitted parameters do not reflect the true characteristics of the sample. In Chapter 4, different RS models are utilizing to fit powder diffraction data from nanostructured boron nitride samples to establish the most likely nanostructure. It is found that models incorporating the powder diffraction effects of stacking disorder and finite crystal size, while not significantly improving the agreement with the observed diffraction data, yielded more accurate and precise refined parameters, and are in better agreement with electron microscopy studies when compared to models assuming a sintered mixture of two nanocrystalline phases. With this result, it is possible to conclude that the most likely nanostructural model is that of sintered bodies composed of a single one-dimensionally disordered nanocrsytalline phase, rather than a two-phase or nanocomposite sintered body. Beyond this, by constructing simulated nanostructures through stochastically sampling refined sample characteristics, it is possible to further conclude that in the samples investigated, the primary manifestation of one-dimensional disorder is the presence of twin boundaries, leading to nanometer scale twin bands or “nanotwins†as proposed by those who synthesized the samples, and ruling out the presence of significantly large bands showing a wurtzite boron nitride structure.

The sol-gel route is a versatile wet chemistry method suitable for the preparation of multi-layer thin films with defined thickness and surface roughness. In this thesis work, sol-gel derived undoped and doped ZnO multi-layers were prepared by spin coating technique on different substrates for a memristive application. The curing and annealing conditions for the ZnO films were adjusted based on the study performed on the ZnO xerogel powders, and taking into account the thermal stability of the engineered substrate used as a bottom electrode for the fabrication of the memristive building block. Chemical, structural and morphological features of the samples were investigated by complementary techniques including electron microscopy, Fourier transform infrared spectroscopy, micro-Raman, X-ray photoelectron spectroscopy and X-ray diffraction analysis. The combined characterization techniques assessed that uniform, dense and flawless films were obtained on the platinum substrate, i.e. the bottom electrode of the memristive cell. In particular, Al-doping was found to significantly affect the surface morphology, grain sizes and overall porosity of the films. According to the electrical measurements performed on undoped and Al-doped ZnO thin films sandwiched between Pt/Ti/SiO2 bottom electrode and different top electrodes including Ag and Pt-dishes, the selected fabrication conditions were suitable for fulfilling the requirements of active layers for the memristive development. The modification approach exploited toward the improvement of the memristive switching performances resulted in memristive responses with low compliance current in absence of electroforming steps. Furthermore, the resistance values at high resistance and low resistance states were reduced in the case of Al-doped films compared to the results obtained from undoped ZnO thin films.

The demand for portable and wireless electronic devices, coupled with the need to decrease reliance on non-renewable energy sources, has led to an increased need for energy harvesting and piezoelectric materials. Energy harvesting materials can transform ambient energy into usable electrical energy, but their performance is often limited by their intrinsic properties. To overcome these limitations, nanocomposites have emerged as a promising solution. These composites consist of a polymeric matrix coupled with a high-performance dielectric/piezoelectric phase, which enhances their mechanical and electrical properties. The interface between the polymer matrix and the ceramic filler plays a crucial role in achieving the desired properties and performance of the composite material. Several methods, including surface modification of the ceramic filler and functionalization of the polymer matrix, have been developed to control the interface. This thesis focuses on producing a composite material with high dielectric and piezoelectric properties through a simple and fast production route. Barium titanate (BaTiO3) ceramic nanoparticles are synthesized via wet chemical methods and then embedded into different polymeric matrices to produce nanocomposites. The synthesis parameters for the ceramic nanofillers are optimized to obtain a highly homogeneous final product with a narrow size distribution. The fillers are characterized both structurally and microstructurally through several spectroscopic techniques such as FTIR (Fourier-Transform Infrared Spectroscopy), XRD (X- Ray Diffraction), and SEM (Scanning Electron Microscopy). Then, to enhance their compatibility with the matrix, they are subjected to hydroxylation treatment and functionalized with different organosilanes and characterized. The effectiveness of the functionalization is evaluated through various techniques, proving a successful reaction with high grafting degree for all samples. The particles are then dispersed in epoxy resin and PDMS (polydimethylsiloxane), and nanocomposites are produced with a process that involves the simultaneous application of both heat and electric field and the impact of the presence of surface coupling agents on the particle dispersibility is evaluated through SEM and EDXS (Energy Dispersive X-Ray Spectroscopy). Then, being PDMS the most suitable candidate for the intended applications, an extensive electric and dielectric characterization is carried out on PDMS-based composites through dielectric spectroscopy in a wide range of frequencies and temperatures and measuring the dielectric breakdown strength to evaluate the energy density of the samples and their suitability for energy harvesting applications. To summarize, the incorporation of organosilanes leads to the creation of stronger interfaces, which result in the production of composites with high dielectric constant, good dielectric breakdown, and improved energy density values, even with lower filler content compared to similar studies. These organosilanes are responsible for activating different polarization mechanisms. Despite the challenges that still need to be addressed, the development of energy harvesting, and piezoelectric materials based on nanocomposites has the potential to revolutionize the way we power electronic devices that can be successfully used in applications such as wearables, soft robotics, sensors, and actuators. Overall, this work unveils the significant potential of dielectric nanocomposites in various applications and highlights the need for continued research and development in this field.

Flash sintering is an electrical field-assisted consolidation technology and represents a very novel technique for producing ceramic materials, which allows to decrease sensibly both processing temperature and time. Starting from 2010, when flash sintering was discovered, different ceramic materials with a wide range of electrical properties have been successfully densified. Up to date, the research on flash sintering has been mainly focused on ionic and electronic conductors and on semiconductor ceramics. In the present work, we studied the flash sintering behavior of a resistive technical ceramic like alumina also in the presence of magnesia silicate glass phase typically used for activating liquid phase sintering. The materials were studied by using different combinations of electric field and current density. Physical, structural and microstructural properties of sintered samples were extensively investigated by Archimedes’ method, SEM, XRD, XPS and pholuminescence spectroscopy. Light emission and electrical behavior during the flash process were studied,as well. The results point out the applicability of flash sintering to alumina and glass-containing alumina using electrical-field in excess of 500 V/cm, allowing an almost complete densification at temperatures lower than 1000°C. Different densification mechanisms were pointed out in the two systems, namely “solid state flash sintering” and “liquid phase flash sintering” for pure alumina and glass containing alumina, respectively. The glass addition allows a significant reduction of the current and power dissipation needed for densification, by promoting liquid phase sintering. The results suggest that unconventional mass transport phenomena are activated by the current flow in the ceramic body and they can be very likely attributed to partial reduction of the oxide induced by the electrical current. The hypothesis that the oxide gets partially reduced during DC-flash sintering experiments is supported by several experimental findings. Finally, strong affinities between flash sintering and other physical processes, like dielectric breakdown, were pointed out.

This PhD thesis focuses on the investigation and development of a feasible technology route for fabricating multifunctional flexible electronic devices through heterogeneous integration of organic/inorganic materials on polymeric substrates. The three types of printing technologies investigated during this research include: (a) Transfer printing of inorganic semiconductors processed through standard microfabrication techniques, (b) Spray coating for deposition of organic dielectrics and metal patterns, and (c) Screen-printing of solution based transducer materials. Fabrication of electronic devices based on transfer printing of high-mobility inorganic semiconductor materials (i.e. Si), aided by high-resolution possible with microfabrication technology, was explored for high performance electronics. A cost-effective processing of printable materials is desired and therefore, through printing technologies, this thesis also explored ways to bring closer the well-established microfabrication and conventional printing tools. Due to commercial interests, the major research focus in flexible electronics thus far has been on applications such as photovoltaics and displays. However, this research is focused on active/passive electronics for sensing applications like electronic skin, which is of significant interest in robotics for safe human-robot interaction and other manipulation and exploration tasks. Optimization of the Transfer Printing for translating Si microwires from SOI (silicon on insulator) wafers on secondary flexible substrates has been investigated. Processing steps have been improved for fabrication of Si microwires on donor wafers and dry transferring them onto flexible PI (polyimide) and PET (polyethylene terephthalate) substrates. The downscaling of Si in the form of microwires and using them as building block for active devices such as field effect transistors were explored in this thesis. The microwires retain the high carrier mobility, robustness, high performance and excellent stability. Arrays of MISFETs (metal insulator field effect transistors) structures were successfully fabricated and the response variations were compared. The differently doped Si microwires were analyzed in an asymmetric metal semiconductor metal (MSM) structures under planar and bend mode conditions. The optical response as well as the thermoelectric properties of the alternately doped pn-Si microwires were also investigated. A feasible fabrication route is presented, where combination of transfer printing for Si microwires and development of the subsequent post-processes by additive manufacturing techniques i.e. Screen-printing, Spray coating and Micro-spotting are mainly investigated. The Si microwires are employed as the semiconductor in the MISFET devices whereas screen-printed metal patterns are used for back-gate and deposition of dielectric layer is performed through spray coating. In parallel, screen-printing is also used for development of large area pressure sensor patches using two different materials i.e. P(VDF-TrFE) (Polyvinylidene Fluoride Trifluoroethylene) and nanocomposites of MWCNTs/PDMS (multiwall carbon nanotubes mixed with poly(dimethylsiloxane) for measuring dynamic and static contact events. Promising results have been achieved by developing a cost-effective way of manufacturing an all Screen-Printed flexible pressure sensors using piezoelectric transducer through P(VDF-TrFE) and piezoresistive based MWCNT/PDMS nanocomposites. Active electronic circuitry is needed for signal conditioning, amplification or processing of the sensory data on the flexible foils, which is deemed to be developed through Si microwires based technology in the next phase of the project. Ultimate goal of the PhD study was to develop a fabrication platform by combining three different printing technologies for large area sensor patches. Major challenges involved in the development of flexible device designs and printing technologies are highlighted and addressed with dependable solutions. The research concludes with proposing an innovative approach towards heterogeneous integration of large area sensory cells made of organic materials to the active devices based on inorganic semiconductors such as Si microwires. This technological platform for heterogeneous integration of devices made of diverse materials (organic, inorganic etc.) on soft substrates is believed to be a step-change needed to advance flexible electronics towards manufacturing.

Accurate statistical characterization of nanomaterials is crucial for their use in emerging technologies. This work investigates how different structural characteristics of metal nanoparticles influence the line profiles of the corresponding powder diffraction pattern. The effects of crystallite size, shape, lattice dynamics, and faulting are all systematically studied in terms of their impact on the line profiles. The studied patterns are simulated from atomistic models of nanoparticles via the Debye function. This approach allows for the existing theories of diffraction to be tested, and extended, in an effort to improve the characterization of small crystallites. It also begins to allow for the incorporation of atomistic simulations into the field of diffraction. Molecular dynamics simulations are shown to be effective in generating realistic structural models and dynamics of an atomic system, and are then used to study the observed features in the powder diffraction pattern. Furthermore, the characterization of a sample of shape controlled Pt nanoparticles is carried out through the use of a developed Debye function analysis routine in an effort to determine the predominant particle shape. The results of this modeling are shown to be in good agreement with complementary characterization methods, like transmission electron microscopy and cyclic voltammetry.

Cuprite (Cu2O) and tenorite (CuO) have been extensively studied because of their potential use in several electronic applications, which include solar cells and gas sensors, just to mention the most appealing ones. Both materials are p-type semiconductors, the one with a wide bandgap (Cu2O, 2.0 eV-2.2 eV), the other with a much narrower one (CuO, 1.2 eV-1.8 eV), and both show interesting optical properties in the visible and near-visible range. This Thesis work is devoted to the synthesis, characterisation and application of nanostructured copper oxides in the field of renewable energies. Within this broad scope the Thesis focuses on: • production of defect-free nanocrystals (Cu2O & CuO) and investigation of the correlation between experimental parameters and resulting microstructure; • production of highly defective nanocrystalline Cu2O powders, with the estimation of the effect of milling on microstructure and phase transformations; • production of inks for photonic applications in photovoltaic cells. Reverse micelle microemulsions (a bottom-up approach) have been employed for the production of the defect-free nanocrystals. Models have been proposed for the nanocrystal formation and growth, validated by means of several techniques such as X-ray Diffraction (XRD), Scanning Electron Microscopy (SEM) and Transmission Electron Microscopy (TEM), UV-Visible and Fourier Transform InfraRed spectroscopy (UV-Vis and FTIR). The produced nanocrystals show good crystallinity with Cu2O and CuO exhibiting cuboidal and rod-like structures, respectively. The nanometric nature of the primary domains (20 nm – 4 nm) leads to quantum confinement phenomena highlighted by photoluminescence measurements. A top-down approach has been exploited to produce highly defective particles to be possibly employed in new-generation intermediate-band solar cells. A high-energy mill, suitably modified to work in controlled temperature and environment, allowed the production of highly defective copper oxides with little or no phase transformation and contamination from the mill. Finely dispersed powders with a high density of line defects (ρ ≈ 4×10-16 m-2) were ultimately obtained. The effect of milling on the microstructure evolution was investigated using both traditional and synchrotron radiation XRD line profile analysis supported by High Resolution TEM and SEM. The synthesised powders were employed for the production of copper oxide inks for photonic applications. Those inks would allow solar cells to be directly printed on a substrate, with a dramatic reduction of production costs and the possibility of coating objects of any shape. Sprayed films usually need high consolidation temperatures: the proposed formulation, on the contrary, allows sintering of the ink-derived films at a relatively low temperature (below 600 °C), thus making possible the deposition on inexpensive substrates such as aluminium. Prototype solar cells based on the copper oxide inks have been fabricated using simple coating techniques. Results can be considered as a first step towards the production of fully recyclable solar cells, made of low-cost raw materials and realized by cost-effective deposition techniques.

In the last years it has been widely proven that the introduction of very small amounts of inorganic nanoparticles in polymeric matrices can lead to noticeable improvements of their mechanical properties, in terms of elastic modulus and tensile properties at yield and at break. Linear low density polyethylene (LLDPE) is widely applied in several industrial applications, especially for the production of transparent high performance film for the packaging industry. The objective of this work is to study the role played by different kinds of amorphous silica (SiO2) micro and nanoparticles on the viscoelastic and fracture behaviour of LLDPE based composites, prepared through a melt compounding process. Different typologies of silica filler have been considered : hydrophilic and hydrophobic fumed silica nanoparticles with different surface area, precipitated silica microparticles, and silica glass microbeads. In this way it has been possible to study the influence of the filler dimensions and morphology on the viscoelastic behaviour of the prepared composites, both in the molten and in the solid states, and on their fracture properties. In the first part of the work, a detailed microstructural characterization was performed to assess the different morphologies and surface properties of the utilized powders. Furthermore a detailed analysis of the dispersion state of the fillers in the matrix and of the thermal behaviour of the prepared composites was also conducted through optical and electron microscopy. In the second part of the work, viscoelastic behaviour of the composites in the molten state was studied through dynamic rheological tests. It was evidenced how the introduction of fumed silica nanoparticles and precipitated silica microparticles could lead very strong enhancement both of the storage (G’) and shear moduli (G’’), and of the viscosity (η), at low frequencies, especially by using high surface area fumed silicas at an high filler loading, while glass filled microcomposites showed the traditional rheological behaviour of microparticles filled polymeric systems, with marginal enhancements of rheological properties. Elaboration of new rheological models allowed us to find important correlations between fitting parameters and microstructural situation of the samples. Viscoelastic behaviour in the solid state was analyzed through quasi-static tensile tests, creep tests and dynamic tensile tests. Elastic moduli of the prepared composites resulted to be strictly related to the surface area of the filler rather than by its dimensions. Even in this case a new model, taking into account the physical interfacial interaction between the matrix and particles, proposed to explain experimental results. The same conclusions could be drawn for the creep behaviour, with important improvements of the creep stability of the material due to the introduction of fumed silica nanoparticles, especially at high filler amounts. Moreover, the limit of the linear viscoelastic region was extended by adding fumed silica nanoparticles. Furthermore, a non linear tensile creep approach was successfully applied to study the dependence of the creep behaviour from the free volume of the samples. The application of the classic time-temperature superposition principle was successfully adopted to the nanocomposite samples, evidencing that the reinforcing effect provided by the nanoparticles was more effective at high temperatures or longer times. Burgers model was adopted to model temperature dependent creep data, revealing interesting correlations between fitting parameters and nanofiller surface area. For as concern tensile dynamic mechanical properties, the introduction of the nanofiller lead to an increase of dynamic moduli (E’ and E’’) and to a lowering of tanδ values, especially when high surface area nanoparticles and elevated filler amounts were used. Even in this case dynamic properties of the material were mainly ruled by the surface area of the filler. The last part of the work was centered on the analysis of the fracture behaviour. Tensile properties at yield and at break increased with the surface area of the nanofiller and were positively affected by the presence of the organosilane on the surface of the nanoparticles. Tensile impact tests confirmed the enhancement of the fracture toughness provided by the nanoparticles. The application of the Essential Work of Fracture (EWF) approach led to the conclusion that the introduction of fumed silica nanoparticles produced a considerable improvement of the essential work of fracture (we) with the nanofiller surface area.

This thesis considers a nanotechnology approach based on the production of metals pre-treatments and organic coatings (a complete protection system at all) designed from the nanoscale. The final aim is to develop protection systems with improved corrosion protection properties and a low environmental impact. In particular, multifunctional silane hybrid molecules were used to design sol-gel pre-treatments for metals and to modify the inner structure of UV curable waterborne organic coatings. In the first part of this thesis thin (hundreds of nanometers) sol-gel films consisting of an experimental mixture of hybrid silicon alkoxides molecules were applied onto aluminium and hot dip galvanized (HDG) steel for the development of effective and environmentally friendly corrosion protection systems A chemical and electrochemical characterization of the sol-gel films highlighted their good corrosion protection properties both for aluminium and HDG steel. To test the effectiveness of the sol-gel coatings as coupling agent between metallic substrates and organic coatings (paints) both a powder coating paint and a cataphoretic coating paint were applied on the silane pre-treated substrates. The electrochemical measurements and the accelerated tests carried out on these protection systems proved the capability of these sol-gel conversion coatings to improve the corrosion protection properties of the traditional protective cycles. The performance of the silane pre-treatments was also compared to commonly used surface conversion coatings for metals. The result of this comparison evidenced that the corrosion protection properties ensured by the sol-gel conversion treatment is comparable or higher than most of the commonly used pretreatments. A study about the incorporation of inorganic nanoparticles into these sol-gel films gave evidences of an improved corrosion resistance due to the addition of certain amount of montmorillonite nanoparticles in the sol-gel matrix. The same hybrid silicon alkoxide molecules used to perform the pre-treatments were used modify the inner structure of UV curable waterborne coatings in order to improve the corrosion protection properties maintaining the environmental compatibility of the protecting system. The design, application and characterisation of urethane, acrylic and epoxy waterborne UV curing coatings modified with the hybrid silicon molecules in order to obtain nanostructured waterborne films with improved corrosion resistance and thermomechanical properties were studied. The characterization proved the great potential of the silicon alkoxide molecules as a tool to modify the properties of the organic matrix of the paint: silicon alkoxides can promote the self assembly of inorganic nanoparticles into the matrix or can act as an effective coupling agent between inorganic nanoparticles and the polymeric matrix. Silicon alkoxide molecules were proved to be an efficient tool to design a protection system from the nanoscale leading to the prospective of an accurate control of the overall properties of the macroscopic systems.