Dynamic services in mobile ad hoc networks

The increasing diffusion of wireless-enabled portable devices is pushing toward the design of novel service scenarios, promoting temporary and opportunistic interactions in infrastructure-less environments. Mobile Ad Hoc Networks (MANET) are the general model of these higly dynamic networks that can be specialized, depending on application cases, in more specific and refined models such as Vehicular Ad Hoc Networks and Wireless Sensor Networks. Two interesting deployment cases are of increasing relevance: resource diffusion among users equipped with portable devices, such as laptops, smart phones or PDAs in crowded areas (termed dense MANET) and dissemination/indexing of monitoring information collected in Vehicular Sensor Networks. The extreme dynamicity of these scenarios calls for novel distributed protocols and services facilitating application development. To this aim we have designed middleware solutions supporting these challenging tasks. REDMAN manages, retrieves, and disseminates replicas of software resources in dense MANET; it implements novel lightweight protocols to maintain a desired replication degree despite participants mobility, and efficiently perform resource retrieval. REDMAN exploits the high-density assumption to achieve scalability and limited network overhead. Sensed data gathering and distributed indexing in Vehicular Networks raise similar issues: we propose a specific middleware support, called MobEyes, exploiting node mobility to opportunistically diffuse data summaries among neighbor vehicles. MobEyes creates a low-cost opportunistic distributed index to query the distributed storage and to determine the location of needed information. Extensive validation and testing of REDMAN and MobEyes prove the effectiveness of our original solutions in limiting communication overhead while maintaining the required accuracy of replication degree and indexing completeness, and demonstrates the feasibility of the middleware approach.

Optically active photoresponsive multifunctional polymeric materials

In the last year [1], Angiolini and co-workers have synthesized and investigated methacrylic polymers bearing in the side chain the chiral cyclic (S)-3-hydroxypyrrolidine moiety interposed between the main chain and the trans-azoaromatic chromophore, substituted or not in the 4’ position by an electron-withdrawing group. In these materials, the presence of a rigid chiral moiety of one prevailing absolute configuration favours the establishment of a chiral conformation of one prevailing helical handedness, at least within chain segments of the macromolecules, which can be observed by circular dichroism (CD). The simultaneous presence of the azoaromatic and chiral functionalities allows the polymers to display both the properties typical of dissymmetric systems (optical activity, exciton splitting of dichroic absorptions), as well as the features typical of photochromic materials (photorefractivity, photoresponsiveness, NLO properties). The first part of this research was to synthesize analogue homopolymers and copolymers based on bisazoaromatic moiety and compare their properties to those of the above mentioned analogue derivatives bearing only one azoaromatic chromophore in the side chain. We focused also the attention on the effects induced on the thermal and chiroptical behaviours by the insertion of particulars achiral comonomers characterized by different side-chain mobility and grown hindrance (MMA, tert-BMA and TrMA). On the other hand carbazole containing polymers [2] have attracted much attention because of their unique features. The use of these materials in advanced micro- and nanotechnologies spreads in many different applications such as photoconductive and photorefractive polymers, electroluminescent devices, programmable optical interconnections, data storage, chemical photoreceptors, NLO, surface relief gratings, blue emitting materials and holographic memory. The second part of the work was focused on the synthesis and the characterization polymeric derivatives bearing in the side chain carbazole or phenylcarbazole moieties linked to the (S)- 2-hydroxy succinimide or the (S)-3-hydroxy pyrrolidinyl ring as chiral groups covalently linked to the main chain through ester bonds. The last objective of this research was to design, synthesize, and characterize multifunctional methacrylic homopolymers and copolymers bearing three distinct functional groups (i.e. azoaromatic, carbazole and chiral group of one single configuration) directly linked in the side chain. This polymeric derivatives could be of potential interest for several advanced application fields, such as optical storage, waveguides, chiroptical switches, chemical photoreceptors, NLO, surface relief gratings, photoconductive materials, etc.

Progettare l'ospitalità: turismi e turisti della città contemporanea

La ricerca si pone come obbiettivo principale quello di individuare gli strumenti in grado di controllare la qualità di una progettazione specifica che risponde alle forti richieste della domanda turistica di un territorio. Parte dalle più semplici teorie che inquadrano una costante condizione dell’uomo, “il VIAGGIARE”. La ricerca si pone come primo interrogativo quello definire una “dimensione” in cui le persone viaggiano, dove il concetto fisico di spazio dedicato alla vita si è spostato come e quanto si sposta la gente. Esiste una sorta di macroluogo (destinazione) che comprende tutti gli spazi dove la gente arriva e da cui spesso riparte. Pensare all'architettura dell’ospitalità significa indagare e comprendere come la casa non è più il solo luogo dove la gente abita. La ricerca affonda le proprie tesi sull’importanza dei “luoghi” appartenenti ad un territorio e come essi debbano riappropriarsi, attraverso un percorso progettuale, della loro più stretta vocazione attrattiva. Così come si sviluppa un’architettura dello stare, si manifesta un’architettura dello spostarsi e tali architetture si confondono e si integrano ad un territorio che per sua natura è esso stesso attrattivo. L’origine terminologica di nomadismo è passaggio necessario per la comprensione di una nuova dimensione architettonica legata a concetti quali mobilità e abitare. Si indaga pertanto all’interno della letteratura “diasporica”, in cui compaiono le prime configurazioni legate alla provvisorietà e alle costruzioni “erranti”. In sintesi, dopo aver posizionato e classificato il fenomeno turistico come nuova forma dell’abitare, senza il quale non si potrebbe svolgere una completa programmazione territoriale in quanto fenomeno oramai imprescindibile, la ricerca procede con l’individuazione di un ambito inteso come strumento di indagine sulle relazioni tra le diverse categorie e “tipologie” turistiche. La Riviera Romagnola è sicuramente molto famosa per la sua ospitalità e per le imponenti infrastrutture turistiche ma a livello industriale non è meno famosa per il porto di Ravenna che costituisce un punto di riferimento logistico per lo scambio di merci e materie prime via mare, oltre che essere, in tutta la sua estensione, caso di eccellenza. La provincia di Ravenna mette insieme tutti i fattori che servono a soddisfare le Total Leisure Experience, cioè esperienze di totale appagamento durante la vacanza. Quello che emerge dalle considerazioni svolte sul territorio ravennate è che il turista moderno non va più in cerca di una vacanza monotematica, in cui stare solo in spiaggia o occuparsi esclusivamente di monumenti e cultura. La richiesta è quella di un piacere procurato da una molteplicità di elementi. Pensiamo ad un distretto turistico dove l’offerta, oltre alla spiaggia o gli itinerari culturali, è anche occasione per fare sport o fitness, per rilassarsi in luoghi sereni, per gustare o acquistare cibi tipici e, allo stesso tempo, godere degli stessi servizi che una persona può avere a disposizione nella propria casa. Il percorso, finalizzato a definire un metodo di progettazione dell’ospitalità, parte dalla acquisizione delle esperienze nazionali ed internazionali avvenute negli ultimi dieci anni. La suddetta fase di ricerca “tipologica” si è conclusa in una valutazione critica che mette in evidenza punti di forza e punti di debolezza delle esperienze prese in esame. La conclusione di questa esplorazione ha prodotto una prima stesura degli “obbiettivi concettuali” legati alla elaborazione di un modello architettonico. Il progetto di ricerca in oggetto converge sul percorso tracciato dai Fiumi Uniti in Ravenna. Tale scelta consente di prendere in considerazione un parametro che mostri fattori di continuità tra costa e città, tra turismo balneare e turismo culturale, considerato quindi come potenziale strumento di connessione tra realtà spesso omologhe o complementari, in vista di una implementazione turistica che il progetto di ricerca ha come primo tra i suoi obiettivi. Il tema dell’architettura dell’ospitalità, che in questo caso si concretizza nell’idea di sperimentare l’ALBERGO DIFFUSO, è quello che permette di evidenziare al meglio la forma specifica della cultura locale, salvandone la vocazione universale. La proposta progettuale si articola in uno studio consequenziale ed organico in grado di promuovere una riflessione originale sul tema del modulo “abitativo” nei luoghi di prossimità delle emergenze territoriali di specifico interesse, attorno alle quali la crescente affluenza di un’utenza fortemente differenziata evidenzia la necessità di nodi singolari che si prestino a soddisfare una molteplicità di usi in contesti di grande pregio.

Middleware per la gestione di interfacce di comunicazione e di sorgenti di contesto in ambienti wireless eterogenei

The full exploitation of multi-hop multi-path connectivity opportunities offered by heterogeneous wireless interfaces could enable innovative Always Best Served (ABS) deployment scenarios where mobile clients dynamically self-organize to offer/exploit Internet connectivity at best. Only novel middleware solutions based on heterogeneous context information can seamlessly enable this scenario: middleware solutions should i) provide a translucent access to low-level components, to achieve both fully aware and simplified pre-configured interactions, ii) permit to fully exploit communication interface capabilities, i.e., not only getting but also providing connectivity in a peer-to-peer fashion, thus relieving final users and application developers from the burden of directly managing wireless interface heterogeneity, and iii) consider user mobility as crucial context information evaluating at provision time the suitability of available Internet points of access differently when the mobile client is still or in motion. The novelty of this research work resides in three primary points. First of all, it proposes a novel model and taxonomy providing a common vocabulary to easily describe and position solutions in the area of context-aware autonomic management of preferred network opportunities. Secondly, it presents PoSIM, a context-aware middleware for the synergic exploitation and control of heterogeneous positioning systems that facilitates the development and portability of location-based services. PoSIM is translucent, i.e., it can provide application developers with differentiated visibility of data characteristics and control possibilities of available positioning solutions, thus dynamically adapting to application-specific deployment requirements and enabling cross-layer management decisions. Finally, it provides the MMHC solution for the self-organization of multi-hop multi-path heterogeneous connectivity. MMHC considers a limited set of practical indicators on node mobility and wireless network characteristics for a coarsegrained estimation of expected reliability/quality of multi-hop paths available at runtime. In particular, MMHC manages the durability/throughput-aware formation and selection of different multi-hop paths simultaneously. Furthermore, MMHC provides a novel solution based on adaptive buffers, proactively managed based on handover prediction, to support continuous services, especially by pre-fetching multimedia contents to avoid streaming interruptions.

Rehabilitation Engineering in Parkinson's disease

Impairment of postural control is a common consequence of Parkinson's disease (PD) that becomes more and more critical with the progression of the disease, in spite of the available medications. Postural instability is one of the most disabling features of PD and induces difficulties with postural transitions, initiation of movements, gait disorders, inability to live independently at home, and is the major cause of falls. Falls are frequent (with over 38% falling each year) and may induce adverse consequences like soft tissue injuries, hip fractures, and immobility due to fear of falling. As the disease progresses, both postural instability and fear of falling worsen, which leads patients with PD to become increasingly immobilized. The main aims of this dissertation are to: 1) detect and assess, in a quantitative way, impairments of postural control in PD subjects, investigate the central mechanisms that control such motor performance, and how these mechanism are affected by levodopa; 2) develop and validate a protocol, using wearable inertial sensors, to measure postural sway and postural transitions prior to step initiation; 3) find quantitative measures sensitive to impairments of postural control in early stages of PD and quantitative biomarkers of disease progression; and 4) test the feasibility and effects of a recently-developed audio-biofeedback system in maintaining balance in subjects with PD. In the first set of studies, we showed how PD reduces functional limits of stability as well as the magnitude and velocity of postural preparation during voluntary, forward and backward leaning while standing. Levodopa improves the limits of stability but not the postural strategies used to achieve the leaning. Further, we found a strong relationship between backward voluntary limits of stability and size of automatic postural response to backward perturbations in control subjects and in PD subjects ON medication. Such relation might suggest that the central nervous system presets postural response parameters based on perceived maximum limits and this presetting is absent in PD patients OFF medication but restored with levodopa replacement. Furthermore, we investigated how the size of preparatory postural adjustments (APAs) prior to step initiation depend on initial stance width. We found that patients with PD did not scale up the size of their APA with stance width as much as control subjects so they had much more difficulty initiating a step from a wide stance than from a narrow stance. This results supports the hypothesis that subjects with PD maintain a narrow stance as a compensation for their inability to sufficiently increase the size of their lateral APA to allow speedy step initiation in wide stance. In the second set of studies, we demonstrated that it is possible to use wearable accelerometers to quantify postural performance during quiet stance and step initiation balance tasks in healthy subjects. We used a model to predict center of pressure displacements associated with accelerations at the upper and lower back and thigh. This approach allows the measurement of balance control without the use of a force platform outside the laboratory environment. We used wearable accelerometers on a population of early, untreated PD patients, and found that postural control in stance and postural preparation prior to a step are impaired early in the disease when the typical balance and gait intiation symptoms are not yet clearly manifested. These novel results suggest that technological measures of postural control can be more sensitive than clinical measures. Furthermore, we assessed spontaneous sway and step initiation longitudinally across 1 year in patients with early, untreated PD. We found that changes in trunk sway, and especially movement smoothness, measured as Jerk, could be used as an objective measure of PD and its progression. In the third set of studies, we studied the feasibility of adapting an existing audio-biofeedback device to improve balance control in patients with PD. Preliminary results showed that PD subjects found the system easy-to-use and helpful, and they were able to correctly follow the audio information when available. Audiobiofeedback improved the properties of trunk sway during quiet stance. Our results have many implications for i) the understanding the central mechanisms that control postural motor performance, and how these mechanisms are affected by levodopa; ii) the design of innovative protocols for measuring and remote monitoring of motor performance in the elderly or subjects with PD; and iii) the development of technologies for improving balance, mobility, and consequently quality of life in patients with balance disorders, such as PD patients with augmented biofeedback paradigms.

Sviluppo, implementazione e valutazione funzionale di un nuovo modello protesico di caviglia

Total ankle arthroplasty (TAA) is still not as satisfactory as total hip and total knee arthroplasty. For the TAA to be considered a valuable alternative to ankle arthrodesis, an effective range of ankle mobility must be recovered. The disappointing clinical results of the current generation of TAA are mostly related to poor understanding of the structures guiding ankle joint mobility. A new design (BOX Ankle) has been developed, uniquely able to restore physiologic ankle mobility and a natural relationship between the implanted components and the retained ligaments. For the first time the shapes of the tibial and talar components in the sagittal plane were designed to be compatible with the demonstrated ligament isometric rotation. This resulted in an unique motion at the replaced ankle where natural sliding as well as rolling motion occurs while at the same time full conformity is maintained between the three components throughout the flexion arc. According to prior research, the design features a spherical convex tibial component, a talar component with radius of curvature in the sagittal plane longer than that of the natural talus, and a fully conforming meniscal component. After computer-based modelling and preliminary observations in several trial implantation in specimens, 126 patients were implanted in the period July 2003 – December 2008. 75 patients with at least 6 months follow-up are here reported. Mean age was 62,6 years (range 22 – 80), mean follow-up 20,2 months. The AOFAS clinical score systems were used to assess patient outcome. Radiographs at maximal dorsiflexion and maximal plantar flexion confirmed the meniscalbearing component moves anteriorly during dorsiflexion and posteriorly during plantarflexion. Frontal and lateral radiographs in the patients, show good alignment of the components, and no signs of radiolucency or loosening. The mean AOFAS score was observed to go from 41 pre-op to 74,6 at 6 month follow-up, with further improvement at the following follow-up. These early results reveal satisfactory clinical scores, with good recovery of range of motion and reduction of pain. Radiographic assessment reveals good osteointegration. All these preliminary results confirm biomechanical studies and the validity of this novel ligamentcompatible prosthesis design. Surely it will be important to re-evaluate these patients later.

Cluster-derived Gold/Iron catalysts for environmental applications

During the last years we assisted to an exponential growth of scientific discoveries for catalysis by gold and many applications have been found for Au-based catalysts. In the literature there are several studies concerning the use of gold-based catalysts for environmental applications and good results are reported for the catalytic combustion of different volatile organic compounds (VOCs). Recently it has also been established that gold-based catalysts are potentially capable of being effectively employed in fuel cells in order to remove CO traces by preferential CO oxidation in H2-rich streams. Bi-metallic catalysts have attracted increasing attention because of their markedly different properties from either of the costituent metals, and above all their enhanced catalytic activity, selectivity and stability. In the literature there are several studies demostrating the beneficial effect due to the addition of an iron component to gold supported catalysts in terms of enhanced activity, selectivity, resistence to deactivation and prolonged lifetime of the catalyst. In this work we tried to develop a methodology for the preparation of iron stabilized gold nanoparticles with controlled size and composition, particularly in terms of obtaining an intimate contact between different phases, since it is well known that the catalytic behaviour of multi-component supported catalysts is strongly influenced by the size of the metal particles and by their reciprocal interaction. Ligand stabilized metal clusters, with nanometric dimensions, are possible precursors for the preparation of catalytically active nanoparticles with controlled dimensions and compositions. Among these, metal carbonyl clusters are quite attractive, since they can be prepared with several different sizes and compositions and, moreover, they are decomposed under very mild conditions. A novel preparation method was developed during this thesis for the preparation of iron and gold/iron supported catalysts using bi-metallic carbonyl clusters as precursors of highly dispersed nanoparticles over TiO2 and CeO2, which are widely considered two of the most suitable supports for gold nanoparticles. Au/FeOx catalysts were prepared by employing the bi-metallic carbonyl cluster salts [NEt4]4[Au4Fe4(CO)16] (Fe/Au=1) and [NEt4][AuFe4(CO)16] (Fe/Au=4), and for comparison FeOx samples were prepared by employing the homometallic [NEt4][HFe3(CO)11] cluster. These clusters were prepared by Prof. Longoni research group (Department of Physical and Inorganic Chemistry- University of Bologna). Particular attention was dedicated to the optimization of a suitable thermal treatment in order to achieve, apart from a good Au and Fe metal dispersion, also the formation of appropriate species with good catalytic properties. A deep IR study was carried out in order to understand the physical interaction between clusters and different supports and detect the occurrence of chemical reactions between them at any stage of the preparation. The characterization by BET, XRD, TEM, H2-TPR, ICP-AES and XPS was performed in order to investigate the catalysts properties, whit particular attention to the interaction between Au and Fe and its influence on the catalytic activity. This novel preparation method resulted in small gold metallic nanoparticles surrounded by highly dispersed iron oxide species, essentially in an amorphous phase, on both TiO2 and CeO2. The results presented in this thesis confirmed that FeOx species can stabilize small Au particles, since keeping costant the gold content but introducing a higher iron amount a higher metal dispersion was achieved. Partial encapsulation of gold atoms by iron species was observed since the Au/Fe surface ratio was found much lower than bulk ratio and a strong interaction between gold and oxide species, both of iron oxide and supports, was achieved. The prepared catalysts were tested in the total oxidation of VOCs, using toluene and methanol as probe molecules for aromatics and alchols, respectively, and in the PROX reaction. Different performances were observed on titania and ceria catalysts, on both toluene and methanol combustion. Toluene combustion on titania catalyst was found to be enhanced increasing iron loading while a moderate effect on FeOx-Ti activity was achieved by Au addition. In this case toluene combustion was improved due to a higher oxygen mobility depending on enhanced oxygen activation by FeOx and Au/FeOx dispersed on titania. On the contrary ceria activity was strongly decreased in the presence of FeOx, while the introduction of gold was found to moderate the detrimental effect of iron species. In fact, excellent ceria performances are due to its ability to adsorb toluene and O2. Since toluene activation is the determining factor for its oxidation, the partial coverage of ceria sites, responsible of toluene adsorption, by FeOx species finely dispersed on the surface resulted in worse efficiency in toluene combustion. Better results were obtained for both ceria and titania catalysts on methanol total oxidation. In this case, the performances achieved on differently supported catalysts indicate that the oxygen mobility is the determining factor in this reaction. The introduction of gold on both TiO2 and CeO2 catalysts, lead to a higher oxygen mobility due to the weakening of both Fe-O and Ce-O bonds and consequently to enhanced methanol combustion. The catalytic activity was found to strongly depend on oxygen mobility and followed the same trend observed for catalysts reducibility. Regarding CO PROX reaction, it was observed that Au/FeOx titania catalysts are less active than ceria ones, due to the lower reducibility of titania compared to ceria. In fact the availability of lattice oxygen involved in PROX reaction is much higher in the latter catalysts. However, the CO PROX performances observed for ceria catalysts are not really high compared to data reported in literature, probably due to the very low Au/Fe surface ratio achieved with this preparation method. CO preferential oxidation was found to strongly depend on Au particle size but also on surface oxygen reducibility, depending on the different oxide species which can be formed using different thermal treatment conditions or varying the iron loading over the support.

Wasserfreie Protonenleiter für Brennstoffzellen auf der Basis von Imidazol und Benzimidazol

Mit Hilfe von Brennstoffzellen wird eine effiziente Energieumwandlung von chemischer in elektrische Energie möglich. Die kommerziellen PEM-Brennstoffzellen benutzen Membra-nen, die zum Erreichen hoher Leitfähigkeiten eine wässrige Phase erfordern, in der der Proto-nentransport stattfindet. Somit wird die Betriebstemperatur durch den Siedepunkt des Wassers limitiert. Die verwendeten Pt-Katalysatoren zeigen bei niedrigen Temperaturen eine höhere Empfindlichkeit gegenüber CO, dass im Reformierungsprozess bei der Erzeugung von Was-serstoff entsteht. Austausch der wässrigen Phase gegen Heterozyklen, die ein zu Wasser ver-gleichbares Wasserstoffbrückennetzwerk aufbauen, in dem der Protonentransport stattfinden kann, ermöglicht eine höhere Betriebstemperatur. Durch das im Laufe des Brennstoffzellen-betriebs gebildete Wasser, können die Heterozyklen verdünnt bzw. komplett aus der Memb-ran ausgewaschen werden. Daher ist es erforderlich, die Ladungsträger an ein Polymerrück-grat zu binden, so dass sie eine hohe Beweglichkeit und Konzentration, die denen in der flüs-sigen Phase einer konventionellen Membran entsprechen, aufweisen. Diese Arbeit beschreibt die Synthese und Charakterisierung von Protonenleitern, die ohne eine flüssige Phase auskommen, da sie bereits protonische Leitfähigkeit als intrinsische Ei-genschaft zeigen. Es wurden verschiedene imidazol- bzw. benzimidazolhaltige Dimere und Polythiophene, in denen Benzimidazol in der Seitenkette über verschieden flexible Spacer mit dem Polymerrückgrat verbunden ist, synthetisiert. Die Materialien wurden in undotierten Zu-stand und nach Dotierung mit geringen Mengen Phosphorsäure umfassend charakterisiert und auf thermisches Verhalten, Stabilität und Leitfähigkeit untersucht. Die benzimidazolhaltigen Dimere weisen mit 250 °C die höchsten Zersetzungstemperaturen auf. Mit zunehmender Temperatur kann in allen Fällen eine Erhöhung der Leitfähigkeit beobachtet werden, die sich in der Arrhenius-Auftragung durch eine Gerade anpassen lässt, somit kann der Protonentrans-port durch einen Protonen-hüpfmechanismus beschrieben werden. Die höchste beobachtete Leitfähigkeit liegt im Bereich von 10-6 S/cm bei 160 °C. Durch Zusatz von Phosphorsäure kann die Leitfähigkeit z.T. um einige Größenordnungen gesteigert werden. Eine Ausnahme bilden die Polythiophene, die sowohl protonische als auch elektronische Leitfähigkeit besit-zen. Hier führt die Säure zu einer Lokalisierung der Ladungsträger, so dass die elektronische Leitfähigkeit eingeschränkt wird.

New proton conducting membranes for fuel cell applications

In order to synthesize proton-conducting materials which retain acids in the membrane during fuel cell operating conditions, the synthesis of poly(vinylphosphonic acid) grafted polybenzimidazole (PVPA grafted PBI) and the fabrication of multilayer membranes are mainly focussed in this dissertation. Synthesis of PVPA grafted PBI membrane can be done according to "grafting through" method. In "grafting through" method (or macromonomer method), monomer (e.g., vinylphosphonic acid) is radically copolymerized with olefin group attached macromonomer (e.g., allyl grafted PBI and vinylbenzyl grafted PBI). This approach is inherently limited to synthesize graft-copolymer with well-defined architectural and structural parameters. The incorporation of poly(vinylphosphonic acid) into PBI lead to improvements in proton conductivity up to 10-2 S/cm. Regarding multilayer membranes, the proton conducting layer-by-layer (LBL) assembly of polymers by various strong acids such as poly(vinylphosphonic acid), poly(vinylsulfonic acid) and poly(styrenesulfonic acid) paired with basic polymers such as poly(4-vinylimidazole) and poly(benzimidazole), which are appropriate for ‘Proton Exchange Membranes for Fuel Cell’ applications have been described. Proton conductivity increases with increasing smoothness of the film and the maximum measured conductivity was 10-4 S/cm at 25°C. Recently, anhydrous proton-conducting membranes with flexible structural backbones, which show proton-conducting properties comparable to Nafion have been focus of current research. The flexible backbone of polymer chains allow for a high segmental mobility and thus, a sufficiently low glass transition temperature (Tg), which is an essential factor to reach highly conductive systems. Among the polymers with a flexible chain backbone, poly(vinylphosphonic acid), poly(vinylbenzylphosphonic acid), poly(2-vinylbenzimidazole), poly(4-styrenesulfonic acid), poly(4-vinylimidazole), poly(4-vinylimidazole-co-vinylphosphonic acid) and poly(4-vinylimidazole-co-4-styrenesulfonic acid) are interesting materials for fuel cell applications. Synthesis of polybenzimidazole with anthracene structural unit was carried out in order to avoid modification reaction in the imidazole ring, because anthracene would encourage the modification reaction with an olefin by Diels-Alder reaction.

La città che cambia: la diffusione urbana. Mobilità residenziale e stili di vita emergenti nel Comune di Argelato (Bologna)

Il presente lavoro di ricerca ha per oggetto il tema della diffusione urbana. Dopo una breve ricostruzione delle varie definizioni presenti in letteratura sul fenomeno - sia qualitative che quantitative - e una descrizione dei limiti di volta in volta presenti all’interno di tali definizioni, si procede con la descrizione dell’evoluzione storica dello sprawl urbano all’interno del mondo occidentale. Una volta definito e contestualizzato storicamente l’oggetto della ricerca, ne vengono analizzate le cause e il complesso sistema di conseguenze che tale fenomeno urbano porta con sé. Successivamente vengono presentate le principali teorie sociologiche attraverso le quali può essere interpretato il fenomeno dello sprawl urbano e vengono descritte le varie forme con cui si può esprimere lo sprawl urbano: non esiste infatti uniformità tra i vari paesaggi suburbani, ma una grande diversità interna alle varie forme in cui si manifesta il fenomeno della dispersione insediativa. Se quanto finora esaminato, soprattutto a livello bibliografico, è riconducibile alla letteratura nordamericana, arrivati a questo punto del lavoro, l’attenzione viene spostata sul continente europeo, prendendo in esame l’emergere del periurbano all’interno del nostro continente e tentando di descrivere sia le contiguità che le differenze tra il fenomeno dell’urban sprawl e quello del periurbano. Infine, adottando un procedimento “ad imbuto”, il lavoro si sofferma sulla situazione del nostro paese in merito alla tematica in questione. L’ultima sezione della ricerca prevede una parte di lavoro empirico. Se, come è emerso nel quadro teorico, molti sono gli elementi che caratterizzano il tema dello sprawl urbano e del periurbano, si è voluto andare a verificare se, ed eventualmente quali, degli elementi descritti, sono presenti in un’area ben delimitata del territorio bolognese, per cercare di capire se si possa parlare di un “periurbano bolognese” e quali caratteristiche esso presenti.

Numerical simulation of interdigitated back contact hetero-junction solar cells

The goal of this thesis is the application of an opto-electronic numerical simulation to heterojunction silicon solar cells featuring an all back contact architecture (Interdigitated Back Contact Hetero-Junction IBC-HJ). The studied structure exhibits both metal contacts, emitter and base, at the back surface of the cell with the objective to reduce the optical losses due to the shadowing by front contact of conventional photovoltaic devices. Overall, IBC-HJ are promising low-cost alternatives to monocrystalline wafer-based solar cells featuring front and back contact schemes, in fact, for IBC-HJ the high concentration doping diffusions are replaced by low-temperature deposition processes of thin amorphous silicon layers. Furthermore, another advantage of IBC solar cells with reference to conventional architectures is the possibility to enable a low-cost assembling of photovoltaic modules, being all contacts on the same side. A preliminary extensive literature survey has been helpful to highlight the specific critical aspects of IBC-HJ solar cells as well as the state-of-the-art of their modeling, processing and performance of practical devices. In order to perform the analysis of IBC-HJ devices, a two-dimensional (2-D) numerical simulation flow has been set up. A commercial device simulator based on finite-difference method to solve numerically the whole set of equations governing the electrical transport in semiconductor materials (Sentuarus Device by Synopsys) has been adopted. The first activity carried out during this work has been the definition of a 2-D geometry corresponding to the simulation domain and the specification of the electrical and optical properties of materials. In order to calculate the main figures of merit of the investigated solar cells, the spatially resolved photon absorption rate map has been calculated by means of an optical simulator. Optical simulations have been performed by using two different methods depending upon the geometrical features of the front interface of the solar cell: the transfer matrix method (TMM) and the raytracing (RT). The first method allows to model light prop-agation by plane waves within one-dimensional spatial domains under the assumption of devices exhibiting stacks of parallel layers with planar interfaces. In addition, TMM is suitable for the simulation of thin multi-layer anti reflection coating layers for the reduction of the amount of reflected light at the front interface. Raytracing is required for three-dimensional optical simulations of upright pyramidal textured surfaces which are widely adopted to significantly reduce the reflection at the front surface. The optical generation profiles are interpolated onto the electrical grid adopted by the device simulator which solves the carriers transport equations coupled with Poisson and continuity equations in a self-consistent way. The main figures of merit are calculated by means of a postprocessing of the output data from device simulation. After the validation of the simulation methodology by means of comparison of the simulation result with literature data, the ultimate efficiency of the IBC-HJ architecture has been calculated. By accounting for all optical losses, IBC-HJ solar cells result in a theoretical maximum efficiency above 23.5% (without texturing at front interface) higher than that of both standard homojunction crystalline silicon (Homogeneous Emitter HE) and front contact heterojuction (Heterojunction with Intrinsic Thin layer HIT) solar cells. However it is clear that the criticalities of this structure are mainly due to the defects density and to the poor carriers transport mobility in the amorphous silicon layers. Lastly, the influence of the most critical geometrical and physical parameters on the main figures of merit have been investigated by applying the numerical simulation tool set-up during the first part of the present thesis. Simulations have highlighted that carrier mobility and defects level in amorphous silicon may lead to a potentially significant reduction of the conversion efficiency.

Anhydrous proton conducting polymer electrolytes based on polymeric ionic liquids

Imidazolium types of ionic liquids were immobilized by tethering it to acrylate backbone. These imidazolium salt containing acrylate monomers were polymerize at 70oC by free radical polymerization to give polymers poly(AcIm-n) with n being the side chain lenght. The chemical structure of the polymer electrolytes obtained by the described synthetic routes was investigated by NMR-spectroscopy. The polymers were doped with various amounts of H3PO4 and LiN(SO2CF3)2, to obtain poly(AcIm-n) x H3PO4 and poly(AcIm-2-Li) x LiN(SO2CF3)2. The TG curves show that the polymer electrolytes are thermally stable up to about 200◦C. DSC results indicates the softening effect of the length of the spacers (n) as well as phosphoric acid. The proton conductivity of the samples increase with x and reaches to 10-2 Scm-1 at 120oC for both poly(AcIm-2)2H3PO4 and poly(AcIm-6)2H3PO4. It was observed that the lithium ion conductivity of the poly(AcIm-2-Li) x LiN(SO2CF3)2 increases with blends (x) up to certain composition and then leveled off independently from blend content. The conductivity reaches to about 10-5 S cm-1 at 30oC and 10-3 at 100oC for poly(AcIm-2-Li) x LiN(SO2CF3)2 where x is 10. The phosphate and phosphoric acid functionality in the resulting polymers, poly(AcIm-n) x H3PO4, undergoes condensation leading to the formation of cross-linked materials at elevated temperature which may improve the mechanical properties to be used as membrane materials in fuel cells. High resolution nuclear magnetic resonance (NMR) spectroscopy was used to obtain information about hydrogen bonding in solids. The low Tg enhances molecular mobility and this leads to better resolved resonances in both the backbone region and side chain region. The mobile and immobile protons can be distinguished by comparing 1H MAS and 1H-DQF NMR spectra. The interaction of the protons which may contribute to the conductivity is observed from the 2D double quantum correlation (DQC) spectra.

Wireless Networks for Body-Centric Communications

Progress in miniaturization of electronic components and design of wireless systems paved the way towards ubiquitous and pervasive communications, enabling anywhere and anytime connectivity. Wireless devices present on, inside, around the human body are becoming commonly used, leading to the class of body-centric communications. The presence of the body with all its peculiar characteristics has to be properly taken into account in the development and design of wireless networks in this context. This thesis addresses various aspects of body-centric communications, with the aim of investigating network performance achievable in different scenarios. The main original contributions pertain to the performance evaluation for Wireless Body Area Networks (WBANs) at the Medium Access Control layer: the application of Link Adaptation to these networks is proposed, Carrier Sense Multiple Access with Collision Avoidance algorithms used for WBAN are extensively investigated, coexistence with other wireless systems is examined. Then, an analytical model for interference in wireless access network is developed, which can be applied to the study of communication between devices located on humans and fixed nodes of an external infrastructure. Finally, results on experimental activities regarding the investigation of human mobility and sociality are presented.

From Radio Channel Modeling to a System Level Perspective in Body-Centric Communications

Body-centric communications are emerging as a new paradigm in the panorama of personal communications. Being concerned with human behaviour, they are suitable for a wide variety of applications. The advances in the miniaturization of portable devices to be placed on or around the body, foster the diffusion of these systems, where the human body is the key element defining communication characteristics. This thesis investigates the human impact on body-centric communications under its distinctive aspects. First of all, the unique propagation environment defined by the body is described through a scenario-based channel modeling approach, according to the communication scenario considered, i.e., on- or on- to off-body. The novelty introduced pertains to the description of radio channel features accounting for multiple sources of variability at the same time. Secondly, the importance of a proper channel characterisation is shown integrating the on-body channel model in a system level simulator, allowing a more realistic comparison of different Physical and Medium Access Control layer solutions. Finally, the structure of a comprehensive simulation framework for system performance evaluation is proposed. It aims at merging in one tool, mobility and social features typical of the human being, together with the propagation aspects, in a scenario where multiple users interact sharing space and resources.

Charge transport in amorphous organic semiconductors

Organic semiconductors with the unique combination of electronic and mechanical properties may offer cost-effective ways of realizing many electronic applications, e.g. large-area flexible displays, printed integrated circuits and plastic solar cells. In order to facilitate the rational compound design of organic semiconductors, it is essential to understand relevant physical properties e.g. charge transport. This, however, is not straightforward, since physical models operating on different time and length scales need to be combined. First, the material morphology has to be known at an atomistic scale. For this atomistic molecular dynamics simulations can be employed, provided that an atomistic force field is available. Otherwise it has to be developed based on the existing force fields and first principle calculations. However, atomistic simulations are typically limited to the nanometer length- and nanosecond time-scales. To overcome these limitations, systematic coarse-graining techniques can be used. In the first part of this thesis, it is demonstrated how a force field can be parameterized for a typical organic molecule. Then different coarse-graining approaches are introduced together with the analysis of their advantages and problems. When atomistic morphology is available, charge transport can be studied by combining the high-temperature Marcus theory with kinetic Monte Carlo simulations. The approach is applied to the hole transport in amorphous films of tris(8-hydroxyquinoline)aluminium (Alq3). First the influence of the force field parameters and the corresponding morphological changes on charge transport is studied. It is shown that the energetic disorder plays an important role for amorphous Alq3, defining charge carrier dynamics. Its spatial correlations govern the Poole-Frenkel behavior of the charge carrier mobility. It is found that hole transport is dispersive for system sizes accessible to simulations, meaning that calculated mobilities depend strongly on the system size. A method for extrapolating calculated mobilities to the infinite system size is proposed, allowing direct comparison of simulation results and time-of-flight experiments. The extracted value of the nondispersive hole mobility and its electric field dependence for amorphous Alq3 agree well with the experimental results.