Nowadays the development of sustainable polymers, with convenient properties to substitute the traditional petroleum-based materials, is one of the major issues for material science. The utilization of renewable resources as feedstock for biopolyesters is a challenging target.The research work described in the present thesis is strictly connected to these urgent necessities and is focused mainly in finding new biopolymers, in particular biopolyesters, which are obtainable from biomass and characterized by a wide range of properties, in order to potentially substitute polyolefins and aromatic polyesters (for example, poly(ethylene terephthalate))

Questa ricerca presenta i risultati di una indagine volta a verificare la reale efficacia di rinforzo corticale su rocce carbonatiche di differenti caratteristiche mineralogiche, utilizzando consolidanti inorganici in soluzione acquosa quali l’Ossalato Ammonico (AmOX) e il Diammonio Fosfato Acido (DAHP). Le matrici carbonatiche scelte sono quelle del marmo invecchiato e una biomicrite. Sui campioni sono state effettuate indagini (SEM,MIP,XRD,MO,TG-DTA) di caratterizzazione prima e dopo i trattamenti volte a valutare eventuali effetti di rinforzo e misure fisiche di suscettività all’acqua. L’efficacia dei consolidanti inorganici è stata comparata con diversi consolidanti organici e ibridi presenti in commercio ed utilizzati in ambito conservativo. L'efficacia si è mostrata fortemente legata al fabric del materiale e alle modalità di strutturazione del prodotto di neomineralizzazione all’interno della compagine deteriorata. Nel caso del trattamento con AmOx il soluzione acquosa al 4%, la whewellite è l’unica fase di neoformazione riscontrata; la sua crescita avviene con un meccanismo essenzialmente topochimico. Nei materiali carbonatici compatti si possono ottenere solo modesti spessori di coating di neoformazione; per le rocce porose, contenenti difetti come lesioni, pori o micro-fratture, l’efficacia del trattamento può risultare più incisiva. Questo trattamento presenta lo svantaggio legato alla rapidissima formazione dei cristalli di whewellite che tendono a passivare le superfici impedendo la progressione della reazione; il vantaggio è connesso alla facile applicazione in cantiere. Nel caso del DAHP sulla matrice carbonatica trattata, si formano cluster cristallini contenenti specie più o meno stabili alcune riconducibili all’idrossiapatite. La quantità e qualità delle fasi, varia fortemente in funzione della temperatura, pH, pressione con conseguenze interferenza nelle modalità di accrescimento dei cristalli. Il trattamento alla stato attuale appare comunque di notevole interesse ma allo stesso tempo difficilmente applicabile e controllabile nelle reali condizioni operative di un cantiere di restauro. / We present the results of a survey aimed at assessing the actual effectiveness of a cortical reinforcement over carbonate rock, using as inorganic consolidants in an aqueous solution the ammonium oxalate (AmOx) and diammonium phosphate acid (DAHP). We chose the carbonate matrix of a marble naturally degraded, and a biomicritic stone with poor physical and mechanical qualities. We carried out over the samples several characterisation exams (SEM,MIP,XRD,MO,TG-DTA) before and after the treatments, aimed at evaluating possible reinforcement effects and physical measures of susceptibility to water. We compared the effectiveness of inorganic consolidants against several organic and hybrid consolidants sold on the market. The relative effectiveness of these treatments is strongly bounded both to the structure of the material and to the structuring of the neomineralisation in the deteriorated structure. Regarding the treatment with AmOx (aq) of weight 4%, the whewellite was the only new formation phase found, and its growth takes part in a topochemical process. In compact materials, it is only possible to obtain small depths of new formation coating, while in porous and deteriorated rock with ruptures and micro-fractures, the treatment results in a more effective reinforcement. This treatment has its disadvantages in the extremely quick formation of whewellite crystals tending to passivate the surfaces and to impede the reaction progression. As an advantage it can be easily used on the working site. Regarding the DAHP, crystalline clusters are formed over the carbonate matrix, and they contain species referable to the hydroxiapatite. The quantity and quality of the phases changes greatly depending on temperature, pH, pressure, and, as a result, the phase of crystal-increase is modified. At this stage the treatment appears to be of great interest but at the same time it is hard to use it and control it in a real working site.

Negli ultimi vent’anni sono state proposte al livello internazionale alcune analisi dei problemi per le scienze nella scuola e diverse strategie per l’innovazione didattica. Molte ricerche hanno fatto riferimento a una nuova nozione di literacy scientifica, quale sapere fondamentale dell’educazione, indipendente dalle scelte professionali successive alla scuola. L’ipotesi di partenza di questa ricerca sostiene che alcune di queste analisi e l’idea di una nuova literacy scientifica di tipo non-vocazionale mostrino notevoli limiti quando rapportate al contesto italiano. Le specificità di quest’ultimo sono state affrontate, innanzitutto, da un punto di vista comparativo, discutendo alcuni documenti internazionali sull’insegnamento delle scienze. Questo confronto ha messo in luce la difficoltà di ottenere un insieme di evidenze chiare e definitive sui problemi dell’educazione scientifica discussi da questi documenti, in particolare per quanto riguarda i dati sulla crisi delle vocazioni scientifiche e sull’attitudine degli studenti verso le scienze. Le raccomandazioni educative e alcuni progetti curricolari internazionali trovano degli ostacoli decisivi nella scuola superiore italiana anche a causa di specificità istituzionali, come particolari principi di selezione e l’articolazione dei vari indirizzi formativi. Il presente lavoro si è basato soprattutto su una ricostruzione storico-pedagogica del curricolo di fisica, attraverso l’analisi delle linee guida nazionali, dei programmi di studio e di alcuni rappresentativi manuali degli ultimi decenni. Questo esame del curricolo “programmato” ha messo in luce, primo, il carattere accademico della fisica liceale e la sua debole rielaborazione culturale e didattica, secondo, l’impatto di temi e problemi internazionali sui materiali didattici. Tale impatto ha prodotto dei cambiamenti sul piano delle finalità educative e degli strumenti di apprendimento incorporati nei manuali. Nonostante l’evoluzione di queste caratteristiche del curricolo, tuttavia, l’analisi delle conoscenze storico-filosofiche utilizzate dai manuali ha messo in luce la scarsa contestualizzazione culturale della fisica quale uno degli ostacoli principali per l’insegnamento di una scienza più rilevante e formativa. / Over the past twenty years there have been some international perspectives on the analysis of the problems of school science and some consequent strategies for educational change. Many studies have pointed to a new concept of scientific literacy as a fundamental knowledge, prior to career choices and relevant for every student. The starting hypothesis of this research argues that some of these analyses and the main idea of a non-vocational scientific literacy show significant limitations when related to the Italian context. The specificities of the latter are addressed, first, from a comparative point of view, discussing few international reports on science education. This comparison has highlighted the difficulty of having a set of clear and definitive evidences on the problems of science education discussed by these documents, in particular through the data concerning the crisis in scientific vocations and students’ attitudes towards science. Also the institutional framework of the Italian high schools shows how the educational recommendations and some curricular projects, discussed within the international community, find some important obstacles due to principles of selection and to different school tracks for the upper secondary level. The present work is based primarily on a historical and pedagogical reconstruction of the physics curriculum, through national guidelines, syllabi, and the analysis of some representative textbooks of the last decades. This study of the “intended” curriculum revealed, firstly, the “academic” nature of high school physics and its weak educational value, secondly, the impact, of the international issues discussed, on educational aims and learning tools embodied in textbooks. Despite the evolution of these features of the curriculum, the analysis of historical and philosophical knowledge used by textbooks has highlighted the lack of a cultural contextualization of physics as one of the main obstacles to promoting a more relevant science education.

Durante l'attività di ricerca sono stati sviluppati tre progetti legati allo sviluppo e ottimizzazione di materiali compositi. In particolare, il primo anno, siamo andati a produrre materiali ceramici ultrarefrattari tenacizzati con fibre di carburo di silicio, riuscendo a migliorare il ciclo produttivo e ottenendo un materiale ottimizzato. Durante il secondo anno di attività ci siamo concentrati nello sviluppo di resine epossidiche rinforzate con particelle di elastomeri florurati che rappresentano un nuovo materiale non presente nel mercato utile per applicazioni meccaniche e navali. L'ultimo anno di ricerca è stato svolto presso il laboratorio materiali di Ansaldo Energia dove è stato studiato il comportamenteo di materiali per turbine a gas. / During the PhD were developed three projects related to the development and optimization of composite materials. In particular, the first year, we went to produce ceramic materials for refractory application, toughened with fibers of silicon carbide, managing to improve the production cycle and to obtain an optimized material. During the second year of operation, we have focused in the development of epoxy resins reinforced with particles of Fluorinated elastomers, that represent a new material not found in the market useful for mechanical and naval application. The last year of research has been done in the Materials laboratory of Ansaldo Energia were has been studied materials for gas turbines and their application.

Gli argomenti trattati all’interno di questa tesi di dottorato riguardano la sintesi e la modifica di polimeri ottenuti a partire da fonti rinnovabili. L’acido polilattico (PLA) è stato modificato per ottenere film estensibili per uso alimentare. La scelta del materiale si è basata sull’analisi del suo ciclo di vita e perché è riconosciuto come sicuro per l’utilizzo nel campo alimentare. Le formulazioni testate, a base di PLA, sono state preparate con l’aggiunta di una serie di additivi utilizzati per migliorare le proprietà meccaniche del materiale. La lavorazione è stata eseguita mediante estrusione, ottenendo dei pellet a composizione omogenea successivamente lavorati nell’estrusore a bolla, modalità industriale di produzione dei film estensibili. È stata poi effettuata la sintesi diretta di nuovi poliesteri insaturi a base di dimetil succinato e 1,6-esandiolo. L’insaturazione della catena è stata ottenuta mediante l’uso, durante la sintesi, di derivati dell’olio di ricino, l’acido ricinoleico e il suo derivato insaturo metil undecenoato. Un’altra molecola insatura utilizzata è stata il citronellolo, scelto tra i terpeni. I polimeri così ottenuti sono stati modificati tramite reazioni radicaliche indotte con radiazioni UV utilizzando sostanze antibatteriche (sale 3-esadecil-1-vinilimidazolo bromuro) al fine di ottenere materiali con attività biocida a lungo termine e senza rilascio. Si è proceduto inoltre alla polimerizzazione reversibile di monomeri furanici con oli vegetali utilizzando una strategia di tipo double click. Si è partiti dalla sintesi di monomeri derivanti da oli vegetali contenenti eterocicli furanici attaccati mediante addizione tiol-enica (prima reazione click chemistry) e si è proseguito con la loro successiva polimerizzazione attraverso una reazione di tipo Diels-Alder con molecole con gruppi maleimmidici (seconda reazione click chemistry). I polimeri così ottenuti sono materiali potenzialmente auto-riparanti, grazie alla possibilità di spostare l’equilibrio verso i prodotti o i reagenti semplicemente variando le condizioni di temperatura. / The topics covered in this thesis concern the synthesis and modification of polymers produced from renewable resources. The poly(lactic acid) (PLA) has been modified with the addition of several additives to improve its mechanical properties and to get stretched films for food applications. The choice of the material was based on the analysis of its LCA, and because its safety is recognized by the Food and Drug Administration. The formulations tested were processed by extrusion in order to obtain homogeneous pellets and then they were processed by bubble extrusion to get stretched film. New unsatured polyesters, based on dimethyl succinate and 1,6-hexanediol, were synthesized. The unsaturation was achieved by adding during the synthesis castor oil derivatives such as ricinoleic acid and methyl undecenoate. Another unsaturated molecule used was citronellol, selected from terpenes. The polymers thus obtained were modified via radical reactions induced by UV radiation using antibacterial substances (3-hexadecyl-1-vinylimidazolium bromide) in order to obtain materials with long term biocidal activity and without release. Monomers based on plant oil derivatives bearing furan heterocycles appended through thiol-ene click chemistry were prepared and, subsequently, polymerized via a second type of click reaction, the Diels-Alder polycondensation between furan and maleimide complementary moieties. The application of the retro-DA reaction to these polymers confirmed their thermoreversible character, the clean-cut return to their respective starting monomers. This original feature opens the way to original macromolecular materials with interesting applications, like mendability and recyclability.

The utilization of borate mineral wastes with glass-ceramic technology was first time studied and primarily not investigated combinations of wastes were incorporated into the research. These wastes consist of; soda lime silica glass, meat bone and meal ash and fly ash. In order to investigate possible and relevant application areas in ceramics, kaolin clay, an essential raw material for ceramic industry was also employed in some studied compositions. As a result, three different glass-ceramic articles obtained by using powder sintering method via individual sintering processes. Light weight micro porous glass-ceramic from borate mining waste, meat bone and meal ash and kaolin clay was developed. In some compositions in related study, soda lime silica glass waste was used as an additive providing lightweight structure with a density below 0.45 g/cm3 and a crushing strength of 1.8±0.1 MPa. In another study within the research, compositions respecting the B2O3–P2O5–SiO2 glass-ceramic ternary system were prepared from; borate wastes, meat bone and meal ash and soda lime silica glass waste and sintered up to 950ºC. Low porous, highly crystallized glass-ceramic structures with density ranging between 1.8 ± 0,7 to 2.0 ± 0,3 g/cm3 and tensile strength ranging between 8,0 ± 2 to 15,0 ± 0,5 MPa were achieved. Lastly, diopside - wollastonite (SiO2-Al2O3-CaO )glass-ceramics from borate wastes, fly ash and soda lime silica glass waste were successfully obtained with controlled rapid sintering between 950 and 1050ºC. The wollastonite and diopside crystal sizes were improved by adopting varied combinations of formulations and heating rates. The properties of the obtained materials show; the articles with a uniform pore structure could be useful for thermal and acoustic insulations and can be embedded in lightweight concrete where low porous glass-ceramics can be employed as building blocks or additive in cement and ceramic industries.

The focus of my research is on contemporary biomedical construction of pain as an object, i.e. the different ways in which pain has been conceptualized and approached as a specific site of investigation in biomedicine. A significant shift in the scientific conception of pain occured in the second half of XXth century. In 1965, Ronald Melzack and Patrick D. Wall propose the Gate Control theory of pain mechanism. This theory denies a fixed and direct relationship between stimulus and pain perception, and emphazises the role played by psychological factors in pain. The IASP utilizes this perspective on the phenomenon, describing pain as “an unpleasant sensory and emotional experience associated to an actual or potential tissue damage or described in the terms of such a damage.” The relationship between pain and damage is pivotal in the definition of pain as a pathological entity. In particular, the biomedical approach to pain appears to be strongly characterized by a dualistic view of its aetiology. Disease conceptions such as “psychogenic pain” and chronic pain are deeply influenced by the ways in which psychological factors have been interpreted as components, or as causes of pain. In the second part of my dissertation, I focus on fibromyalgia, which is emblematic of the problematic acknowledgment of chronic pain as a disease. Even if fibromyalgia is actually treated in Rheumatology, its status as a disease is blurred, mainly because of its complex symptomatology including both physiological manifestations and psychological ones. In the conclusion, I present a scenario of the different ways in which this disease is dealt with in biomedical knowledge, through medical literature, clinical practice, and patients’ accounts. The findings of an ethnographic enquiry in the Rheumatology Division of a local clinic and a visual research on patients’ experiences are analyzed and discussed.

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.

Nel corso degli ultimi anni si è assistito ad un ampio dibattito sull’uso della valutazione della ricerca nelle università e nelle strutture di ricerca. Nell’ambito di tale dibattito, nella presente tesi, vengono analizzate le più importanti metodologie per la valutazione della ricerca presenti a livello internazionale, i principali strumenti qualitativi di valutazione della ricerca (in particolare la peer review), gli strumenti quantitativi, quali la bibliometria, e le caratteristiche dei più importanti archivi bibliografici citazionali (es. Scopus, Web of Science), approfondendo i principali indicatori citazionali utilizzati nelle scienze umane e sociali (es. Indice H). Inoltre la tesi affronta il tema dell’impatto socio-economico della ricerca e le principali criticità di questo innovativo strumento, attraverso uno studio di caso realizzato nel Regno Unito. Una successiva analisi empirica riguarda le principali liste di riviste realizzate a livello internazionale e nazionale, nel settore scientifico di Storia e Filosofia della scienza. I risultati degli studi mostrano che le liste internazionali di riviste possono rappresentare, un punto di partenza a cui devono necessariamente essere affiancati altri strumenti di valutazione (peer review, analisi citazionali, etc); mentre le liste nazionali rischiano, invece, di essere uno strumento poco utile ed in alcuni casi inadeguato al fine di una corretta valutazione della ricerca, a causa della scarsa internazionalizzazione dei repertori e dei giudizi generalmente troppo elevati attribuiti alle riviste. Un ulteriore risultato raggiunto nella presente tesi riguarda la valutazione della ricerca nelle diverse discipline scientifiche: nelle Scienze umane e sociali risulta esserci uno scarso grado di presenza di pubblicazioni scientifiche nei principali archivi bibliografici e citazionali internazionali. Questa situazione limita fortemente l’attendibilità delle analisi statistiche basate su indici e indicatori quantitativi, per valutare la produttività scientifica di un ricercatore, oppure di una istituzione di ricerca. / Over the last few years there has been an extensive debate on the use of evaluation of research in universities and research facilities. As part of this debate, in this thesis, we analyze the most important methods for the assessment of research on an international level, the main qualitative tools for the evaluation of research, in particular the peer review, and quantitative tools, such as bibliometrics, and the characteristics of the main bibliographic archives (eg, Scopus, Web of Science), deepening the main indicators used in human and social sciences (eg H Index). In addition, the thesis is connected with the socio-economic impact of research and the main problems of this innovative tool, through a case study conducted in the United Kingdom. A subsequent empirical analysis covers the main lists of journals at international and national levels, in the scientific field of History and Philosophy of Science. The results of the studies show that the lists of international journals can be, a starting point which must necessarily be joined by other instruments of assessment (peer review, citation analysis, etc.), while the national lists, however, can’t be an instrument, which is in some cases inadequate in order to a proper evaluation of the research, due to the low internationalization of repertoires and judgments generally too high attributed to the journals. A further result is that the evaluation of research in different scientific disciplines shows that in the humanities and social sciences there is a low presence of scientific publications in major international citation and bibliographic databases (Web of Science, Scopus). This situation limits the reliability of the statistical analysis based on indices and quantitative indicators (first Impact Factor and Index H), to evaluate the scientific productivity of a researcher or an institution research.

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.