The above factors emphasize the scope of this thesis for further investigations on zirconia, the improvement of all-ceramic zirconia restorations, and especially the interaction of zirconia and veneering and its influence on the performance of the whole restoration. The introduction, chapter 1, gave a literature overview on zirconia ceramics. In chapter 2, the objective of the study was to evaluate the effect of abrading before and after sintering using alumina-based abrasives on the surface of yttria-tetragonal zirconia polycrystals. Particular attention was paid to the amount of surface stress–assisted phase transformation (tetragonal→monoclinic) and the presence of microcracks. Chapter 3 is based on the idea that the conventional sintering techniques for zirconia based materials, which are commonly used in dental reconstruction, may not provide a uniform heating, with consequent generation of microstructural flaws in the final component. As a consequence of the sintering system, using microwave heating, may represent a viable alternative. The purpose of the study was to compare the dimensional variations and physical and microstructural characteristics of commercial zirconia (Y-TZP), used as a dental restoration material, sintered in conventional and microwave furnaces. Chapter 4 described the effect of sandblasting before and after sintering on the surface roughness of zirconia and the microtensile bond strength of a pressable veneering ceramic to zirconia.

The thesis is divided in three chapters, each one covering one topic. Initially, the thermo-mechanical and impact properties of materials used for back protectors have been analysed. Dynamical mechanical analysis (DMTA) has shown that materials used for soft-shell protectors present frequency-sensitive properties. Furthermore, through impact tests, the shock absorbing characteristics of the materials have been investigated proving the differences between soft and hard-shell protectors; moreover it has been demonstrated that the materials used for soft-shell protectors maintain their protective properties after multi-impacts. The second chapter covers the effect of the visco-elastic properties of the thermoplastic polymers on the flexural and rebound behaviours of ski boots. DMTA analysis on the materials and flexural and rebound testing on the boots have been performed. A comparison of the results highlighted a correlation between the visco-elastic properties and the flexural and rebound behaviour of ski boots. The same experimental methods have been used to investigate the influence of the design on the flexural and rebound behaviours. Finally in the third chapter the thermoplastic materials employed for the construction of ski boots soles have been characterized in terms of chemical composition, hardness, crystallinity, surface roughness and coefficient of friction (COF). The results showed a relation between material hardness and grip, in particular softer materials provide more grip with respect to harder materials. On the contrary, the surface roughness has a negative effect on friction because of the decrease in contact area. The measure of grip on inclined wet surfaces showed again a relation between hardness and grip. The performance ranking of the different materials has been the same for the COF and for the slip angle tests, indicating that COF can be used as a parameter for the choice of the optimal material to be used for the soles of ski boots.

Le pietre artificiali ed i cementi artistici utilizzati durante la stagione Liberty rappresentano tutt’oggi un patrimonio artistico non ancora sufficientemente studiato. In seguito ad una ricerca bibliografica su testi e riviste dei primi anni del Novecento, è stata eseguita una ricognizione del patrimonio architettonico emiliano-romagnolo, al fine di valutarne i materiali e le tipologie di degrado più diffuse. Le città e le zone oggetto di studio sono state: Bologna, Ferrara, Modena e provincia, Reggio Emilia, Parma, Firenze, la Romagna e le Marche settentrionali. Tra gli edifici individuati sono state analizzate le decorazioni e gli intonaci di tre edifici ritenuti particolarmente significativi: il villino Pennazzi (noto anche come Villa Gina) a Borgo Panigale (Bologna), villa Verde a Bologna e l’ex-albergo Dorando Pietri a Carpi. Da tali edifici sono stati selezionati campioni rappresentativi delle diverse tipologie di decorazioni in pietra artificiale e successivamente sono stati caratterizzati in laboratorio tramite diffrattometria a raggi x (XRD), termogravimetria (TGA), microscopio ottico in sezioni lucide, microscopio elettronico a scansione (SEM) e porosimetria ad intrusione di mercurio (MIP). In particolare per Villa Verde sono state formulate e caratterizzate diverse tipologie di malte variando il tipo di legante ed il rapporto acqua/cemento, al fine di garantire la compatibilità fisico-meccanica con il supporto negli interventi di risarcimento delle lacune previsti nel restauro. L’attività sperimentale svolta ha permesso di mettere a punto un vero e proprio protocollo diagnostico per il restauro di questo tipo di decorazioni che potrà essere utilizzato sia nei casi di studio analizzati che per ogni futuro intervento. / Artificial stones used during Liberty season are still today an artistic patrimony not sufficiently studied yet. After a bibliographical research on books and journals of the first years of the XX century, a recognition of the architectural patrimony of Emilia-Romagna was performed, with the purpose of evaluating the most diffused typologies of decay. Cities and regions that were taken into account are: Bologna, Ferrara, Modena, Reggio Emilia, Parma, Florence, Romagna region and the northern Marche region. Among the studied buildings, the decorations and the plasters of three buildings, considered as more relevant, were analyzed: villa Pennazzi (known also as Villa Gina) in Borgo Panigale suburb (Bologna), Villa Verde in Bologna and the ex-hotel Dorando Pietri in Carpi. From such buildings, representative samples of the different typologies of decorations have been selected and characterized in laboratory using: X-Ray Diffraction (XRD), Thermogravimetry (TG), Optical Microscope in polished section, Scanning Electron Microscope (SEM) and Mercury Intrusion Porosimetry (MIP). In particular, for Villa Verde different typologies of repair mortars were formulated, varying the type of binder and water/cement ratio, with the purpose of guaranteeing the physical-mechanical compatibility with the support. The performed activity allowed to set a real diagnostic protocol for the restoration of this type of decorations, which can be used not only in the analyzed cases of study but also for every future restoration.

Scopo dello studio: valutare i cambiamenti indotti da diversi trattamenti di mordenzatura sulla morfologia superficiale e sulla microstruttura di due vetro-ceramiche a base disilicato di litio (IPS e.max® Press e IPS e.max® CAD) ed esaminarne gli effetti sia sull’adesione con un cemento resinoso che sulla resistenza alla flessione. Materiali e metodi: Settanta dischetti (12 mm di diametro, 2 mm di spessore) di ogni ceramica sono stati preparati e divisi in 5 gruppi: nessun trattamento (G1), HF 5% 20s (G2), HF 5% 60s (G3), HF 9.6% 20s (G4), HF 9.6% 60s (G5). Un campione per ogni gruppo è stato analizzato mediante profilometro ottico e osservato al SEM. Per gli altri campioni è stato determinato lo shear bond strength (SBS) con un cemento resinoso. Dopo l’SBS test, i campioni sono stati caricati fino a frattura utilizzando il piston-on-three-ball test per determinarne la resistenza biassiale alla flessione. Risultati: L’analisi morfologica e microstrutturale dei campioni ha rivelato come diversi trattamenti di mordenzatura producano delle modifiche nella rugosità superficiale che non sono direttamente collegate ad un aumento dei valori di adesione e dei cambiamenti microstrutturali che sono più rilevanti con l’aumento del tempo di mordenzatura e di concentrazione dell’acido. I valori medi di adesione (MPa) per IPS e.max® CAD sono significativamente più alti in G2 e G3 (21,28 +/- 4,9 e 19,55 +/- 5,41 rispettivamente); per IPS e.max® Press, i valori più elevati sono in G3 (16,80 +/- 3,96). La resistenza biassiale alla flessione media (MPa) è più alta in IPS e.max® CAD (695 +/- 161) che in IPS e.max® Press (588 +/- 117), ma non è non influenzata dalla mordenzatura con HF. Conclusioni: il disilicato di litio va mordenzato preferibilmente con HF al 5%. La mordenzatura produce alcuni cambiamenti superficiali e microstrutturali nel materiale, ma tali cambiamenti non ne influenzano la resistenza in flessione. / Purpose: The aim of this study was to evaluate the changes induced by different etching treatments on the surface morphology and microstructure of two lithium disilicate-based glass ceramic (IPS e.max® Press and IPS e.max® CAD) and examine the effects on the bond strength between ceramic and composite resin and on the biaxial flexural strength. Materials and methods: Seventy discs (12 mm diameter, 2 mm thickness) of each ceramic were prepared and divided in 5 groups: no treatment (G1), HF 5% 20s (G2), HF 5% 60s (G3), HF 9.6% 20s (G4), HF 9.6% 60s (G5). One specimen for each group was examined by optical profilometer and observed under scanning electron microscopy. On the other specimens was determined the shear bond strength (SBS) with a resin cement. After SBS test, specimens were loaded to failure using a piston-on-three-ball test to determine the biaxial flexural strength. Results: morphological analysis of treated specimens showed that different etching treatments produces changes in surface roughness but this changes are not directly related to an increasing adhesion value. The SEM analysis revealed that etching causes microstructural changes in lithium disilicate which are more relevant with the increasing of etching time and acid concentration. The mean bond strength values (MPa) for IPS e.max® CAD are statistically higher in G2 and G3 (21,28 +/- 4,9 and 19,55 +/- 5,41 respectively); for IPS e.max® Press, G3 has significant higher adhesion value (16,80 +/- 3,96). The mean biaxial flexural strength values (MPa) are significantly higher in IPS e.max® CAD (695 +/- 161) than in IPS e.max® Press (588 +/- 117). Etching with HF does not affect the flexural strength of the material. Conclusions: lithium disilicate has to be etched preferably with 5% HF. Etching produces several changes in surface and microstructure of the material, but does not compromise the flexural strength.

Recentemente, sempre più attenzione è stata rivolta all' utilizzo di coloranti organici come assorbitori di luce per la preparazione di strati fotoattivi in celle solari organiche (OPV). I coloranti organici presentano un'elevata abilità nella cattura della luce solare grazie all'elevato coefficiente di estinzione molare e buone proprietà fotofisiche. Per questi motivi sono eccellenti candidati per l'incremento della conversione fotoelettrica in OPV. In questa tesi viene descritta una nuova strategia per l'incorporazione di derivati porfirinici in catena laterale a copolimeri tiofenici. Gli studi svolti hanno dimostrato che poli(3-bromoesil)tiofene può essere variamente funzionalizzato con idrossitetrafenilporfirina (TPPOH), per l'ottenimento di copolimeri utilizzabili come materiali p-donatori nella realizzazione di OPV. I copolimeri poli[3-(6-bromoesil)tiofene-co-(3-[5-(4-fenossi)-10,15,20-trifenilporfirinil]esil tiofene] P[T6Br-co-T6TPP] contenenti differenti quantità di porfirina, sono stati sintetizzati sia con metodi non regiospecifici che regiospecifici, con lo scopo di confrontarene le proprietà e di verificare se la strutture macromolecolare che presenta una regiochimica di sostituzione sempre uguale, promuove o meno il trasporto della carica elettrica, migliorando di conseguenza l'efficienza. E' stato inoltre effettuato un ulteriore confronto tra questi derivati e derivati simili P[T6H-co-T6TPP] che non contengono l'atomo di bromo in catena laterale con lo scopo di verificare se l'assenza del gruppo reattivo, migliora o meno la stabilità termica e chimica dei film polimerici, agendo favorevolmete sulle performance dei dispositivi fotovoltaici. Tutti i copolimeri sono stati caratterizzati con differenti tecniche: spettroscopia NMR, FT-IR e UV-Vis, analisi termiche DSC e TGA, e GPC. Le celle solari Bulk Heterojunction, preparate utilizzando PCBM come materiale elettron-accettore e i copolimeri come materilai elettron-donatori, sono state testate utilizzando un multimetro Keithley e il Solar Simulator. / Recently, more and more attention has been directed to the application of organic dyes as light absorbers for the preparation of active polymeric layers in organic photovoltaic (OPV) solar cells. Organic dyes usually present a strong light-harvesting ability, thanks to their high extinction coefficient, and useful photophysical properties and are good candidates for the improvement of OPV solar cells photocurrent. In this work is described a new strategy for the incorporation of a porphyrin derivatives in the side chain of a polythiophene copolymers. The studies carried out have shown that poly[3-(6-bromohexyl)thiophene] can be variously functionalized with hydroxytetraphenylporphyrin [TPPOH] to obtain copolymers used as p-donors materials for the realization of the photoactive blend in OPV. The copolymers poly[3-(6-bromohexyl)thiophene-co-(3-[5-(4-phenoxy)-10,15,20-triphenylporphyrinyl]hexyl thiophene] P[T6Br-co-T6TPP] prepared at different chromophore contents were obtained through both not-regiospecific and regiospecific methods, with the aim to compare the properties and verify whether the macromolecular structure that presents the same regiochemistry of substitution along the system, promote the transport of electric charge, improving the efficiency. Was also carried out a further comparison between these derivatives and similar compounds P[T6H-co-T6TPP] which doesn’t link the bromine atom in the side chain, with the purpose to verify if the absence of the reactive group may improve the thermal and chemical stability of the polymer films, acting on the performance of photovoltaic devices. All the soluble and easily filmable copolymers, have been deeply characterized using different techniques, such as NMR, FT-IR and UV-Vis spectroscopy, DSC and TGA analyses, and GPC. The bulk heterojunction solar cells prepared using PCBM as electron-acceptor molecule and the copolymers as electron-donor molecules were tested using Keithley multimeter and Solar Simulator.

Charge transport in conjugated polymers as well as in bulk-heterojunction (BHJ) solar cells made of blends between conjugated polymers, as electron-donors (D), and fullerenes, as electron-acceptors (A), has been investigated. It is shown how charge carrier mobility of a series of anthracene-containing poly(p-phenylene-ethynylene)-alt-poly(p-phenylene-vinylene)s (AnE-PVs) is highly dependent on the lateral chain of the polymers, on a moderate variation of the macromolecular parameters (molecular weight and polydispersity), and on the processing conditions of the films. For the first time, the good ambipolar transport properties of this relevant class of conjugated polymers have been demonstrated, consistent with the high delocalization of both the frontier molecular orbitals. Charge transport is one of the key parameters in the operation of BHJ solar cells and depends both on charge carrier mobility in pristine materials and on the nanoscale morphology of the D/A blend, as proved by the results here reported. A straight correlation between hole mobility in pristine AnE-PVs and the fill factor of the related solar cells has been found. The great impact of charge transport for the performance of BHJ solar cells is clearly demonstrated by the results obtained on BHJ solar cells made of neat-C70, instead of the common soluble fullerene derivatives (PCBM or PC70BM). The investigation of neat-C70 solar cells was motivated by the extremely low cost of non-functionalized fullerenes, compared with that of their soluble derivatives (about one-tenth). For these cells, an improper morphology of the blend leads to a deterioration of charge carrier mobility, which, in turn, increases charge carrier recombination. Thanks to the appropriate choice of the donor component, solar cells made of neat-C70 exhibiting an efficiency of 4.22% have been realized, with an efficiency loss of just 12% with respect to the counterpart made with costly PC70BM.

Skeletal tissue has a good ability to self-regenerate after injury through the processes of bone healing. However, bone can suffer from a wide range of pathologies, cancers or congenital defects which lead to loss of bone mass and density. Current progresses in tissue engineering have shown great potential for creating biological alternatives and new perspectives for the treatment of bone damage and defects. In this approach, scaffolding plays a pivotal role. In particular, the principles of biomimesis have to be followed and the scaffolds have to be designed to this purpose. Furthermore, these tissue engineered systems have not only to support and guide the new tissue formation, but they have to induce a complete tissue functionality. The aim of this research work was the application of these advanced principles to produce and evaluate scaffolds for bone regeneration. Starting from the idea to mimic the extracellular matrix (ECM), template that characterizes the early step of the bone healing process, we design scaffolds for the evaluation of biological outputs considering the initial ECM produced by cells. We used two polymers, naturally (silk fibroin) or synthetically (poly-d,l-lactic acid) derived, and we modulated scaffold geometry (random vs ordered pore distribution), pore size and chemical composition, combining spongy and fibrous structures. The scaffolds were indeed considered as models, to investigate if they control cell production of type I collagen, principle component of the natural template for the final mineralization. Moreover, due to the key role of vessel formation in tissue engineering and the correlation between osteoblasts and endothelial cells, the influence of the scaffolds on angiogenesis and vascularisation was assessed. The innovation of this study consists in the evaluation shift from the final healing stage to the earlier stages. In fact, the results emphasize the possibility to correlate the scaffold morphology to type I collagen assembly, which in turn affects the final mineralization process, allowing to evaluate the tissue produced by osteoblasts from the first steps of bone formation. Moreover, we were able to control some cell behaviours changing construct properties. In a future research, a segmental bone defect models should be considered to better characterize the role of scaffold features during bone healing process and to determine if it would be better to use scaffolds which favour angiogenesis or mineralization to speed up a physiological bone regeneration process.

Functional multi-purpose contact lenses have recently attracted attention as suitable means to exploit the characteristics of the eye to diagnose diseases and for drug delivery. Such enrichment of the normal contact lenses are mainly achieved by the integration of different components like micro sensors and microelectronics onto the contact lens substrate. The surface of our eye is an interesting chemical interface, which acts like a window into the human body. For example, intraocular pressure is a surrogate marker of cardiovascular health. Just like the blood, the eye tear contains many health parameters which could be used to diagnose various illness. Therefore, a contact lens with integrated biosensors shall provide health professionals with a new tool for research studies and for diagnosing diseases in a novel way without traditional lab works. Motivated by this fact, this thesis deals with the integration of biosensors on contact lens to sense the eye tear film solution. The contact lens is made of polydimethylsiloxane (PDMS) and the sensor is bare gold electrodes patterned using micro fabrication technology. However there are several challenges that need to be addressed before reaching the final functional contact lens with incorporated micro devices and micro sensors for biomedical applications. One such challenge is related to the metallization on polymer substrates. The results are presented in the direction of realizing robust metal patterns on polymer substrates. Comparison study of various metallization techniques on different polymer substrates like PDMS, PET(Polyethylene terephthalate) to name a few and different metals patterned like Ag, Au to name a few are presented and thus emphasizing the reasons for the selection of polymer and micro fabrication technique used for the final device. Surface characterization of the patterned metal is performed using various techniques and the analyzed data are presented. Specific steps and solutions to issues like crack formation and adhesion of the metal on the polymer substrates are also discussed. An electrochemical sensor for the diagnosis of Keratoconjuctivitis sicca or dry eye syndrome (DES) is presented. Aqueous layer in the tear film plays an important role in maintaining the moisture inside the eye. This layer consists of proteins, carbohydrates, oxygen and some inorganic salts. It has been shown that in dry eye patients, the salt content in the tear film is higher compared to that of a healthy person. So to diagnose dry eye syndrome, we developed an impedimetric sensor to measure the resistance of the eye tear solution and we conduct associated experiments to analyze the performance. An inverse relationship between solution resistance and saline concentration in a log10vslog10 plot was confirmed. The fabricated sensors were tested for reproducibility of the results and the DES severity scale falls well inside the detection limit of the sensor. The work is wrapped up by the proof of concept experiments performed for the wireless transmission of the data from the sensor using resonance RLC circuit.

It is probably needless to mention that organic coatings are of paramount importance nowadays. Although the huge number of applications and their wide spread can suggest that organic coatings have now reached a level of maturity, they are still mysterious from a certain point of view. The behaviour of these systems is not completely understood yet, especially as regarding the relationships between the chemical formulation and the manufacturing/applications technologies on one side, and the final properties on the other side. In this scenario, durability is regarded the most crucial point and finding satisfying design solutions is not straightforward. Automotive and architecture are perhaps two of the most challenging areas where the durability is claimed at overcoming hurdles and satisfying increasing expectations. The first part of this research handled durability issues in these two fields. Novel strategies for attaining high performance organic coatings were explored. In order to validate the proposed strategies, the research has been carried out in collaboration with industrial partners operating in these areas, thus making it possible to produce and test real organic coatings. The second part of the investigation was aimed at exploring the corrosion protection capabilities of self-repairing organic coatings. The attention was specifically focused onto the preemptive healing polyurethane coatings and their barrier properties.

The primary objectives of this thesis were to investigate and compare the fracture and creep behaviour of micro- and nanocomposites based on polyethylene (PE) produced by melt mixing. To achieve these objectives, different fillers were considered: micrometric copper particles, nanometric carbon blacks (CBs) and multiwalled carbon nanotubes (MWCNTs). In the first part of this dissertation, the fracture behaviour of PE-CB composites was investigated via the Essential Work of Fracture (EWF) approach by producing composites with different CBs in order to investigate the effect of the filler particle size. Moreover, several processing (i.e., extrusion) parameters were varied to obtain different degrees of filler dispersion. Experimental results reveal that fracture toughness increases significantly when CB particle size is smaller and as the extent of dispersion of the filler in the polymer matrix is better. Fracture toughness depends on the thermo-mechanical degradation of the polymer matrix that occurs during extrusion. In the second part of this project, creep behaviour of PE-based composites was investigated at several temperatures with assistance from the principle of time-temperature superposition. In particular, the effect of filler dimensions was analyzed by comparing viscoelastic results for composites that contain micrometric copper particles (with an average diameter of 15 and 45 Î1⁄4m) and nanometric carbon blacks (with an average diameter of 15 and 30 nm). In general, these fillers substantially increase the creep resistance of PE, and this phenomenon was more prominent at smaller particle size. This effect was detectable in the linear viscoelastic region (i.e. at low stresses or temperatures), and it became more evident in the non-linear viscoelastic region (i.e. at high stresses or temperatures). In particular, creep compliance and creep rate decrease at smaller particle size. It is postulated that filler particles function as physical crosslink junctions which hinder polymer chain motion and reduce creep deformation. When particle size is reduced at constant filler volume fraction, the physical crosslink density increases such that chain mobility decreases significantly under stress. Finally, the creep behaviour of PE-MWCNT composites were investigated via direct dispersion of MWCNT in the polymer matrix and by using a commercial masterbatch of MWCNT. In all cases, the increase in creep resistance is statistically significant in the linear viscoelastic region (i.e. at low stresses or temperatures) when sufficient dispersion of the nanotubes is achieved. Interestingly enough, creep resistance increases in the non-linear viscoelastic region (i.e. at high stresses or temperatures) regardless of the degree of nanotube dispersion in the matrix. This phenomenon is attributed to nanotube orientation induced by high levels of stress.