Sistemi liquido cristallini complessi: simulazioni al calcolatore e studi ESR

The aim of this PhD thesis was to study at a microscopic level different liquid crystal (LC) systems, in order to determine their physical properties, resorting to two distinct methodologies, one involving computer simulations, and the other spectroscopic techniques, in particular electron spin resonance (ESR) spectroscopy. By means of the computer simulation approach we tried to demonstrate this tool effectiveness for calculating anisotropic static properties of a LC material, as well as for predicting its behaviour and features. This required the development and adoption of suitable molecular models based on a convenient intermolecular potentials reflecting the essential molecular features of the investigated system. In particular, concerning the simulation approach, we have set up models for discotic liquid crystal dimers and we have studied, by means of Monte Carlo simulations, their phase behaviour and self­-assembling properties, with respect to the simple monomer case. Each discotic dimer is described by two oblate Gay­Berne ellipsoids connected by a flexible spacer, modelled by a harmonic "spring" of three different lengths. In particular we investigated the effects of dimerization on the transition temperatures, as well as on the characteristics of molecular aggregation displayed and the relative orientational order. Moving to the experimental results, among the many experimental techniques that are typically employed to evaluate LC system distinctive features, ESR has proved to be a powerful tool in microscopic scale investigation of the properties, structure, order and dynamics of these materials. We have taken advantage of the high sensitivity of the ESR spin probe technique to investigate increasingly complex LC systems ranging from devices constituted by a polymer matrix in which LC molecules are confined in shape of nano- droplets, as well as biaxial liquid crystalline elastomers, and dimers whose monomeric units or lateral groups are constituted by rod-like mesogens (11BCB). Reflection-mode holographic-polymer dispersed liquid crystals (H-PDLCs) are devices in which LCs are confined into nanosized (50­-300 nm) droplets, arranged in layers which alternate with polymer layers, forming a diffraction grating. We have determined the configuration of the LC local director and we have derived a model of the nanodroplet organization inside the layers. Resorting also to additional information on the nanodroplet size and shape distribution provided by SEM images of the H-PDLC cross-section, the observed director configuration has been modeled as a bidimensional distribution of elongated nanodroplets whose long axis is, on the average, parallel to the layers and whose internal director configuration is a uniaxial quasi- monodomain aligned along the nanodroplet long axis. The results suggest that the molecular organization is dictated mainly by the confinement, explaining, at least in part, the need for switching voltages significantly higher and the observed faster turn-off times in H-PDLCs compared to standard PDLC devices. Liquid crystal elastomers consist in cross-linked polymers, in which mesogens represent the monomers constituting the main chain or the laterally attached side groups. They bring together three important aspects: orientational order in amorphous soft materials, responsive molecular shape and quenched topological constraints. In biaxial nematic liquid crystalline elastomers (BLCEs), two orthogonal directions, rather than the one of normal uniaxial nematic, can be controlled, greatly enhancing their potential value for applications as novel actuators. Two versions of a side-chain BLCEs were characterized: side­-on and end­-on. Many tests have been carried out on both types of LCE, the main features detected being the lack of a significant dynamical behaviour, together with a strong permanent alignment along the principal director, and the confirmation of the transition temperatures already determined by DSC measurements. The end­-on sample demonstrates a less hindered rotation of the side group mesogenic units and a greater freedom of alignment to the magnetic field, as already shown by previous NMR studies. Biaxial nematic ESR static spectra were also obtained on the basis of Molecular Dynamics generated biaxial configurations, to be compared to the experimentally determined ones, as a mean to establish a possible relation between biaxiality and the spectral features. This provides a concrete example of the advantages of combining the computer simulation and spectroscopic approaches. Finally, the dimer α,ω-bis(4'-cyanobiphenyl-4-yl)undecane (11BCB), synthesized in the "quest" for the biaxial nematic phase has been analysed. Its importance lies in the dimer significance as building blocks in the development of new materials to be employed in innovative technological applications, such as faster switching displays, resorting to the easier aligning ability of the secondary director in biaxial phases. A preliminary series of tests were performed revealing the population of mesogenic molecules as divided into two groups: one of elongated straightened conformers sharing a common director, and one of bent molecules, which display no order, being equally distributed in the three dimensions. Employing this model, the calculated values show a consistent trend, confirming at the same time the transition temperatures indicated by the DSC measurements, together with rotational diffusion tensor values that follow closely those of the constituting monomer 5CB.

Toward a peripheral view of manufacturing networks

This doctoral thesis unfolds into a collection of three distinct articles that share an interest in supply firms, or “peripheral firms”. The three studies offer a novel theoretical perspective that I call the peripheral view of manufacturing networks. Building on the relational view literature, this new perspective identifies the supplier-based theoretical standpoint to analyze and explain the antecedents of relational rents in manufacturing networks. The first article, the namesake of the dissertation, is a theoretical contribution that explains the foundations of the “peripheral view of manufacturing networks”. The second article “Framing The Strategic Peripheries: A Novel Typology of Suppliers” is an empirical study with the aim to offer an interpretation of peripheries’ characteristics and dynamics. The third article, “What is Behind Absorptive Capacity? Dispelling the Opacity of R&D” presents an example of general theory development by using data from peripheral firms.

Processi e impatti della migrazione. L'esperienza di chi resta in tre famiglie peruviane

Questo studio propone un’esplorazione dei nessi tra fenomeno migratorio, dinamiche transnazionali e quadri familiari, in un contesto specificato che è quello peruviano. Dal confronto critico con i paradigmi disciplinari in uso negli ambiti dell’antropologia delle migrazioni, degli studi sul transnazionalismo e sulle famiglie transnazionali, e dell’etnografia multi-situata, si è tentata una lettura teorica e metodologica che renda conto del contesto socio-familiare di partenza non come parte periferica di una completa visione del migrante, ma quale oggetto specifico della ricerca. L’obbiettivo è verificare, a livello locale, quale siano gli impatti della migrazione esterna di uno o più membri sulle strutture e sulle dinamiche, sui codici e sui ruoli del nucleo parentale originario. E individuare, sul piano transnazionale, quali reti, quali rituali o pratiche di connessione funzionino tra coloro che vanno e coloro che restano, quali discorsi e quali culture migratorie si sviluppino e si condividano. La ricerca si è svolta in Perù tra il 2009 ed il 2011. Il campo dell’indagine si è diviso tra due località nell’area della Costa del Perù. Lima, la capitale, e Chiclín, un villaggio rurale nella regione settentrionale de La Libertad. Attraverso le tecniche d’inchiesta della pratica etnografica, una permanenza prolungata sul terreno e l’osservazione partecipante, si è lavorato con i membri adulti di ambo i sessi di tre gruppi parentali distribuiti tra i due luoghi menzionati, selezionati in partenza sulla base dei contatti forniti da alcuni dei loro familiari emigrati in Italia tra il 1990 ed il 2000. Centrare l’analisi sulle figure per certi aspetti marginali dell’esperienza della migrazione normalmente considerata, è servito da un lato a rovesciare parzialmente la prospettiva transnazionale aggiustandola proprio rispetto a quegli attori sociali; dall’altro e ad un tempo, ha permesso di fare luce su dinamiche migratorie più generali, di ricostruirle e di ri-teorizzarle.

Analisi del popolamento e delle dinamiche culturali del Neolitico nella Puglia Centrale : un approccio territoriale per la Bassa Murgia

L’obiettivo della ricerca condotta dal candidato è stato sin dal principio la proposta di un’analisi del popolamento e delle dinamiche culturali dell’età neolitica nella Puglia Centrale. Tale aspirazione derivava dal fatto che il territorio oggetto di tale ricerca è stato, negli ultimi decenni, assai meno investigato rispetto alle limitrofe aree, come la piana del Tavoliere ed il Salento in particolare. Questa mancanza di informazioni rendeva necessaria una rivisitazione delle ricerche e degli studi, attraverso la costruzione di un atlante del popolamento, al fine di colmare questo vuoto. Infatti, una valutazione del popolamento dell’età neolitica nell’Italia sud-orientale non può essere considerata per aree culturali distinte e geograficamente limitate. Nonostante vi siano importanti differenziazioni di facies archeologiche, è solo attraverso una visione complessiva e con un controllo articolato delle informazioni che è possibile descrivere i processi e le dinamiche che hanno portato ad un popolamento così imponente, dalla sua espansione al repentino collasso, causando la trasformazione del paesaggio pugliese. La scelta di guardare alla complessità neolitica di questo versante della Puglia si lega culturalmente, oltre che geograficamente, alla ricerca già effettuata sulla grande diffusione del neolitico nella piana del Tavoliere di Puglia, unico esempio europeo in quanto a colonizzazione capillare del territorio..Ciò ha permesso di disegnare un quadro globale, che al momento esclude solo la penisola salentina, del popolamento neolitico della Puglia settentrionale e centrale. Le caratteristiche che differenziano i due complessi, sono strettamente legate sia all’habitat insediativo, inteso come scelte insediamentali, che nella regione indagata appare organizzato su diversi livelli (area costiera adriatica, area prospiciente antichi alvei torrentizi, propaggini dell’altopiano delle Murge), che alle forme culturali, intese come produzione artigianale e soprattutto aspetti rituali connessi alla frequentazione delle grotte naturali.

Displacement Analysis of Under-Constrained Cable-Driven Parallel Robots

This dissertation studies the geometric static problem of under-constrained cable-driven parallel robots (CDPRs) supported by n cables, with n ≤ 6. The task consists of determining the overall robot configuration when a set of n variables is assigned. When variables relating to the platform posture are assigned, an inverse geometric static problem (IGP) must be solved; whereas, when cable lengths are given, a direct geometric static problem (DGP) must be considered. Both problems are challenging, as the robot continues to preserve some degrees of freedom even after n variables are assigned, with the final configuration determined by the applied forces. Hence, kinematics and statics are coupled and must be resolved simultaneously. In this dissertation, a general methodology is presented for modelling the aforementioned scenario with a set of algebraic equations. An elimination procedure is provided, aimed at solving the governing equations analytically and obtaining a least-degree univariate polynomial in the corresponding ideal for any value of n. Although an analytical procedure based on elimination is important from a mathematical point of view, providing an upper bound on the number of solutions in the complex field, it is not practical to compute these solutions as it would be very time-consuming. Thus, for the efficient computation of the solution set, a numerical procedure based on homotopy continuation is implemented. A continuation algorithm is also applied to find a set of robot parameters with the maximum number of real assembly modes for a given DGP. Finally, the end-effector pose depends on the applied load and may change due to external disturbances. An investigation into equilibrium stability is therefore performed.

A multi-instrumental approach to the study of equatorial ionosphere over South America

An extensive study of the morphology and the dynamics of the equatorial ionosphere over South America is presented here. A multi parametric approach is used to describe the physical characteristics of the ionosphere in the regions where the combination of the thermospheric electric field and the horizontal geomagnetic field creates the so-called Equatorial Ionization Anomalies. Ground based measurements from GNSS receivers are used to link the Total Electron Content (TEC), its spatial gradients and the phenomenon known as scintillation that can lead to a GNSS signal degradation or even to a GNSS signal ‘loss of lock’. A new algorithm to highlight the features characterizing the TEC distribution is developed in the framework of this thesis and the results obtained are validated and used to improve the performance of a GNSS positioning technique (long baseline RTK). In addition, the correlation between scintillation and dynamics of the ionospheric irregularities is investigated. By means of a software, here implemented, the velocity of the ionospheric irregularities is evaluated using high sampling rate GNSS measurements. The results highlight the parallel behaviour of the amplitude scintillation index (S4) occurrence and the zonal velocity of the ionospheric irregularities at least during severe scintillations conditions (post-sunset hours). This suggests that scintillations are driven by TEC gradients as well as by the dynamics of the ionospheric plasma. Finally, given the importance of such studies for technological applications (e.g. GNSS high-precision applications), a validation of the NeQuick model (i.e. the model used in the new GALILEO satellites for TEC modelling) is performed. The NeQuick performance dramatically improves when data from HF radar sounding (ionograms) are ingested. A custom designed algorithm, based on the image recognition technique, is developed to properly select the ingested data, leading to further improvement of the NeQuick performance.

Computational insight into materials properties

The aim of the work was to explore the practical applicability of molecular dynamics at different length and time scales. From nanoparticles system over colloids and polymers to biological systems like membranes and finally living cells, a broad range of materials was considered from a theoretical standpoint. In this dissertation five chemistry-related problem are addressed by means of theoretical and computational methods. The main results can be outlined as follows. (1) A systematic study of the effect of the concentration, chain length, and charge of surfactants on fullerene aggregation is presented. The long-discussed problem of the location of C60 in micelles was addressed and fullerenes were found in the hydrophobic region of the micelles. (2) The interactions between graphene sheet of increasing size and phospholipid membrane are quantitatively investigated. (3) A model was proposed to study structure, stability, and dynamics of MoS2, a material well-known for its tribological properties. The telescopic movement of nested nanotubes and the sliding of MoS2 layers is simulated. (4) A mathematical model to gain understaning of the coupled diffusion-swelling process in poly(lactic-co-glycolic acid), PLGA, was proposed. (5) A soft matter cell model is developed to explore the interaction of living cell with artificial surfaces. The effect of the surface properties on the adhesion dynamics of cells are discussed.