Effect of pH-induced nanopowder deagglomeration on sintering, microstructure and dielectric properties of Ba0.77Ca0.23TiO3 ceramics

Ba0.77Ca0.23TiO3 ceramics were produced in this work starting from nanopowders synthesized via a polymeric precursor method. By adjusting the pH values of the precursor solutions above 7, it was possible to prepare powders weakly aggregated and with a smaller particle size, both facts which traduced into an enhanced nanopowders' sintering process at comparatively lower temperatures. Irrespective of the initial pH value, highly-dense and second phase-free ceramics were obtained following optimal sintering parameters (temperature and time) extracted from dilatometric and density measurements. By considering these and other sintering conditions, moreover, polycrystalline materials with an average grain size varying from 0.35 to 8 mm were produced, the grain growth process involving liquid phase-assisted sintering for heat treatments achieved at 1320 °C. The study of grain size effects on the ferroelectric properties of these materials was conducted, the results being discussed in the light of previous debates, including grain size-dependent degree of tetragonal distortion in such materials, as verified in this work.

Parametric analysis of effective material properties of thickness-shear piezoelectric macro-fibre composites

A previous study on the characterization of effective material properties of a d15 thickness-shear piezoelectric Macro-Fibre Composite (MFC) made of seven layers (Kapton, Acrylic, Electrode, Piezoceramic Fibre and Epoxy Composite, Electrode, Acrylic, Kapton) using a finite element homogenization method has shown that the packaging reduces significantly the shear stiffness of the piezoceramic material and, thus, leads to significantly smaller effective electromechanical coupling coefficient k15 and piezoelectric stress constant e15 when compared to the piezoceramic fibre properties. Therefore, the main objective of this work is to perform a parametric analysis in which the effect of the variations of fibre volume fraction, Epoxy elastic modulus, electrode thickness and active layer thickness on the MFC effective material properties is evaluated. Results indicate that an effective d15 MFC should use relatively thick fibres having relatively high shear modulus and relatively stiff epoxy filler. On the other hand, the electrode thickness does not affect significantly the MFC performance.

Effective properties evaluation for smart composite materials

The purpose of this article is to present a method which consists in the development of unit cell numerical models for smart composite materials with piezoelectric fibers made of PZT embedded in a non-piezoelectric matrix (epoxy resin). This method evaluates a globally homogeneous medium equivalent to the original composite, using a representative volume element (RVE). The suitable boundary conditions allow the simulation of all modes of the overall deformation arising from any arbitrary combination of mechanical and electrical loading. In the first instance, the unit cell is applied to predict the effective material coefficients of the transversely isotropic piezoelectric composite with circular cross section fibers. The numerical results are compared to other methods reported in the literature and also to results previously published, in order to evaluate the method proposal. In the second step, the method is applied to calculate the equivalent properties for smart composite materials with square cross section fibers. Results of comparison between different combinations of circular and square fiber geometries, observing the influence of the boundary conditions and arrangements are presented.

How low-level laser therapy can change mechanical properties of cells.

Low level laser therapy is used as a treatment of several conditions, including inflammatory processes and wound healing. Possible changes in mechanical properties of cells, caused by illumination, are investigated with optical magnetic twisting cytometry (OMTC), which is a technique used to evaluate mechanical properties in cell culture. Ferromagnetic micro beads are bound to cell cytoskeleton, the beads are magnetized vertically and a horizontal twisting magnetic field is applied causing a torque that moves the beads and deforms the cell, the beads rotate and displace. Based on the lateral displacement of the beads, elastic shear and loss moduli are obtained. Samples of human bronchial epithelial cell culture were divided in two groups: one was illuminated with a 660 nm red laser, 30 mW power, 0.75 W/cm2 irradiance, during different time intervals, and the other one, the control group, was not illuminated. The values of the mechanical constants of the cells of the control group showed a tendency of increasing with the time out of the incubator. On the other hand, the illuminated group showed constancy on the behavior of both moduli, keeping the normal conditions of the cell culture. Those results indicate that illumination can induce cells to homeostasis, and OMTC is sensitive to observe departures from the steady conditions. Hence, OMTC is an important technique which can be used to aggregate knowledge on the light effect in cell cytoskeleton and even on the low level laser therapy mechanisms in inflammatory processes and/or wound healing.

How low-level laser therapy can change mechanical properties of cells.

Low level laser therapy is used as a treatment of several conditions, including inflammatory processes and wound healing. Possible changes in mechanical properties of cells, caused by illumination, are investigated with optical magnetic twisting cytometry (OMTC), which is a technique used to evaluate mechanical properties in cell culture. Ferromagnetic micro beads are bound to cell cytoskeleton, the beads are magnetized vertically and a horizontal twisting magnetic field is applied causing a torque that moves the beads and deforms the cell, the beads rotate and displace. Based on the lateral displacement of the beads, elastic shear and loss moduli are obtained. Samples of human bronchial epithelial cell culture were divided in two groups: one was illuminated with a 660 nm red laser, 30 mW power, 0.75 W/cm2 irradiance, during different time intervals, and the other one, the control group, was not illuminated. The values of the mechanical constants of the cells of the control group showed a tendency of increasing with the time out of the incubator. On the other hand, the illuminated group showed constancy on the behavior of both moduli, keeping the normal conditions of the cell culture. Those results indicate that illumination can induce cells to homeostasis, and OMTC is sensitive to observe departures from the steady conditions. Hence, OMTC is an important technique which can be used to aggregate knowledge on the light effect in cell cytoskeleton and even on the low level laser therapy mechanisms in inflammatory processes and/or wound healing.

Properties of a new poly-ether-glycol copolymer.

Triblock copolymers are made of monomer segments, being the central part usually hydrophobic and the outer parts hydrophilic. By varying sizes, molecular weights and monomer types of the segments one obtains different final molecules, with different physico-chemical properties, which are directly related to the performance of the final product. Looking for new products to be used, among other possibilities, in biological applications, a new polymer (Figure 1) was synthesized by the Dow Chemical and studied by Size Exclusion Chromatography, Fourier Transformed Infrared Spectrometry, Small-angle X-ray Scattering (SAXS) and its cloud point was determined by measuring light transmittance. The studies showed low molecular polydispersivety, but different polarities in the macromolecules fractions. Due to the low solubility of Diol in water, a mixture of water/butyl diglycol was used as solvent. An extensive analysis by SAXS was performed for concentrations from 50 wt% to 80 wt% of Diol in solution. Small concentrations showed very low signal to noise ratio, making it impossible to be analysed. The scattering intensity including the form factor of polydisperse non-homogeneous spheres, and the structure factor of interacting hard spheres was fitted to the curves. As the polymer concentration is high, the fitting of form factors of direct and reverse micelles were compared. The results for direct micelles were better up to 80 wt%, whereas at 90 wt% and 95 wt% the curves were better fitted by reverse micelles. It might seem odd that direct micelles are present up to such high concentrations, but it might have been caused by the presence of butyl diglycol, which increases the solubility of Diol in water. The inner and outer radius of the micelles, electron density distribution, and interaction radius of the micelles were obtained. The polydispersivety increases with Diol concentration. Besides, the interaction radius increases with solvent concentration, even when reversed micelles are present. In the last case, accompanied by an increase of inner radius (water content), as there are fewer Diol molecules to involve the water nuclei, which become larger, further apart, and in less number.

Theoretical studies of Membrane Proteins : Properties, Prediction Methods and Genome-wide analysis

Membrane proteins are a large and important class of proteins. They are responsible for several of the key functions in a living cell, e.g. transport of nutrients and ions, cell-cell signaling, and cell-cell adhesion. Despite their importance it has not been possible to study their structure and organization in much detail because of the difficulty to obtain 3D structures. In this thesis theoretical studies of membrane protein sequences and structures have been carried out by analyzing existing experimental data. The data comes from several sources including sequence databases, genome sequencing projects, and 3D structures. Prediction of the membrane spanning regions by hydrophobicity analysis is a key technique used in several of the studies. A novel method for this is also presented and compared to other methods. The primary questions addressed in the thesis are: What properties are common to all membrane proteins? What is the overall architecture of a membrane protein? What properties govern the integration into the membrane? How many membrane proteins are there and how are they distributed in different organisms? Several of the findings have now been backed up by experiments. An analysis of the large family of G-protein coupled receptors pinpoints differences in length and amino acid composition of loops between proteins with and without a signal peptide and also differences between extra- and intracellular loops. Known 3D structures of membrane proteins have been studied in terms of hydrophobicity, distribution of secondary structure and amino acid types, position specific residue variability, and differences between loops and membrane spanning regions. An analysis of several fully and partially sequenced genomes from eukaryotes, prokaryotes, and archaea has been carried out. Several differences in the membrane protein content between organisms were found, the most important being the total number of membrane proteins and the distribution of membrane proteins with a given number of transmembrane segments. Of the properties that were found to be similar in all organisms, the most obvious is the bias in the distribution of positive charges between the extra- and intracellular loops. Finally, an analysis of homologues to membrane proteins with known topology uncovered two related, multi-spanning proteins with opposite predicted orientations. The predicted topologies were verified experimentally, providing a first example of "divergent topology evolution".

Spark Plasma Sintering of Si3N4-based Ceramics : Sintering mechanism-Tailoring microstructure-Evaluationg properties

Spark Plasma Sintering (SPS) is a promising rapid consolidation technique that allows a better understanding and manipulating of sintering kinetics and therefore makes it possible to obtain Si3N4-based ceramics with tailored microstructures, consisting of grains with either equiaxed or elongated morphology. The presence of an extra liquid phase is necessary for forming tough interlocking microstructures in Yb/Y-stabilised α-sialon by HP. The liquid is introduced by a new method, namely by increasing the O/N ratio in the general formula RExSi12-(3x+n)Al3x+nOnN16-n while keeping the cation ratios of RE, Si and Al constant. Monophasic α-sialon ceramics with tailored microstructures, consisting of either fine equiaxed or elongated grains, have been obtained by using SPS, whether or not such an extra liquid phase is involved. The three processes, namely densification, phase transformation and grain growth, which usually occur simultaneously during conventional HP consolidation of Si3N4-based ceramics, have been precisely followed and separately investigated in the SPS process. The enhanced densification is attributed to the non-equilibrium nature of the liquid phase formed during heating. The dominating mechanism during densification is the enhanced grain boundary sliding accompanied by diffusion- and/or reaction-controlled processes. The rapid grain growth is ascribed to a dynamic ripening mechanism based on the formation of a liquid phase that is grossly out of equilibrium, which in turn generates an extra chemical driving force for mass transfer. Monophasic α-sialon ceramics with interlocking microstructures exhibit improved damage tolerance. Y/Yb- stabilised monophasic α-sialon ceramics containing approximately 3 vol% liquid with refined interlocking microstructures have excellent thermal-shock resistance, comparable to the best β-sialon ceramics with 20 vol% additional liquid phase prepared by HP. The obtained sialon ceramics with fine-grained microstructure show formidably improved superplasticity in the presence of an electric field. The compressive strain rate reaches the order of 10-2 s-1 at temperatures above 1500oC, that is, two orders of magnitude higher than that has been realised so far by any other conventional approaches. The high deformation rate recorded in this work opens up possibilities for making ceramic components with complex shapes through super-plastic forming.

Statistical properties of Radio Halos and the re-acceleration model

Galaxy clusters occupy a special position in the cosmic hierarchy as they are the largest bound structures in the Universe. There is now general agreement on a hierarchical picture for the formation of cosmic structures, in which galaxy clusters are supposed to form by accretion of matter and merging between smaller units. During merger events, shocks are driven by the gravity of the dark matter in the diffuse barionic component, which is heated up to the observed temperature. Radio and hard-X ray observations have discovered non-thermal components mixed with the thermal Intra Cluster Medium (ICM) and this is of great importance as it calls for a “revision” of the physics of the ICM. The bulk of present information comes from the radio observations which discovered an increasing number of Mpcsized emissions from the ICM, Radio Halos (at the cluster center) and Radio Relics (at the cluster periphery). These sources are due to synchrotron emission from ultra relativistic electrons diffusing through µG turbulent magnetic fields. Radio Halos are the most spectacular evidence of non-thermal components in the ICM and understanding the origin and evolution of these sources represents one of the most challenging goal of the theory of the ICM. Cluster mergers are the most energetic events in the Universe and a fraction of the energy dissipated during these mergers could be channelled into the amplification of the magnetic fields and into the acceleration of high energy particles via shocks and turbulence driven by these mergers. Present observations of Radio Halos (and possibly of hard X-rays) can be best interpreted in terms of the reacceleration scenario in which MHD turbulence injected during these cluster mergers re-accelerates high energy particles in the ICM. The physics involved in this scenario is very complex and model details are difficult to test, however this model clearly predicts some simple properties of Radio Halos (and resulting IC emission in the hard X-ray band) which are almost independent of the details of the adopted physics. In particular in the re-acceleration scenario MHD turbulence is injected and dissipated during cluster mergers and thus Radio Halos (and also the resulting hard X-ray IC emission) should be transient phenomena (with a typical lifetime <» 1 Gyr) associated with dynamically disturbed clusters. The physics of the re-acceleration scenario should produce an unavoidable cut-off in the spectrum of the re-accelerated electrons, which is due to the balance between turbulent acceleration and radiative losses. The energy at which this cut-off occurs, and thus the maximum frequency at which synchrotron radiation is produced, depends essentially on the efficiency of the acceleration mechanism so that observations at high frequencies are expected to catch only the most efficient phenomena while, in principle, low frequency radio surveys may found these phenomena much common in the Universe. These basic properties should leave an important imprint in the statistical properties of Radio Halos (and of non-thermal phenomena in general) which, however, have not been addressed yet by present modellings. The main focus of this PhD thesis is to calculate, for the first time, the expected statistics of Radio Halos in the context of the re-acceleration scenario. In particular, we shall address the following main questions: • Is it possible to model “self-consistently” the evolution of these sources together with that of the parent clusters? • How the occurrence of Radio Halos is expected to change with cluster mass and to evolve with redshift? How the efficiency to catch Radio Halos in galaxy clusters changes with the observing radio frequency? • How many Radio Halos are expected to form in the Universe? At which redshift is expected the bulk of these sources? • Is it possible to reproduce in the re-acceleration scenario the observed occurrence and number of Radio Halos in the Universe and the observed correlations between thermal and non-thermal properties of galaxy clusters? • Is it possible to constrain the magnetic field intensity and profile in galaxy clusters and the energetic of turbulence in the ICM from the comparison between model expectations and observations? Several astrophysical ingredients are necessary to model the evolution and statistical properties of Radio Halos in the context of re-acceleration model and to address the points given above. For these reason we deserve some space in this PhD thesis to review the important aspects of the physics of the ICM which are of interest to catch our goals. In Chapt. 1 we discuss the physics of galaxy clusters, and in particular, the clusters formation process; in Chapt. 2 we review the main observational properties of non-thermal components in the ICM; and in Chapt. 3 we focus on the physics of magnetic field and of particle acceleration in galaxy clusters. As a relevant application, the theory of Alfv´enic particle acceleration is applied in Chapt. 4 where we report the most important results from calculations we have done in the framework of the re-acceleration scenario. In this Chapter we show that a fraction of the energy of fluid turbulence driven in the ICM by the cluster mergers can be channelled into the injection of Alfv´en waves at small scales and that these waves can efficiently re-accelerate particles and trigger Radio Halos and hard X-ray emission. The main part of this PhD work, the calculation of the statistical properties of Radio Halos and non-thermal phenomena as expected in the context of the re-acceleration model and their comparison with observations, is presented in Chapts.5, 6, 7 and 8. In Chapt.5 we present a first approach to semi-analytical calculations of statistical properties of giant Radio Halos. The main goal of this Chapter is to model cluster formation, the injection of turbulence in the ICM and the resulting particle acceleration process. We adopt the semi–analytic extended Press & Schechter (PS) theory to follow the formation of a large synthetic population of galaxy clusters and assume that during a merger a fraction of the PdV work done by the infalling subclusters in passing through the most massive one is injected in the form of magnetosonic waves. Then the processes of stochastic acceleration of the relativistic electrons by these waves and the properties of the ensuing synchrotron (Radio Halos) and inverse Compton (IC, hard X-ray) emission of merging clusters are computed under the assumption of a constant rms average magnetic field strength in emitting volume. The main finding of these calculations is that giant Radio Halos are naturally expected only in the more massive clusters, and that the expected fraction of clusters with Radio Halos is consistent with the observed one. In Chapt. 6 we extend the previous calculations by including a scaling of the magnetic field strength with cluster mass. The inclusion of this scaling allows us to derive the expected correlations between the synchrotron radio power of Radio Halos and the X-ray properties (T, LX) and mass of the hosting clusters. For the first time, we show that these correlations, calculated in the context of the re-acceleration model, are consistent with the observed ones for typical µG strengths of the average B intensity in massive clusters. The calculations presented in this Chapter allow us to derive the evolution of the probability to form Radio Halos as a function of the cluster mass and redshift. The most relevant finding presented in this Chapter is that the luminosity functions of giant Radio Halos at 1.4 GHz are expected to peak around a radio power » 1024 W/Hz and to flatten (or cut-off) at lower radio powers because of the decrease of the electron re-acceleration efficiency in smaller galaxy clusters. In Chapt. 6 we also derive the expected number counts of Radio Halos and compare them with available observations: we claim that » 100 Radio Halos in the Universe can be observed at 1.4 GHz with deep surveys, while more than 1000 Radio Halos are expected to be discovered in the next future by LOFAR at 150 MHz. This is the first (and so far unique) model expectation for the number counts of Radio Halos at lower frequency and allows to design future radio surveys. Based on the results of Chapt. 6, in Chapt.7 we present a work in progress on a “revision” of the occurrence of Radio Halos. We combine past results from the NVSS radio survey (z » 0.05 − 0.2) with our ongoing GMRT Radio Halos Pointed Observations of 50 X-ray luminous galaxy clusters (at z » 0.2−0.4) and discuss the possibility to test our model expectations with the number counts of Radio Halos at z » 0.05 − 0.4. The most relevant limitation in the calculations presented in Chapt. 5 and 6 is the assumption of an “averaged” size of Radio Halos independently of their radio luminosity and of the mass of the parent clusters. This assumption cannot be released in the context of the PS formalism used to describe the formation process of clusters, while a more detailed analysis of the physics of cluster mergers and of the injection process of turbulence in the ICM would require an approach based on numerical (possible MHD) simulations of a very large volume of the Universe which is however well beyond the aim of this PhD thesis. On the other hand, in Chapt.8 we report our discovery of novel correlations between the size (RH) of Radio Halos and their radio power and between RH and the cluster mass within the Radio Halo region, MH. In particular this last “geometrical” MH − RH correlation allows us to “observationally” overcome the limitation of the “average” size of Radio Halos. Thus in this Chapter, by making use of this “geometrical” correlation and of a simplified form of the re-acceleration model based on the results of Chapt. 5 and 6 we are able to discuss expected correlations between the synchrotron power and the thermal cluster quantities relative to the radio emitting region. This is a new powerful tool of investigation and we show that all the observed correlations (PR − RH, PR − MH, PR − T, PR − LX, . . . ) now become well understood in the context of the re-acceleration model. In addition, we find that observationally the size of Radio Halos scales non-linearly with the virial radius of the parent cluster, and this immediately means that the fraction of the cluster volume which is radio emitting increases with cluster mass and thus that the non-thermal component in clusters is not self-similar.

Multiwavelenght study of cluster mergers and consequences for the radio emission properties of galaxy clusters

In the present thesis a thourough multiwavelength analysis of a number of galaxy clusters known to be experiencing a merger event is presented. The bulk of the thesis consists in the analysis of deep radio observations of six merging clusters, which host extended radio emission on the cluster scale. A composite optical and X–ray analysis is performed in order to obtain a detailed and comprehensive picture of the cluster dynamics and possibly derive hints about the properties of the ongoing merger, such as the involved mass ratio, geometry and time scale. The combination of the high quality radio, optical and X–ray data allows us to investigate the implications of the ongoing merger for the cluster radio properties, focusing on the phenomenon of cluster scale diffuse radio sources, known as radio halos and relics. A total number of six merging clusters was selected for the present study: A3562, A697, A209, A521, RXCJ 1314.4–2515 and RXCJ 2003.5–2323. All of them were known, or suspected, to possess extended radio emission on the cluster scale, in the form of a radio halo and/or a relic. High sensitivity radio observations were carried out for all clusters using the Giant Metrewave Radio Telescope (GMRT) at low frequency (i.e. ≤ 610 MHz), in order to test the presence of a diffuse radio source and/or analyse in detail the properties of the hosted extended radio emission. For three clusters, the GMRT information was combined with higher frequency data from Very Large Array (VLA) observations. A re–analysis of the optical and X–ray data available in the public archives was carried out for all sources. Propriety deep XMM–Newton and Chandra observations were used to investigate the merger dynamics in A3562. Thanks to our multiwavelength analysis, we were able to confirm the existence of a radio halo and/or a relic in all clusters, and to connect their properties and origin to the reconstructed merging scenario for most of the investigated cases. • The existence of a small size and low power radio halo in A3562 was successfully explained in the theoretical framework of the particle re–acceleration model for the origin of radio halos, which invokes the re–acceleration of pre–existing relativistic electrons in the intracluster medium by merger–driven turbulence. • A giant radio halo was found in the massive galaxy cluster A209, which has likely undergone a past major merger and is currently experiencing a new merging process in a direction roughly orthogonal to the old merger axis. A giant radio halo was also detected in A697, whose optical and X–ray properties may be suggestive of a strong merger event along the line of sight. Given the cluster mass and the kind of merger, the existence of a giant radio halo in both clusters is expected in the framework of the re–acceleration scenario. • A radio relic was detected at the outskirts of A521, a highly dynamically disturbed cluster which is accreting a number of small mass concentrations. A possible explanation for its origin requires the presence of a merger–driven shock front at the location of the source. The spectral properties of the relic may support such interpretation and require a Mach number M < ∼ 3 for the shock. • The galaxy cluster RXCJ 1314.4–2515 is exceptional and unique in hosting two peripheral relic sources, extending on the Mpc scale, and a central small size radio halo. The existence of these sources requires the presence of an ongoing energetic merger. Our combined optical and X–ray investigation suggests that a strong merging process between two or more massive subclumps may be ongoing in this cluster. Thanks to forthcoming optical and X–ray observations, we will reconstruct in detail the merger dynamics and derive its energetics, to be related to the energy necessary for the particle re–acceleration in this cluster. • Finally, RXCJ 2003.5–2323 was found to possess a giant radio halo. This source is among the largest, most powerful and most distant (z=0.317) halos imaged so far. Unlike other radio halos, it shows a very peculiar morphology with bright clumps and filaments of emission, whose origin might be related to the relatively high redshift of the hosting cluster. Although very little optical and X–ray information is available about the cluster dynamical stage, the results of our optical analysis suggest the presence of two massive substructures which may be interacting with the cluster. Forthcoming observations in the optical and X–ray bands will allow us to confirm the expected high merging activity in this cluster. Throughout the present thesis a cosmology with H0 = 70 km s−1 Mpc−1, m=0.3 and =0.7 is assumed.

Empirical and fundamental mechanical tests in the evaluation of dough and bread rheological properties

Bread dough and particularly wheat dough, due to its viscoelastic behaviour, is probably the most dynamic and complicated rheological system and its characteristics are very important since they highly affect final products’ textural and sensorial properties. The study of dough rheology has been a very challenging task for many researchers since it can provide numerous information about dough formulation, structure and processing. This explains why dough rheology has been a matter of investigation for several decades. In this research rheological assessment of doughs and breads was performed by using empirical and fundamental methods at both small and large deformation, in order to characterize different types of doughs and final products such as bread. In order to study the structural aspects of food products, image analysis techniques was used for the integration of the information coming from empirical and fundamental rheological measurements. Evaluation of dough properties was carried out by texture profile analysis (TPA), dough stickiness (Chen and Hoseney cell) and uniaxial extensibility determination (Kieffer test) by using a Texture Analyser; small deformation rheological measurements, were performed on a controlled stress–strain rheometer; moreover the structure of different doughs was observed by using the image analysis; while bread characteristics were studied by using texture profile analysis (TPA) and image analysis. The objective of this research was to understand if the different rheological measurements were able to characterize and differentiate the different samples analysed. This in order to investigate the effect of different formulation and processing conditions on dough and final product from a structural point of view. For this aim the following different materials were performed and analysed: - frozen dough realized without yeast; - frozen dough and bread made with frozen dough; - doughs obtained by using different fermentation method; - doughs made by Kamut® flour; - dough and bread realized with the addition of ginger powder; - final products coming from different bakeries. The influence of sub-zero storage time on non-fermented and fermented dough viscoelastic performance and on final product (bread) was evaluated by using small deformation and large deformation methods. In general, the longer the sub-zero storage time the lower the positive viscoelastic attributes. The effect of fermentation time and of different type of fermentation (straight-dough method; sponge-and-dough procedure and poolish method) on rheological properties of doughs were investigated using empirical and fundamental analysis and image analysis was used to integrate this information throughout the evaluation of the dough’s structure. The results of fundamental rheological test showed that the incorporation of sourdough (poolish method) provoked changes that were different from those seen in the others type of fermentation. The affirmative action of some ingredients (extra-virgin olive oil and a liposomic lecithin emulsifier) to improve rheological characteristics of Kamut® dough has been confirmed also when subjected to low temperatures (24 hours and 48 hours at 4°C). Small deformation oscillatory measurements and large deformation mechanical tests performed provided useful information on the rheological properties of samples realized by using different amounts of ginger powder, showing that the sample with the highest amount of ginger powder (6%) had worse rheological characteristics compared to the other samples. Moisture content, specific volume, texture and crumb grain characteristics are the major quality attributes of bread products. The different sample analyzed, “Coppia Ferrarese”, “Pane Comune Romagnolo” and “Filone Terra di San Marino”, showed a decrease of crumb moisture and an increase in hardness over the storage time. Parameters such as cohesiveness and springiness, evaluated by TPA that are indicator of quality of fresh bread, decreased during the storage. By using empirical rheological tests we found several differences among the samples, due to the different ingredients used in formulation and the different process adopted to prepare the sample, but since these products are handmade, the differences could be account as a surplus value. In conclusion small deformation (in fundamental units) and large deformation methods showed a significant role in monitoring the influence of different ingredients used in formulation, different processing and storage conditions on dough viscoelastic performance and on final product. Finally the knowledge of formulation, processing and storage conditions together with the evaluation of structural and rheological characteristics is fundamental for the study of complex matrices like bakery products, where numerous variable can influence their final quality (e.g. raw material, bread-making procedure, time and temperature of the fermentation and baking).

The effect of linseed oil on the properties of lime-based restoration mortars

The traditional lime mortar is composed of hydrated lime, sand and water. Besides these constituents it may also contain additives aiming to modify fresh mortar´s properties and/or to improve hardened mortar´s strength and durability. Already in the first civilizations various additives were used to enhance mortar´s quality, among the organic additives, linseed oil was one of the most common. From literature we know that it was used already in Roman period to reduce water permeability of a mortar, but the mechanism and the technology, e.g. effects of different dosages, are not clearly explained. There are only few works studying the effect of oil experimentally. Knowing the function of oil in historical mortars is important for designing a new compatible repair mortar. Moreover, linseed oil addition could increase the sometimes insufficient durability of lime-based mortars used for reparation and it could be a natural alternative to synthetic additives. In the present study, the effect of linseed oil on the properties of six various lime-based mortars has been studied. Mortars´ compositions have been selected with respect to composition of historical mortars, but also mortars used in a modern restoration practise have been tested. Oil was added in two different concentrations – 1% and 3% by the weight of binder. The addition of 1% of linseed oil has proved to have positive effect on mortars´ properties. It improves mechanical characteristics and limits water absorption into mortar without affecting significantly the total open porosity or decreasing the degree of carbonation. On the other hand, the 3% addition of linseed oil is making mortar to be almost hydrophobic, but it markedly decreases mortars´ strength. However, all types of tested lime-based mortars with the oil addition showed significantly decreased water and salt solution absorption by capillary rise. Addition of oil into mortars is also decreasing the proportion of pores which are easily accessible to water. Furthermore, mortars with linseed oil showed significantly improved resistance to salt crystallization and freeze-thaw cycles. On the base of the obtained results, the addition of 1% of linseed oil can be taken into consideration in the design of mortars meant to repair or replace historic mortars.

Simulative Investigation on the Electronic, Vibrational and Optical Properties of the Ge2Sb2Te5 Chalcogenide

Chalcogenides are chemical compounds with at least one of the following three chemical elements: Sulfur (S), Selenium (Sn), and Tellurium (Te). As opposed to other materials, chalcogenide atomic arrangement can quickly and reversibly inter-change between crystalline, amorphous and liquid phases. Therefore they are also called phase change materials. As a results, chalcogenide thermal, optical, structural, electronic, electrical properties change pronouncedly and significantly with the phase they are in, leading to a host of different applications in different areas. The noticeable optical reflectivity difference between crystalline and amorphous phases has allowed optical storage devices to be made. Their very high thermal conductivity and heat fusion provided remarkable benefits in the frame of thermal energy storage for heating and cooling in residential and commercial buildings. The outstanding resistivity difference between crystalline and amorphous phases led to a significant improvement of solid state storage devices from the power consumption to the re-writability to say nothing of the shrinkability. This work focuses on a better understanding from a simulative stand point of the electronic, vibrational and optical properties for the crystalline phases (hexagonal and faced-centered cubic). The electronic properties are calculated implementing the density functional theory combined with pseudo-potentials, plane waves and the local density approximation. The phonon properties are computed using the density functional perturbation theory. The phonon dispersion and spectrum are calculated using the density functional perturbation theory. As it relates to the optical constants, the real part dielectric function is calculated through the Drude-Lorentz expression. The imaginary part results from the real part through the Kramers-Kronig transformation. The refractive index, the extinctive and absorption coefficients are analytically calculated from the dielectric function. The transmission and reflection coefficients are calculated using the Fresnel equations. All calculated optical constants compare well the experimental ones.

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.