Con gli strumenti informatici disponibili oggi per le industrie, in particolar modo coi software CAE, le possibile simulare in maniera più che soddisfacente i fenomeni fisici presenti in natura. Anche il raffreddamento di un manufatto in polimero può venire simulato, a patto che si conoscano tutti i dati dei materiali e delle condizioni al contorno. Per quanto riguarda i dati dei materiali, i produttori di polimeri sono molto spesso in grado di fornirli, mentre le condizioni al contorno devono essere padroneggiate dal detentore della tecnologia. Nella pratica, tale conoscenza è al più incompleta, quindi si fanno ipotesi per colmare le lacune. Una tra le ipotesi più forti fatte è quella di una perfetta conduzione all'interfaccia tra due corpi. Questo è un vincolo troppo forte, se paragonato alla precisione di tutti gli altri dati necessari alla simulazione, e quindi si è deciso di eseguire una campagna sperimentale per stimare la resistenza al passaggio flusso termico all'interfaccia polimero-stampo ovvero determinare la conduttanza termica di contatto. L'attività svolta in questa tesi di dottorato ha come scopo quello di fornire un contributo significativo allo sviluppo e al miglioramento dell'efficienza termica degli stampi di formatura dei polimeri termoplastici con tecnologia a compressione. / Today's computational resources allow a more than satisfactory simulation of most industrial processes, including closure manufacturing. The cooling and cristalization step of the manufacturing process may be simulated, provided all polymer data, process parameters and boundary conditions are known. As to the latter two issues, it is the manufacturer's task to gain the necessary information, but this knowledge is in practice lacking at best, which makes assumptions compulsory. One of the strongest assumptions is that of perfect thermal contact at the interface between mold and polymer, too limiting a hypothesis if compared to the precision with which other conditions and parameters are known. To fill this gap an experimental campaign was devised, starting from scratch, to determine by means of inverse thermal analysis the value of the thermal contact conductance in the case of two families of polymeric materials and its dependence on the main process parameters at play in compression molding. The results, both qualitative and quantitative highlighted which aspects may be discarded and which play a fundamental role in the cooling process.

This doctoral dissertation presents a new method to asses the influence of clearancein the kinematic pairs on the configuration of planar and spatial mechanisms. The subject has been widely investigated in both past and present scientific literature, and is approached in different ways: a static/kinetostatic way, which looks for the clearance take-up due to the external loads on the mechanism; a probabilistic way, which expresses clearance-due displacements using probability density functions; a dynamic way, which evaluates dynamic effects like the actual forces in the pairs caused by impacts, or the consequent vibrations. This dissertation presents a new method to approach the problem of clearance. The problem is studied from a purely kinematic perspective. With reference to a given mechanism configuration, the pose (position and orientation) error of the mechanism link of interest is expressed as a vector function of the degrees of freedom introduced in each pair by clearance: the presence of clearance in a kinematic pair, in facts, causes the actual pair to have more degrees of freedom than the theoretical clearance-free one. The clearance-due degrees of freedom are bounded by the pair geometry. A proper modelling of clearance-affected pairs allows expressing such bounding through analytical functions. It is then possible to study the problem as a maximization problem, where a continuous function (the pose error of the link of interest) subject to some constraints (the analytical functions bounding clearance- due degrees of freedom) has to be maximize. Revolute, prismatic, cylindrical, and spherical clearance-affected pairs have been analytically modelled; with reference to mechanisms involving such pairs, the solution to the maximization problem has been obtained in a closed form. / L’attività di ricerca presentata nella tesi di dottorato concerne lo studio dell’influenza del gioco nelle coppie cinematiche in meccanismi piani e spaziali. Tale tema è stato spesso oggetto di studi, tanto nella letteratura scientifica passata quanto in quella attuale. Da uno studio approfondito, si possono dedurre diverse metodologie per affrontare il problema: metodologie di tipo statico/cinetostatico, che determinano la ripresa nel gioco nelle coppie a seguito dell’azione di un carico; metodologie di tipo probabilistico, che esprimono lo spostamento nelle coppie con gioco in termini di funzioni densità di probabilità; infine, metodologie che si interessano al problema dinamico, volte a determinare effetti quali le effettive forze nelle coppie, o gli urti successivi al distacco e le conseguenti vibrazioni. La tesi in oggetto presenta una nuova metodologia per affrontare il problema. Tale metodologia differisce dalle precedenti poichè presenta un’analisi di tipo puramente cinematico. Con riferimento ad una configurazione assegnata per un meccanismo, l’errore di posizione del membro di riferimento viene espresso come funzione vettoriale dei gradi di libertà introdotti dal gioco. La presenza di gioco in una coppia, infatti, introduce gradi di libertà aggiuntivi; questi gradi di libertà sono però vincolati. Un’opportuna modellazione delle coppie cinematiche affette da gioco permette di esprimere analiticamente per mezzo di opportune funzioni il vincolo sui gradi di libertà introdotti. E’ quindi possibile studiare la funzione che rappresenta l’errore di posizionamento del membro di riferimento riconducendo il problema alla massimizzazione di una funzione continua definita su un dominio compatto. La soluzione al problema è ottenuta analiticamente in forma chiusa, modellando coppie di tipo rotoidale, prismatico, cilindrico e sferico per meccanismi piani e spaziali.

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.

Photovoltaic (PV) solar panels generally produce electricity in the 6% to 16% efficiency range, the rest being dissipated in thermal losses. To recover this amount, hybrid photovoltaic thermal systems (PVT) have been devised. These are devices that simultaneously convert solar energy into electricity and heat. It is thus interesting to study the PVT system globally from different point of views in order to evaluate advantages and disadvantages of this technology and its possible uses. In particular in Chapter II, the development of the PVT absorber numerical optimization by a genetic algorithm has been carried out analyzing different internal channel profiles in order to find a right compromise between performance and technical and economical feasibility. Therefore in Chapter III ,thanks to a mobile structure built into the university lab, it has been compared experimentally electrical and thermal output power from PVT panels with separated photovoltaic and solar thermal productions. Collecting a lot of experimental data based on different seasonal conditions (ambient temperature,irradiation, wind...),the aim of this mobile structure has been to evaluate average both thermal and electrical increasing and decreasing efficiency values obtained respect to separate productions through the year. In Chapter IV , new PVT and solar thermal equation based models in steady state conditions have been developed by software Dymola that uses Modelica language. This permits ,in a simplified way respect to previous system modelling softwares, to model and evaluate different concepts about PVT panel regarding its structure before prototyping and measuring it. Chapter V concerns instead the definition of PVT boundary conditions into a HVAC system . This was made trough year simulations by software Polysun in order to finally assess the best solar assisted integrated structure thanks to F_save(solar saving energy)factor. Finally, Chapter VI presents the conclusion and the perspectives of this PhD work.

I test di qualifica a vibrazioni vengono usati in fase di progettazione di un componente per verificarne la resistenza meccanica alle sollecitazioni dinamiche (di natura vibratoria) applicate durante la sua vita utile. La durata delle vibrazioni applicate al componente durante la sua vita utile (migliaia di ore) deve essere ridotta al fine di realizzare test fattibili in laboratorio, condotti in genere utilizzando uno shaker elettrodinamico. L’idea è quella di aumentare l’intensità delle vibrazioni riducendone la durata. Esistono diverse procedure di Test Tailoring che tramite un metodo di sintesi definiscono un profilo vibratorio da applicare in laboratorio a partire dalle reali vibrazioni applicate al componente: una delle metodologie più comuni si basa sull’equivalenza del danno a fatica prodotto dalle reali vibrazioni e dalle vibrazioni sintetizzate. Questo approccio è piuttosto diffuso tuttavia all’autore non risulta presente nessun riferimento in letteratura che ne certifichi la validità tramite evidenza sperimentalmente. L’obiettivo dell’attività di ricerca è stato di verificare la validità del metodo tramite una campagna sperimentale condotta su opportuni provini. Il metodo viene inizialmente usato per sintetizzare un profilo vibratorio (random stazionario) avente la stessa durata di un profilo vibratorio non stazionario acquisito in condizioni reali. Il danno a fatica prodotto dalla vibrazione sintetizzata è stato confrontato con quello della vibrazione reale in termini di tempo di rottura dei provini. I risultati mostrano che il danno prodotto dalla vibrazione sintetizzata è sovrastimato, quindi l’equivalenza non è rispettata. Sono stati individuati alcuni punti critici e sono state proposte alcune modifiche al metodo per rendere la teoria più robusta. Il metodo è stato verificato con altri test e i risultati confermano la validità del metodo a condizione che i punti critici individuati siano correttamente analizzati. / Qualification with respect to input vibrations is an important step in the development of a product since it provides fundamental information relative to the product fatigue life. For the sake of test feasibility, environmental vibrations that excite the product during its lifetime (thousand of hours) must be reduced to test profiles suitable for an experimental campaign to be performed in a laboratory (typically by means of an electromechanical shaker). The idea is to increase the amplitude of the input vibrations while decreasing the corresponding duration. Some Test Tailoring procedures exist for the definition of test vibration profiles starting from environmental data properly acquired: one of the most common is based on the equivalence of the fatigue damage caused by both the environmental data and the test profiles. This approach is reasonable and quite widespread: however, in the author’s knowledge, the literature offers no paper dealing with the demonstration of the method reliability based on experimental evidence. In the present thesis, the intense experimental campaign carried out to validate the method (on a proper specimen) is presented. The method is firstly applied to synthesize a test profile (that is random stationary) having the same duration of the non-stationary environmental vibration. The damage potential of the synthesized vibration is then compared to the environmental vibration one, in terms of the specimen time to failure. Results show that the test profile damage potential is highly overestimated and therefore the equivalence is not respected. Some critical issues are pointed out to try to explain and overcome the high error. The method is applied in many other cases and the final results basically confirm the soundness of the method provided that critical issues are properly accounted and compensated for.

The topic of this thesis is the feedback stabilization of the attitude of magnetically actuated spacecraft. The use of magnetic coils is an attractive solution for the generation of control torques on small satellites flying inclined low Earth orbits, since magnetic control systems are characterized by reduced weight and cost, higher reliability, and require less power with respect to other kinds of actuators. At the same time, the possibility of smooth modulation of control torques reduces coupling of the attitude control system with flexible modes, thus preserving pointing precision with respect to the case when pulse-modulated thrusters are used. The principle based on the interaction between the Earth's magnetic field and the magnetic field generated by the set of coils introduces an inherent nonlinearity, because control torques can be delivered only in a plane that is orthogonal to the direction of the geomagnetic field vector. In other words, the system is underactuated, because the rotational degrees of freedom of the spacecraft, modeled as a rigid body, exceed the number of independent control actions. The solution of the control issue for underactuated spacecraft is also interesting in the case of actuator failure, e.g. after the loss of a reaction-wheel in a three-axes stabilized spacecraft with no redundancy. The application of well known control strategies is no longer possible in this case for both regulation and tracking, so that new methods have been suggested for tackling this particular problem. The main contribution of this thesis is to propose continuous time-varying controllers that globally stabilize the attitude of a spacecraft, when magneto-torquers alone are used and when a momentum-wheel supports magnetic control in order to overcome the inherent underactuation. A kinematic maneuver planning scheme, stability analyses, and detailed simulation results are also provided, with new theoretical developments and particular attention toward application considerations.

The objective of this thesis is the power transient analysis concerning experimental devices placed within the reflector of Jules Horowitz Reactor (JHR). Since JHR material testing facility is designed to achieve 100 MW core thermal power, a large reflector hosts fissile material samples that are irradiated up to total relevant power of 3 MW. MADISON devices are expected to attain 130 kW, conversely ADELINE nominal power is of some 60 kW. In addition, MOLFI test samples are envisaged to reach 360 kW for what concerns LEU configuration and up to 650 kW according to HEU frame. Safety issues concern shutdown transients and need particular verifications about thermal power decreasing of these fissile samples with respect to core kinetics, as far as single device reactivity determination is concerned. Calculation model is conceived and applied in order to properly account for different nuclear heating processes and relative time-dependent features of device transients. An innovative methodology is carried out since flux shape modification during control rod insertions is investigated regarding the impact on device power through core-reflector coupling coefficients. In fact, previous methods considering only nominal core-reflector parameters are then improved. Moreover, delayed emissions effect is evaluated about spatial impact on devices of a diffuse in-core delayed neutron source. Delayed gammas transport related to fission products concentration is taken into account through evolution calculations of different fuel compositions in equilibrium cycle. Provided accurate device reactivity control, power transients are then computed for every sample according to envisaged shutdown procedures. Results obtained in this study are aimed at design feedback and reactor management optimization by JHR project team. Moreover, Safety Report is intended to utilize present analysis for improved device characterization.

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.

This work presents the results of theoretical and experimental characterization of thermodynamic, mechanical and transport properties in polymer solvent systems. The polymer solvent pairs considered ranged to those in which the polymer is rubbery, to those in which the initially glassy polymeric matrix is plasticized by the action of the low molecular weight species. Advanced Equation of State models have been adopted for thermodynamic modeling,along with a rigorous procedure that enables to extend their applicability to the non equilibrium, glassy region. Mass sorption kinetics had been modeled with phenomenological models and with advanced kinetic models. / Questo lavoro verte sulla caratterizzazione teorica e sperimentale delle proprietà termodinamiche, meccaniche e di trasporto di sistemi polimero-solvente. In particolare sono stati presi in considerazione sia sistemi polimero-solvente in cui la matrice polimerica si trova allo stato di gomma, che sistemi in cui la matrice polimerica esibisce comportamento vetroso, nonché sistemi nei quali si verifica la transizione vetrosa indotta dall'effetto plasticizzante del solvente. La modellazione termodinamica è stata effettuata utilizzando equazioni di stato avanzate e metodi idonei ad estenderne il campo di utilizzo alla condizione di non equilibrio, propria dello stato vetroso. Cinetiche di assorbimento non Fickiane sono state modellate utilizzando approcci fenomenologici e modelli cinetici avanzati.