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.

History of Restoration in Iran: Origins and Developments from 1900 to 1978

This thesis tends to study the origins and developments of the restoration in Iran from its very first moments till the Islamic revolution of 1978. The thesis is its first study of its kind. While almost all recent occidental ideologies regarding the thematic of restoration and conservation of historic monuments are translated and published in Iran, very little efforts have been done regarding the study of the origins of the formation of restoration in the country. The diversity of Iranian contexts, multiplicity of the intervening factors and other factors characterized a different background for the raise and developments of restoration in the country; in the thesis the influencing and characterizing factors in the formation and development of restoration in Iran will be defined and studied in detail with relative examples; due to the complexity of the Iranian context and in order to consider all influencing and characterizing factors the thesis, parallel to have formation and development of restoration, as the main scope of the research, the developments influencing factors will be confronted with necessary flashbacks to the main theme, when and where necessary. A great care will be given to the period of the activity of the restoration experts of IsMEO which is thesis will be called as the period of the introduction of the modern principles of restoration into Iranian context; the fundamental ideologies, practical and theoretical principles of IsMEO will be identified and studied in details; important case of studies of the restoration of IsMEO will be analyzed in details and the innovative aspect of the presence of Italian experts of IsMEO will be revealed.

Testing the effectiveness of phytoscreening to monitor shallow groundwater contamination by chlorinated ethenes

The research presented herein aims to investigate the strengths and weaknesses of a relatively new technique called phytoscreening. Parallel to the well-known phytoremediation, it consists of exploiting the absorbing potential of trees to delineate groundwater contamination plumes, especially for chlorinated ethenes (i.e., PCE, TCE, 1,2-cis DCE, and VC). The latter are prevalent contaminants in groundwater but their fate and transport in surface ecosystems, such as trees, are still poorly understood and subjected to high variability. Moreover, the analytical validity of tree-coring is still limited in many countries due to a lack of knowledge of its application opportunities. Tree-cores are extracted from trunks and generally analyzed by gas chromatography/mass spectrometry. A systematic review of former literature on phytoscreening for chlorinated ethenes is presented in this PhD thesis to evaluate the factors influencing the effectiveness of the technique. Besides, we tested the technique by probing eight sites contaminated by chlorinated ethenes in Italy (Emilia-Romagna) in different hydrogeological and seasonal settings. We coupled the technique with the assessment of gaseous-phase concentrations directly on-site, inserting detector tubes or a photoionization detector in the tree-holes left by the coring tool. Finally, we applied rank order statistic analysis on field data along with literature data to assess under which conditions phytoscreening should be applied to either screen or monitor environmental contamination issues. A relatively high correlation exists between tree-core and groundwater concentrations (Spearman’s ρ > 0.6), being higher for compounds with higher sorption, for sites with shallower and thinner aquifers, and when sampling specific tree types with standardized sampling and extraction protocols. These results indicate the opportunities for assessing the occurrence, type, and concentration of solvents directly from the stem of trees. This can reduce the costs of characterization surveys, allowing rapid identification of hotspots and plume direction and thus optimizing the drilling of boreholes.

Numerical and physical modelling of axially loaded piles for offshore wind turbines

The scope of the thesis is to broaden the knowledge about axially loaded pipe piles, that can play as foundations for offshore wind turbines based on jacket structures. The goal of the work was pursued by interpreting experimental data on large-scale model piles and by developing numerical tools for the prediction of their monotonic response to tensile and compressive loads to failure. The availability of experimental results on large scale model piles produced in two different campaigns at Fraunhofer IWES (Hannover, Germany) represented the reference for the whole work. Data from CPTs, blow counts during installation and load-displacement curves allowed to develop considerations on the experimental results and comparison with empirical methods from literature, such as CPT-based methods and Load Transfer methods. The understanding of soil-structure interaction mechanisms has been involved in the study in order to better assess the mechanical response of the sand with the scope to help in developing predictive tools of the experiments. A lack of information on the response of Rohsand 3152 when in contact with steel was highlighted, so the necessity of better assessing its response was fulfilled with a comprehensive campaign of interface shear test. It was found how the response of the sand to ultimate conditions evolve with the roughness of the steel, which is a precious information to take account of when attempting the prediction of a pile capacity. Parallel to this topic, the work has developed a numerical modelling procedure that was validated on the available large-scale model piles at IWES. The modelling strategy is intended to build a FE model whose mechanical properties of the sand come from an interpretation of commonly available geotechnical tests. The results of the FE model were compared with other predictive tools currently used in the engineering practice.