Novel bio-based amine curing agents for epoxy resins: the way towards fully bio-based composite materials

Epoxy resins are widely used in many applications, such as paints, adhesives and matrices for composites materials, since they present the possibility to be easily and conveniently tailored in order to display a unique combination of characteristics. In literature, various examples of bio-based epoxy resins produced from a wide range of renewable sources can be found. Nevertheless, the toxicity and safety of curing agents have not been deeply investigated and it was observed that all of them still present some environmental drawback. Therefore, the development of new environmentally friendly fully bio-based epoxy systems is of great importance for designing green and sustainable materials. In this context, the present project aims at further exploring the possibility of using bio-based compounds as curing agents for epoxy resin precursors. A preliminary evaluation of several amine-based compounds demonstrated the feasibility of using Adenine as epoxy resin hardener. In order to better understand the crosslinking mechanism, the reaction of Adenine with the mono-epoxy compound Glycidyl 2-methylphenyl ether (G2MPE), was study by 1H-NMR analysis. Then Adenine was investigated as hardener of Diglycidil ether of bisphenol A (DGEBA), which is the simplest epoxy resin based on bisphenol A, in order to determine the best hardener/resin stoichiometric ratio, and evaluate the crosslinking kinetics and conversion and the final mechanical properties of the cured resin. Then, Adenine was tested as hardener of commercial epoxy resins, in particular the infusion resin Elan-tron® EC 157 (Elantas), the impregnation resin EPON™ Resin 828 (Hexion) and the bio-based resin SUPER SAP® CLR (Entropyresins). Such systems were used for the production of composites materials reinforced with chopped recycled carbon fibers and natural fibers (flax and jute). The thermo-mechanical properties of these materials have been studied in comparison with those ones of composites obtained with the same thermosetting resin reinforced with chopped virgin carbon fibers.

Mode-I fracture parameters of quasi-brittle materials: direct evaluation using DIC and relationship with Mode-II interfacial parameters

The objective of this thesis is the investigation of the Mode-I fracture mechanics parameters of quasi-brittle materials to shed light onto the influence of the width and size of the specimen on the fracture response of notched beams. To further the knowledge on the fracture process, 3D digital image correlation (DIC) was employed. A new method is proposed to determine experimentally the critical value of the crack opening, which is then used to determine the size of the fracture process zone (FPZ). In addition, the Mode-I fracture mechanics parameters are compared with the Mode-II interfacial properties of composites materials that feature as matrices the quasi-brittle materials studied in Mode-I conditions. To investigate the Mode II fracture parameters, single-lap direct shear tests are performed. Notched concrete beams with six cross-sections has been tested using a three-point bending (TPB) test set-up (Mode-I fracture mechanics). Two depths and three widths of the beam are considered. In addition to concrete beams, alkali-activated mortar beams (AAMs) that differ by the type and size of the aggregates have been tested using the same TPB set-up. Two dimensions of AAMs are considered. The load-deflection response obtained from DIC is compared with the load-deflection response obtained from the readings of two linear variable displacement transformers (LVDT). Load responses, peak loads, strain profiles along the ligament from DIC, fracture energy and failure modes of TPB tests are discussed. The Mode-II problem is investigated by testing steel reinforced grout (SRG) composites bonded to masonry and concrete elements under single-lap direct shear tests. Two types of anchorage systems are proposed for SRG reinforced masonry and concrete element to study their effectiveness. An indirect method is proposed to find the interfacial properties, compare them with the Mode-I fracture properties of the matrix and to model the effect of the anchorage.

Active fibre-reinforced composites with embedded shape memory alloys

This dissertation concerns active fibre-reinforced composites with embedded shape memory alloy wires. The structural application of active materials allows to develop adaptive structures which actively respond to changes in the environment, such as morphing structures, self-healing structures and power harvesting devices. In particular, shape memory alloy actuators integrated within a composite actively control the structural shape or stiffness, thus influencing the composite static and dynamic properties. Envisaged applications include, among others, the prevention of thermal buckling of the outer skin of air vehicles, shape changes in panels for improved aerodynamic characteristics and the deployment of large space structures. The study and design of active composites is a complex and multidisciplinary topic, requiring in-depth understanding of both the coupled behaviour of active materials and the interaction between the different composite constituents. Both fibre-reinforced composites and shape memory alloys are extremely active research topics, whose modelling and experimental characterisation still present a number of open problems. Thus, while this dissertation focuses on active composites, some of the research results presented here can be usefully applied to traditional fibre-reinforced composites or other shape memory alloy applications. The dissertation is composed of four chapters. In the first chapter, active fibre-reinforced composites are introduced by giving an overview of the most common choices available for the reinforcement, matrix and production process, together with a brief introduction and classification of active materials. The second chapter presents a number of original contributions regarding the modelling of fibre-reinforced composites. Different two-dimensional laminate theories are derived from a parent three-dimensional theory, introducing a procedure for the a posteriori reconstruction of transverse stresses along the laminate thickness. Accurate through the thickness stresses are crucial for the composite modelling as they are responsible for some common failure mechanisms. A new finite element based on the First-order Shear Deformation Theory and a hybrid stress approach is proposed for the numerical solution of the two-dimensional laminate problem. The element is simple and computationally efficient. The transverse stresses through the laminate thickness are reconstructed starting from a general finite element solution. A two stages procedure is devised, based on Recovery by Compatibility in Patches and three-dimensional equilibrium. Finally, the determination of the elastic parameters of laminated structures via numerical-experimental Bayesian techniques is investigated. Two different estimators are analysed and compared, leading to the definition of an alternative procedure to improve convergence of the estimation process. The third chapter focuses on shape memory alloys, describing their properties and applications. A number of constitutive models proposed in the literature, both one-dimensional and three-dimensional, are critically discussed and compared, underlining their potential and limitations, which are mainly related to the definition of the phase diagram and the choice of internal variables. Some new experimental results on shape memory alloy material characterisation are also presented. These experimental observations display some features of the shape memory alloy behaviour which are generally not included in the current models, thus some ideas are proposed for the development of a new constitutive model. The fourth chapter, finally, focuses on active composite plates with embedded shape memory alloy wires. A number of di®erent approaches can be used to predict the behaviour of such structures, each model presenting different advantages and drawbacks related to complexity and versatility. A simple model able to describe both shape and stiffness control configurations within the same context is proposed and implemented. The model is then validated considering the shape control configuration, which is the most sensitive to model parameters. The experimental work is divided in two parts. In the first part, an active composite is built by gluing prestrained shape memory alloy wires on a carbon fibre laminate strip. This structure is relatively simple to build, however it is useful in order to experimentally demonstrate the feasibility of the concept proposed in the first part of the chapter. In the second part, the making of a fibre-reinforced composite with embedded shape memory alloy wires is investigated, considering different possible choices of materials and manufacturing processes. Although a number of technological issues still need to be faced, the experimental results allow to demonstrate the mechanism of shape control via embedded shape memory alloy wires, while showing a good agreement with the proposed model predictions.

Development and characterization of non-oxide ceramic composites for mechanical and tribological applications

The main reasons for the attention focused on ceramics as possible structural materials are their wear resistance and the ability to operate with limited oxidation and ablation at temperatures above 2000°C. Hence, this work is devoted to the study of two classes of materials which can satisfy these requirements: silicon carbide -based ceramics (SiC) for wear applications and borides and carbides of transition metals for ultra-high temperatures applications (UHTCs). SiC-based materials: Silicon carbide is a hard ceramic, which finds applications in many industrial sectors, from heat production, to automotive engineering and metals processing. In view of new fields of uses, SiC-based ceramics were produced with addition of 10-30 vol% of MoSi2, in order to obtain electro conductive ceramics. MoSi2, indeed, is an intermetallic compound which possesses high temperature oxidation resistance, high electrical conductivity (21·10-6 Ω·cm), relatively low density (6.31 g/cm3), high melting point (2030°C) and high stiffness (440 GPa). The SiC-based ceramics were hot pressed at 1900°C with addition of Al2O3-Y2O3 or Y2O3-AlN as sintering additives. The microstructure of the composites and of the reference materials, SiC and MoSi2, were studied by means of conventional analytical techniques, such as X-ray diffraction (XRD), scanning electron microscopy (SEM) and energy dispersive spectroscopy (SEM-EDS). The composites showed a homogeneous microstructure, with good dispersion of the secondary phases and low residual porosity. The following thermo-mechanical properties of the SiC-based materials were measured: Vickers hardness (HV), Young’s modulus (E), fracture toughness (KIc) and room to high temperature flexural strength (σ). The mechanical properties of the composites were compared to those of two monolithic SiC and MoSi2 materials and resulted in a higher stiffness, fracture toughness and slightly higher flexural resistance. Tribological tests were also performed in two configurations disco-on-pin and slideron cylinder, aiming at studying the wear behaviour of SiC-MoSi2 composites with Al2O3 as counterfacing materials. The tests pointed out that the addition of MoSi2 was detrimental owing to a lower hardness in comparison with the pure SiC matrix. On the contrary, electrical measurements revealed that the addition of 30 vol% of MoSi2, rendered the composite electroconductive, lowering the electrical resistance of three orders of magnitude. Ultra High Temperature Ceramics: Carbides, borides and nitrides of transition metals (Ti, Zr, Hf, Ta, Nb, Mo) possess very high melting points and interesting engineering properties, such as high hardness (20-25 GPa), high stiffness (400-500 GPa), flexural strengths which remain unaltered from room temperature to 1500°C and excellent corrosion resistance in aggressive environment. All these properties place the UHTCs as potential candidates for the development of manoeuvrable hypersonic flight vehicles with sharp leading edges. To this scope Zr- and Hf- carbide and boride materials were produced with addition of 5-20 vol% of MoSi2. This secondary phase enabled the achievement of full dense composites at temperature lower than 2000°C and without the application of pressure. Besides the conventional microstructure analyses XRD and SEM-EDS, transmission electron microscopy (TEM) was employed to explore the microstructure on a small length scale to disclose the effective densification mechanisms. A thorough literature analysis revealed that neither detailed TEM work nor reports on densification mechanisms are available for this class of materials, which however are essential to optimize the sintering aids utilized and the processing parameters applied. Microstructural analyses, along with thermodynamics and crystallographic considerations, led to disclose of the effective role of MoSi2 during sintering of Zrand Hf- carbides and borides. Among the investigated mechanical properties (HV, E, KIc, σ from room temperature to 1500°C), the high temperature flexural strength was improved due to the protective and sealing effect of a silica-based glassy phase, especially for the borides. Nanoindentation tests were also performed on HfC-MoSi2 composites in order to extract hardness and elastic modulus of the single phases. Finally, arc jet tests on HfC- and HfB2-based composites confirmed the excellent oxidation behaviour of these materials under temperature exceeding 2000°C; no cracking or spallation occurred and the modified layer was only 80-90 μm thick.

Conductive Polymer Composites

In recent years, nanotechnologies have led to the production of materials with new and sometimes unexpected qualities through the manipulation of nanoscale components. This research aimed primarily to the study of the correlation between hierarchical structures of hybrid organic-inorganic materials such as conductive polymer composites (CPCs). Using a bottom-up methodology, we could synthesize a wide range of inorganic nanometric materials with a high degree of homogeneity and purity, such as thiol capped metal nanoparticles, stoichiometric geomimetic chrysotile nanotubes and metal dioxide nanoparticles. It was also possible to produce inorganic systems formed from the interaction between the synthesized materials. These synthesized materials and others like multiwalled carbon nanotubes and grapheme oxide were used to produce conductive polymer composites. Electrospinning causes polymer fibers to become elongated using an electric field. This technique was used to produce fibers with a nanometric diameter of a polymer blend based on two different intrinsically conducting polymers polymers (ICPs): polyaniline (PANI) and poly(3-hexylthiophene) (P3HT). Using different materials as second phase in the initial electrospun polymer fibers caused significant changes to the material hierarchical structure, leading to the creation of CPCs with modified electrical properties. Further study of the properties of these new materials resulted in a better understanding of the electrical conductivity mechanisms in these electrospun materials.

Biodegradable systems for the development of functional materials

This PhD work was aimed to design, develop, and characterize gelatin-based scaffolds, for the repair of defects in the muscle-skeletal system. Gelatin is a biopolymer widely used for pharmaceutical and medical applications, thanks to its biodegradability and biocompatibility. It is obtained from collagen via thermal denaturation or chemical-physical degradation. Despite its high potential as biomaterial, gelatin exhibits poor mechanical properties and a low resistance in aqueous environment. Crosslinking treatment and enrichment with reinforcement materials are thus required for biomedical applications. In this work, gelatin based scaffolds were prepared following three different strategies: films were prepared through the solvent casting method, electrospinning technique was applied for the preparation of porous mats, and 3D porous scaffolds were prepared through freeze-drying. The results obtained on films put into evidence the influence of pH, crosslinking and reinforcement with montmorillonite (MMT), on the structure, stability and mechanical properties of gelatin and MMT/gelatin composites. The information acquired on the effect of crosslinking in different conditions was utilized to optimize the preparation procedure of electrospun and freeze-dried scaffolds. A successful method was developed to prepare gelatin nanofibrous scaffolds electrospun from acetic acid/water solution and stabilized with a non-toxic crosslinking agent, genipin, able to preserve their original morphology after exposure to water. Moreover, the co-electrospinning technique was used to prepare nanofibrous scaffolds at variable content of gelatin and polylactic acid. Preliminary in vitro tests indicated that the scaffolds are suitable for cartilage tissue engineering, and that their potential applications can be extended to cartilage-bone interface tissue engineering. Finally, 3D porous gelatin scaffolds, enriched with calcium phosphate, were prepared with the freeze-drying method. The results indicated that the crystallinity of the inorganic phase influences porosity, interconnectivity and mechanical properties. Preliminary in vitro tests show good osteoblast response in terms of proliferation and adhesion on all the scaffolds.

Development of an innovative pyrolysis plant for the production of secondary raw materials

This project was born with the aim of developing an environmentally and financially sustainable process to dispose of end-life tires. In this perspective was devised an innovative static bed batch pilot reactor where pyrolysis can be carried out on the whole tires in order to recover energy and materials and simultaneously save the energy costs of their shredding. The innovative plant is also able to guarantee a high safety of the process thanks to the presence of a hydraulic guard. The pilot plant was used to pyrolyze new and end-life tires at temperatures from 400 to 600°C with step of 50°C in presence of steam. The main objective of this research was to evaluate the influence of the maximum process temperature on yields and chemical-physics properties of pyrolysis products. In addition, in view of a scale-up of the plant in continuous mode, the influence of the nature of several different tires as well as the effects of the aging on the final products were studied. The same pilot plant was also used to carry out pyrolysis on polymeric matrix composites in order to obtain chemical feedstocks from the resin degradation together with the recovery of the reinforcement in the form of fibers. Carbon fibers reinforced composites ad fiberglass was treated in the 450-600°C range and the products was fully characterized. A second oxidative step was performed on the pyrolysis solid residue in order to obtain the fibers in a suitable condition for a subsequent re-impregnation in order to close the composite Life Cycle in a cradle-to-cradle approach. These investigations have demonstrated that steel wires, char, carbon and glass fibers recovered in the prototypal plant as solid residues can be a viable alternative to pristine materials, making use of them to obtain new products with a commercial added value.

Homogenization of nonlinear composites for multiscale analysis

A composite is a material made out of two or more constituents (phases) combined together in order to achieve desirable mechanical or thermal properties. Such innovative materials have been widely used in a large variety of engineering fields in the past decades. The design of a composite structure requires the resolution of a multiscale problem that involves a macroscale (i.e. the structural scale) and a microscale. The latter plays a crucial role in the determination of the material behavior at the macroscale, especially when dealing with constituents characterized by nonlinearities. For this reason, numerical tools are required in order to design composite structures by taking into account of their microstructure. These tools need to provide an accurate yet efficient solution in terms of time and memory requirements, due to the large number of internal variables of the problem. This issue is addressed by different methods that overcome this problem by reducing the number of internal variables. Within this framework, this thesis focuses on the development of a new homogenization technique named Mixed TFA (MxTFA) in order to solve the homogenization problem for nonlinear composites. This technique is based on a mixed-stress variational approach involving self-equilibrated stresses and plastic multiplier as independent variables on the Reference Volume Element (RVE). The MxTFA is developed for the case of elastoplasticity and viscoplasticity, and it is implemented into a multiscale analysis for nonlinear composites. Numerical results show the efficiency of the presented techniques, both at microscale and at macroscale level.

Experimental and numerical investigation on short and long term performance of macro-synthetic fibre reinforced concrete materials

Fibre Reinforced Concretes are innovative composite materials whose applications are growing considerably nowadays. Being composite materials, their performance depends on the mechanical properties of both components, fibre and matrix and, above all, on the interface. The variables to account for the mechanical characterization of the material, could be proper of the material itself, i.e. fibre and concrete type, or external factors, i.e. environmental conditions. The first part of the research presented is focused on the experimental and numerical characterization of the interface properties and short term response of fibre reinforced concretes with macro-synthetic fibers. The experimental database produced represents the starting point for numerical models calibration and validation with two principal purposes: the calibration of a local constitutive law and calibration and validation of a model predictive of the whole material response. In the perspective of the design of sustainable admixtures, the optimization of the matrix of cement-based fibre reinforced composites is realized with partial substitution of the cement amount. In the second part of the research, the effect of time dependent phenomena on MSFRCs response is studied. An extended experimental campaign of creep tests is performed analysing the effect of time and temperature variations in different loading conditions. On the results achieved, a numerical model able to account for the viscoelastic nature of both concrete and reinforcement, together with the environmental conditions, is calibrated with the LDPM theory. Different type of regression models are also elaborated correlating the mechanical properties investigated, bond strength and residual flexural behaviour, regarding the short term analysis and creep coefficient on time, for the time dependent behaviour, with the variable investigated. The experimental studies carried out emphasize the several aspects influencing the material mechanical performance allowing also the identification of those properties that the numerical approach should consider in order to be reliable.

“Nanoglial interfaces: nanostructured materials, interfaces and devices to unveil the role of astrocytes in brain function and dysfunction”

The role of non-neuronal brain cells, called astrocytes, is emerging as crucial in brain function and dysfunction, encompassing the neurocentric concept that was envisioning glia as passive components. Ion and water channels and calcium signalling, expressed in functional micro and nano domains, underpin astrocytes’ homeostatic function, synaptic transmission, neurovascular coupling acting either locally and globally. In this respect, a major issue arises on the mechanism through which astrocytes can control processes across scales. Finally, astrocytes can sense and react to extracellular stimuli such as chemical, physical, mechanical, electrical, photonic ones at the nanoscale. Given their emerging importance and their sensing properties, my PhD research program had the general goal to validate nanomaterials, interfaces and devices approaches that were developed ad-hoc to study astrocytes. The results achieved are reported in the form of collection of papers. Specifically, we demonstrated that i) electrospun nanofibers made of polycaprolactone and polyaniline conductive composites can shape primary astrocytes’ morphology, without affecting their function ii) gold coated silicon nanowires devices enable extracellular recording of unprecedented slow wave in primary differentiated astrocytes iii) colloidal hydrotalcites films allow to get insight in cell volume regulation process in differentiated astrocytes and to describe novel cytoskeletal actin dynamics iv) gold nanoclusters represent nanoprobe to trigger astrocytes structure and function v) nanopillars of photoexcitable organic polymer are potential tool to achieve nanoscale photostimulation of astrocytes. The results were achieved by a multidisciplinary team working with national and international collaborators that are listed and acknowledged in the text. Collectively, the results showed that astrocytes represent a novel opportunity and target for Nanoscience, and that Nanoglial interface might help to unveil clues on brain function or represent novel therapeutic approach to treat brain dysfunctions.

PCM-based battery thermal management systems, energy saving materials and LCA strategy for automotive

This PhD work arises from the necessity to give a contribution to the energy saving field, regarding automotive applications. The aim was to produce a multidisciplinary work to show how much important is to consider different aspects of an electric car realization: from innovative materials to cutting-edge battery thermal management systems (BTMSs), also dealing with the life cycle assessment (LCA) of the battery packs (BPs). Regarding the materials, it has been chosen to focus on carbon fiber composites as their use allows realizing light products with great mechanical properties. Processes and methods to produce carbon fiber goods have been analysed with a special attention on the university solar car Emilia 4. The work proceeds dealing with the common BTMSs on the market (air-cooled, cooling plates, heat pipes) and then it deepens some of the most innovative systems such as the PCM-based BTMSs after a previous experimental campaign to characterize the PCMs. After that, a complex experimental campaign regarding the PCM-based BTMSs has been carried on, considering both uninsulated and insulated systems. About the first category the tested systems have been pure PCM-based and copper-foam-loaded-PCM-based BTMSs; the insulated tested systems have been pure PCM-based and copper-foam-loaded-PCM-based BTMSs and both of these systems equipped with a liquid cooling circuit. The choice of lighter building materials and the optimization of the BTMS are strategies which helps in reducing the energy consumption, considering both the energy required by the car to move and the BP state of health (SOH). Focusing on this last factor, a clear explanation regarding the importance of taking care about the SOH is given by the analysis of a BP production energy consumption. This is why a final dissertation about the life cycle assessment (LCA) of a BP unit has been presented in this thesis.

Theoretical and experimental study of novel hybrid composite and metal-composites interfaces

The growing demand for lightweight solutions in every field of engineering is driving the industry to seek new technological solutions to exploit the full potential of different materials. The combination of dissimilar materials with distinct property ranges embodies a transparent allocation of component functions while allowing an optimal mix of their characteristics. From both technological and design perspectives, the interaction between dissimilar materials can lead to severe defects that compromise a multi-material hybrid component's performance and its structural integrity. This thesis aims to develop methodologies for designing, manufacturing, and monitoring of hybrid metal-composite joints and hybrid composite components. In Chapter 1, a methodology for designing and manufacturing hybrid aluminum/composite co-cured tubes is assessed. In Chapter 2, a full-field methodology for fiber misalignment detection and stiffness prediction for hybrid, long fiber reinforced composite systems is shown and demonstrated. Chapter 3 reports the development of a novel technology for joining short fiber systems and metals in a one-step co-curing process using lattice structures. Chapter 4 is dedicated to a novel analytical framework for the design optimization of two lattice architectures.

Production and characterization of novel thermoplastic (nano)composite materials for additive manufacturing applications

The increasing environmental global regulations have directed scientific research towards more sustainable materials, even in the field of composite materials for additive manufacturing. In this context, the presented research is devoted to the development of thermoplastic composites for FDM application with a low environmental impact, focusing on the possibility to use wastes from different industrial processes as filler for the production of composite filaments for FDM 3D printing. In particular carbon fibers recycled by pyro-gasification process of CFRP scraps were used as reinforcing agent for PLA, a biobased polymeric matrix. Since the high value of CFs, the ability to re-use recycled CFs, replacing virgin ones, seems to be a promising option in terms of sustainability and circular economy. Moreover, wastes from different agricultural industries, i.e. wheat and rice production processes, were valorised and used as biofillers for the production of PLA-biocomposites. The integration of these agricultural wastes into PLA bioplastic allowed to obtain biocomposites with improved eco-sustainability, biodegradability, lightweight, and lower cost. Finally, the study of novel composites for FDM was extended towards elastomeric nanocomposite materials, in particular TPU reinforced with graphene. The research procedure of all projects involves the optimization of production methods of composite filaments with a particular attention on the possible degradation of polymeric matrices. Then, main thermal properties of 3D printed object are evaluated by TGA, DSC characterization. Additionally, specific heat capacity (CP) and Coefficient of Linear Thermal Expansion (CLTE) measurements are useful to estimate the attitude of composites for the prevention of typical FDM issues, i.e. shrinkage and warping. Finally, the mechanical properties of 3D printed composites and their anisotropy are investigated by tensile test using distinct kinds of specimens with different printing angles with respect to the testing direction.

Development and characterization of innovative graphene-based composites

Over the last decade, graphene and related materials (GRM) have drawn significant interest and resources for their development into the next generation of composite materials. This is because these nanoparticles have the ability to operate as reinforcing additives capable of imparting considerable mechanical property increases while also embedding multi-functional advantages on the host matrix. Because graphene and 2D materials are still in their early stages, the relative maturity of different types of composite systems varies. As a result, certain nanocomposite systems are currently commercially accessible, while others are not yet sufficiently developed to enter the market. A substantial emphasis has been placed on developing thermoplastic and thermosetting materials that combine a variety of mechanical and functional qualities. These include higher strength and stiffness, increased thermal and electrical conductivity, improved barrier properties, fire retardancy, and others, with the ultimate goal of providing multifunctionality to already employed composites. The work presented in this thesis investigates the use and benefits that GRM could bring to composites for a variety of applications, with the goal of realizing multifunctional components with improved properties that leads to lightweight and, as a result, energy and cost savings and pollution reduction in the environment. In particular, we worked on the following topics: • Benchmarking of commercial GRM-based master batches; • GRM-coatings for water uptake reduction; • GRM as thermo-electrical anti-icing /de-icing system; • GRM for Out of Oven curing of composites.

Electrospinning of polymeric composites with GRMs for different industrial applications

Electrospinning is the most common and industrially scalable technique for the production of polymeric nanofibers. Currently, nanocomposites are drawing much interest for their excellent properties in terms of flexibility, electrical conductivity and high surface area, which enhances the interaction with the surrounding environment. The objective of this thesis was the optimization of different electrospinning setups for the production of nanostructured polymeric composites using graphene-related materials as nanofillers. Such composites were obtained using different polymers as matrix (polyamide 6, polyinylidene fluoride and polylactic acid) that were selected and combined with the appropriate reinforcements based on their properties and their interest for specific applications. Moreover, this study highlighted the possibility to tune the morphology and size of the produced nanofibers by the addition of appropriate nanofillers even in low amounts. The addition of only 0.5% of GO allowed the production of smooth nanofibers with diameters up to 75% thinner (in the case of PLA) than the ones obtained from the pristine polymer. PVdF was charged with GO to produce triboelectric materials that can be exploited in a wearable nanogenerator for the conversion of human motion energy in electrical energy. The addition of GO improved the open-circuit voltage and power-output of a generator prototype by 3.5 times. Electrospun PA6 membranes were coated with rGO using a simple two-step technique to produce conductive textiles for wearable electronic applications. The sheet resistance of the produced materials was measured in approximately 500 Ω/sq and their resistance to washing and bending was successfully tested. These materials could be exploited as strain sensors or heating elements in smart textiles. PLA was co-electrospun with GO and cellulose nanofibers to produce high-surface area and porosity mats that could be exploited for the production of functionalized highly selective adsorption membranes with low pressure drops.