Photocatalytic activity of nanostructured anatase coatings obtained by cold gas spray

[EN] This article describes a photocatalytic nanostructured anatase coating deposited by cold gas spray (CGS) supported on titanium sub-oxide (TiO22x) coatings obtained by atmospheric plasma spray (APS) onto stainless steel cylinders. The photocatalytic coating was homogeneous and preserved the composition and nanostructure of the starting powder. The inner titanium sub-oxide coating favored the deposition of anatase particles in the solid state. Agglomerated nano-TiO2 particles fragmented when impacting onto the hard surface of the APS TiO22x bond coat. The rough surface provided by APS provided an ideal scenario for entrapping the nanostructured particles, which may be adhered onto the bond coat due to chemical bonding; a possible bonding mechanism is described. Photocatalytic experiments showed that CGS nano-TiO2 coating was active for photodegrading phenol and formic acid under aqueous conditions. The results were similar to the performance obtained by competitor technologies and materials such as dip-coating P25 photocatalysts. Disparity in the final performance of the photoactive materials may have been caused by differences in grain size and the crystalline composition of titanium dioxide.

Sviluppo e validazione di un modello di film fluido per simulazioni CFD di motori a combustione interna

A wall film model has been implemented in a customized version of KIVA code developed at University of Bologna. Under the hypothesis of `thin laminar ow' the model simulates the dynamics of a liquid wall film generated by impinging sprays. Particular care has been taken in numerical implementation of the model. The major phenomena taken into account in the present model are: wall film formation by impinging spray; body forces, such as gravity or acceleration of the wall; shear stress at the interface with the gas and no slip condition on the wall; momentum contribution and dynamic pressure generated by the tangential and normal component of the impinging drops; film evaporation by heat exchange with wall and surrounding gas. The model doesn't consider the effect of the wavy film motion and suppose that all the impinging droplets adhere to the film. The governing equations have been integrated in space by using a finite volume approach with a first order upwind differencing scheme and they have been integrated in time with a fully explicit method. The model is validated using two different test cases reproducing PFI gasoline and DI Diesel engine wall film conditions.

Biomimetic Materials for Biomedical Applications

Objects with complex shape and functions have always attracted attention and interest. The morphological diversity and complexity of naturally occurring forms and patterns have been a motivation for humans to copy and adopt ideas from Nature to achieve functional, aesthetic and social value. Biomimetics is addressed to the design and development of new synthetic materials using strategies adopted by living organisms to produce biological materials. In particular, biomineralized tissues are often sophisticate composite materials, in which the components and the interfaces between them have been defined and optimized, and that present unusual and optimal chemical-physical, morphological and mechanical properties. Moreover, biominerals are generally produced by easily traceable raw materials, in aqueous media and at room pressure and temperature, that is through cheap process and materials. Thus, it is not surprising that the idea to mimic those strategies proper of Nature has been employed in several areas of applied sciences, such as for the preparation of liquid crystals, ceramic thin films computer switches and many other advanced materials. On this basis, this PhD thesis is focused on the investigation of the interaction of biologically active ions and molecules with calcium phosphates with the aim to develop new materials for the substitution and repair of skeletal tissue, according to the following lines: I. Modified calcium phosphates. A relevant part of this PhD thesis has been addressed to study the interaction of Strontium with calcium phosphates. It was demonstrated that strontium ion can substitute for calcium into hydroxyapatite, causing appreciable structural and morphological modifications. The detailed structural analysis carried out on the nanocrystals at different strontium content provided new insight into its interaction with the structure of hydroxyapatite. At variance with the behaviour of Sr towards HA, it was found that this ion inhibits the synthesis of octacalcium phosphate. However, it can substitute for calcium in this structure up to 15 atom %, in agreement with the increase of the cell parameters observed on increasing ion concentration. A similar behaviour was found for Magnesium ion, whereas Manganese inhibits the synthesis of octacalcium phosphate and it promotes the precipitation of dicalcium phosphate dehydrate. It was also found that Strontium affects the kinetics of the reaction of hydrolysis of α-TCP. It inhibits the conversion from α-TCP to hydroxyapatite. However, the resulting apatitic phase contains significant amounts of Sr2+ suggesting that the addition of Sr2+ to the composition of α-TCP bone cements could be successfully exploited for its local delivery in bone defects. The hydrolysis of α-TCP has been investigated also in the presence of increasing amounts of gelatin: the results indicated that this biopolymer accelerates the hydrolysis reaction and promotes the conversion of α-TCP into OCP, suggesting that its addition in the composition of calcium phosphate cements can be employed to modulate the OCP/HA ratio, and as a consequence the solubility, of the set cement. II. Deposition of modified calcium phosphates on metallic substrates. Coating with a thin film of calcium phosphates is frequently applied on the surface of metallic implants in order to combine the high mechanical strength of the metal with the excellent bioactivity of the calcium phosphates surface layers. During this PhD thesis, thank to the collaboration with prof. I.N. Mihailescu, head of the Laser-Surface-Plasma Interactions Laboratory (National Institute for Lasers, Plasma and Radiation Physics – Laser Department, Bucharest) Pulsed Laser Deposition has been successfully applied to deposit thin films of Sr substituted HA on Titanium substrates. The synthesized coatings displayed a uniform Sr distribution, a granular surface and a good degree of crystallinity which slightly decreased on increasing Sr content. The results of in vitro tests carried out on osteoblast-like and osteoclast cells suggested that the presence of Sr in HA thin films can enhance the positive effect of HA coatings on osteointegration and bone regeneration, and prevent undesirable bone resorption. The possibility to introduce an active molecule in the implant site was explored using Matrix Assisted Pulsed Laser Evaporation to deposit hydroxyapatite nanocrystals at different content of alendronate, a bisphosphonate widely employed in the treatments of pathological diseases associated to bone loss. The coatings displayed a good degree of crystallinity, and the results of in vitro tests indicated that alendronate promotes proliferation and differentiation of osteoblasts even when incorporated into hydroxyapatite. III. Synthesis of drug carriers with a delayed release modulated by a calcium phosphate coating. A core-shell system for modulated drug delivery and release has been developed through optimization of the experimental conditions to cover gelatin microspheres with a uniform layer of calcium phosphate. The kinetics of the release from uncoated and coated microspheres was investigated using aspirin as a model drug. It was shown that the presence of the calcium phosphate shell delays the release of aspirin and allows to modulate its action.

Testo e memoria tra semiotica e scienze cognitive: una situazione sperimentale intorno al ricordo di un film

The research project presented in this dissertation is about text and memory. The title of the work is "Text and memory between Semiotics and Cognitive Science: an experimental setting about remembering a movie". The object of the research is the relationship between texts or "textuality" - using a more general semiotic term - and memory. The goal is to analyze the link between those semiotic artifacts that a culture defines as autonomous meaningful objects - namely texts - and the cognitive performance of memory that allows to remember them. An active dialogue between Semiotics and Cognitive Science is the theoretical paradigm in which this research is set, the major intend is to establish a productive alignment between the "theory of text" developed in Semiotics and the "theory of memory" outlined in Cognitive Science. In particular the research is an attempt to study how human subjects remember and/or misremember a film, as a specific case study; in semiotics, films are “cinematographic texts”. The research is based on the production of a corpus of data gained through the qualitative method of interviewing. After an initial screening of a fulllength feature film each participant of the experiment has been interviewed twice, according to a pre-established set of questions. The first interview immediately after the screening: the subsequent, follow-up interview three months from screening. The purpose of this design is to elicit two types of recall from the participants. In order to conduce a comparative inquiry, three films have been used in the experimental setting. Each film has been watched by thirteen subjects, that have been interviewed twice. The corpus of data is then made by seventy-eight interviews. The present dissertation displays the results of the investigation of these interviews. It is divided into six main parts. Chapter one presents a theoretical framework about the two main issues: memory and text. The issue of the memory is introduced through many recherches drown up in the field of Cognitive Science and Neuroscience. It is developed, at the same time, a possible relationship with a semiotic approach. The theoretical debate about textuality, characterizing the field of Semiotics, is examined in the same chapter. Chapter two deals with methodology, showing the process of definition of the whole method used for production of the corpus of data. The interview is explored in detail: how it is born, what are the expected results, what are the main underlying hypothesis. In Chapter three the investigation of the answers given by the spectators starts. It is examined the phenomenon of the outstanding details of the process of remembering, trying to define them in a semiotic way. Moreover there is an investigation of the most remembered scenes in the movie. Chapter four considers how the spectators deal with the whole narrative. At the same time it is examined what they think about the global meaning of the film. Chapter five is about affects. It tries to define the role of emotions in the process of comprehension and remembering. Chapter six presents a study of how the spectators account for a single scene of the movie. The complete work offers a broad perspective about the semiotic issue of textuality, using both a semiotic competence and a cognitive one. At the same time it presents a new outlook on the issue of memory, opening several direction of research.

Atomistic simulations of bulk and free standing film smectics

In questa tesi viene descritto lo studio delle fasi liquido-cristalline del 4-n-ottil-4-cianobifenile eseguito tramite simulazioni al calcolatore molecular dynamics, sia per campioni bulk che per film smectici sottili. Impiegando un campo di forze "molecular mechanics" precedentemente usato con successo per studiare sistemi composti da 250 molecole della serie degli n-cianobifenili (nCB, con n pari a 4-8 atomi di carbonio nella catena alifatica), si è simulato il comportamento di un sistema bulk di 750 molecole e di un film smectico di 1500 molecole. Nel primo caso, sottoponendo il campione a un graduale raffreddamento, si è osservata la formazione spontanea di fasi ordinate quali quella nematica e quella smectica. Nel secondo caso, invece, si è studiata l'influenza dell'interfaccia con il vuoto sull'ordine posizionale e orientazionale di film sottili di diverso spessore e temperatura. Si sono confrontate le proprietà di entrambi i sistemi simulati con i dati sperimentali disponibili in letteratura, confermando la bontà del modello nel riprodurre fedelmente le caratteristiche dei campioni reali.

In situ real-time investigation of Organic Ultra-Thin-Film transistors: growth, electrical properties and biosensing applications

Organic electronics has grown enormously during the last decades driven by the encouraging results and the potentiality of these materials for allowing innovative applications, such as flexible-large-area displays, low-cost printable circuits, plastic solar cells and lab-on-a-chip devices. Moreover, their possible field of applications reaches from medicine, biotechnology, process control and environmental monitoring to defense and security requirements. However, a large number of questions regarding the mechanism of device operation remain unanswered. Along the most significant is the charge carrier transport in organic semiconductors, which is not yet well understood. Other example is the correlation between the morphology and the electrical response. Even if it is recognized that growth mode plays a crucial role into the performance of devices, it has not been exhaustively investigated. The main goal of this thesis was the finding of a correlation between growth modes, electrical properties and morphology in organic thin-film transistors (OTFTs). In order to study the thickness dependence of electrical performance in organic ultra-thin-film transistors, we have designed and developed a home-built experimental setup for performing real-time electrical monitoring and post-growth in situ electrical characterization techniques. We have grown pentacene TFTs under high vacuum conditions, varying systematically the deposition rate at a fixed room temperature. The drain source current IDS and the gate source current IGS were monitored in real-time; while a complete post-growth in situ electrical characterization was carried out. At the end, an ex situ morphological investigation was performed by using the atomic force microscope (AFM). In this work, we present the correlation for pentacene TFTs between growth conditions, Debye length and morphology (through the correlation length parameter). We have demonstrated that there is a layered charge carriers distribution, which is strongly dependent of the growth mode (i.e. rate deposition for a fixed temperature), leading to a variation of the conduction channel from 2 to 7 monolayers (MLs). We conciliate earlier reported results that were apparently contradictory. Our results made evident the necessity of reconsidering the concept of Debye length in a layered low-dimensional device. Additionally, we introduce by the first time a breakthrough technique. This technique makes evident the percolation of the first MLs on pentacene TFTs by monitoring the IGS in real-time, correlating morphological phenomena with the device electrical response. The present thesis is organized in the following five chapters. Chapter 1 makes an introduction to the organic electronics, illustrating the operation principle of TFTs. Chapter 2 presents the organic growth from theoretical and experimental points of view. The second part of this chapter presents the electrical characterization of OTFTs and the typical performance of pentacene devices is shown. In addition, we introduce a correcting technique for the reconstruction of measurements hampered by leakage current. In chapter 3, we describe in details the design and operation of our innovative home-built experimental setup for performing real-time and in situ electrical measurements. Some preliminary results and the breakthrough technique for correlating morphological and electrical changes are presented. Chapter 4 meets the most important results obtained in real-time and in situ conditions, which correlate growth conditions, electrical properties and morphology of pentacene TFTs. In chapter 5 we describe applicative experiments where the electrical performance of pentacene TFTs has been investigated in ambient conditions, in contact to water or aqueous solutions and, finally, in the detection of DNA concentration as label-free sensor, within the biosensing framework.

Außerirdische im amerikanischen Sciencefiction-Film

Die vorliegende Dissertation untersucht die Darstellung von außerirdischen Lebensformen im amerikanischen Sciencefiction-Film in Form eines filmhistorischen Gesamtüberblicks.Noch bevor der 1. Weltkrieg begann, waren die meisten Genremerkmale, die den Sciencefiction-Film bis heute charakterisieren, bereits erdacht. Die wenigen Sciencefiction-Filme, die Außerirdische zeigten, fügten sich jedoch sehr gut in den verspielten, märchenhaften Sciencefiction-Film der Vorkriegszeit. Bis sich das Topos des Außerirdischen als eigenes Subgenre etablieren konnte, sollten aber noch einige Jahrzehnte vergehen. Im Jahr 1950 nahm das Interesse am Weltraum schlagartig zu. Bei der Darstellung der fremden Wesen orientierte man sich zunächst an irdischen Vorbildern und es entstanden zahlreiche humanoide, tierische, pflanzliche, mineralische und amorphe außerirdische Lebensformen, die dem Menschen oft überlegen waren. In den 60ern brach der Mensch häufiger selbst in den Weltraum auf - immer öfter standen Menschen und Außerirdische nun auf gleicher Stufe. In den 70ern wurden die märchencharakteristischen Begriffe Gut und Böse durch Außerirdische verkörpert. In den 80ern gelang es dem Guten, sich durchzusetzen. Einige wunderbare Freundschaften zwischen Menschen und Außerirdischen entwickelten sich und Außerirdische wurden in die menschliche Gesellschaft integriert. Damit scheinen aber alle Spielarten des Guten gezeigt zu sein und in den 90ern ist wieder Raum für Geschichten, in denen Außerirdische das Böse verkörpern.

Teoria e prassi del product placement. Il caso dei film contemporanei per adolescenti (ITA/USA 2006-2010)

Through this research I have tried to demonstrate how the evolution of the newest marketing strategies - that work towards engaging relationships with consumers, thus building an emotional connection between the brand and the user- can be considered as a response to the evolution of young audiences and consumers. More specifically, I have analized product placement as a cultural and social phenomena above all, and not only as an economical one, thus demonstrating all the social and cultural practices that this tool implies. The approach I have chosen to do so, is historical-analytical, particularly focusing on the evolution of the society and of the consumer, especially for what teenagers (both as audiences and as consumers) are concerned.

Identità e diaspora attraverso lo specchio doppio del processo traduttivo. La traduzione del romanzo "The Namesake" - "L'omonimo" di J. Lahiri e il doppiaggio del film "The Namesake" - "Il destino nel nome" di M. Nair

La ricerca si propone come studio teorico e analitico basato sulla traduzione letteraria e audiovisiva del genere diasporico, esemplificato nel romanzo The Namesake – L’omonimo di J. Lahiri e nel film The Namesake – Il destino nel nome di M. Nair. Si sviluppa, quindi, un doppio percorso di analisi, concentrandosi sulla traduzione interlinguistica di due modalità testuali differenti, quella letteraria (il testo narrativo) e quella audiovisiva (in particolare, il doppiaggio). L’approccio teorico è di stampo interdisciplinare, come risulta sempre più imprescindibile nel campo dei Translation Studies: infatti, si cerca di coniugare prospettive di natura più linguistica, quali i Descriptive Translation Studies (in particolare, Toury 1995) e lo sviluppo degli studi sui cosiddetti ‘universali traduttivi’, con approcci di stampo più culturalista, in particolare gli studi sulla traduzione post-coloniali, con le loro riflessioni sui concetti di ‘alterità’ e ‘ibridismo’. Completa il quadro teorico di riferimento una necessaria definizione e descrizione del genere diasporico relativo alla cultura indiana, in rapporto sia al contesto di partenza (statunitense) sia al contesto di arrivo (italiano) per entrambi i testi presi in considerazione. La metodologia scelta per l’indagine è principalmente di natura linguistica, con l’adozione del modello elaborato dallo studioso J. Malone (1988). L’analisi empirica, accompagnata da una serie di riflessioni teoriche e linguistiche specifiche, si concentra su tre aspetti cruciali per entrambe le tipologie testuali, quali: la resa della naturalezza dei dialoghi nel discorso letterario e in quello filmico, la rappresentazione del multiculturalismo e delle varietà linguistiche caratterizzanti i due testi di partenza e i numerosi riferimenti culturo-specifici delle due opere e la loro traduzione in italiano. Si propongono, infine, alcune considerazioni in ottica intersemiotica in relazione alle tre aree individuate, a integrazione dell’indagine in chiave interlinguistica.