Multiresponsive supramolecular systems for information processing at the molecular level

Dissertação para obtenção do Grau de Doutor em Química Sustentável

In-line rheo-optical characterization during small-scale polymer processing and compounding

As increasingly more sophisticated materials and products are being developed and times-to-market need to be minimized, it is important to make available fast response characterization tools using small amounts of sample, capable of conveying data on the relationships between rheological response, process-induced material structure and product characteristics. For this purpose, a single / twin-screw mini-extrusion system of modular construction, with well-controlled outputs in the range 30-300 g/h, was coupled to a in- house developed rheo-optical slit die able to measure shear viscosity and normal-stress differences, as well as performing rheo-optical experiments, namely small angle light scattering (SALS) and polarized optical microscopy (POM). In addition, the mini-extruder is equipped with ports that allow sample collection, and the extrudate can be further processed into products to be tested later. Here, we present the concept and experimental set-up [1, 2]. As a typical application, we report on the characterization of the processing of a polymer blend and of the properties of extruded sheets. The morphological evolution of a PS/PMMA industrial blend along the extruder, the flow-induced structures developed and the corresponding rheological characteristics are presented, together with the mechanical and structural characteristics of produced sheets. The application of this experimental tool to other material systems will also be discussed.

Enrollment time as a requirement for biometric hand recognition systems

Biometric systems are increasingly being used as a means for authentication to provide system security in modern technologies. The performance of a biometric system depends on the accuracy, the processing speed, the template size, and the time necessary for enrollment. While much research has focused on the first three factors, enrollment time has not received as much attention. In this work, we present the findings of our research focused upon studying user’s behavior when enrolling in a biometric system. Specifically, we collected information about the user’s availability for enrollment in respect to the hand recognition systems (e.g., hand geometry, palm geometry or any other requiring positioning the hand on an optical scanner). A sample of 19 participants, chosen randomly apart their age, gender, profession and nationality, were used as test subjects in an experiment to study the patience of users enrolling in a biometric hand recognition system.

Thin films composed of gold nanoparticles dispersed in a dielectric matrix: the influence of the host matrix on the optical and mechanical responses

Gold nanoparticles were dispersed in two different dielectric matrices, TiO2 and Al2O3, using magnetron sputtering and a post-deposition annealing treatment. The main goal of the present work was to study how the two different host dielectric matrices, and the resulting microstructure evolution (including both the nanoparticles and the host matrix itself) promoted by thermal annealing, influenced the physical properties of the films. In particular, the structure and morphology of the nanocomposites were correlated with the optical response of the thin films, namely their localized surface plasmon resonance (LSPR) characteristics. Furthermore, and in order to scan the future application of the two thin film system in different types of sensors (namely biological ones), their functional behaviour (hardness and Young's modulus change) was also evaluated. Despite the similar Au concentrations in both matrices (~ 11 at.%), very different microstructural features were observed, which were found to depend strongly on the annealing temperature. The main structural differences included: (i) the early crystallization of the TiO2 host matrix, while the Al2O3 one remained amorphous up to 800 °C; (ii) different grain size evolution behaviours with the annealing temperature, namely an almost linear increase for the Au:TiO2 system (from 3 to 11 nm), and the approximately constant values observed in the Au:Al2O3 system (4–5 nm). The results from the nanoparticle size distributions were also found to be quite sensitive to the surrounding matrix, suggesting different mechanisms for the nanoparticle growth (particle migration and coalescence dominating in TiO2 and Ostwald ripening in Al2O3). These different clustering behaviours induced different transmittance-LSPR responses and a good mechanical stability, which opens the possibility for future use of these nanocomposite thin film systems in some envisaged applications (e.g. LSPR-biosensors).

Quantum field theory approach to the optical conductivity of strained and deformed graphene

The computation of the optical conductivity of strained and deformed graphene is discussed within the framework of quantum field theory in curved spaces. The analytical solutions of the Dirac equation in an arbitrary static background geometry for one dimensional periodic deformations are computed, together with the corresponding Dirac propagator. Analytical expressions are given for the optical conductivity of strained and deformed graphene associated with both intra and interbrand transitions. The special case of small deformations is discussed and the result compared to the prediction of the tight-binding model.

Dissolution enhancement of active pharmaceutical ingredients by therapeutic deep eutectic systems

A therapeutic deep eutectic system (THEDES) is here defined as a deep eutectic solvent (DES) having an active pharmaceutical ingredient (API) as one of the components. In this work, THEDESs are proposed as enhanced transporters and delivery vehicles for bioactive molecules. THEDESs based on choline chloride (ChCl) or menthol conjugated with three different APIs, namely acetylsalicylic acid (AA), benzoic acid (BA) and phenylacetic acid (PA), were synthesized and characterized for thermal behaviour, structural features, dissolution rate and antibacterial activity. Differential scanning calorimetry and polarized optical microscopy showed that ChCl:PA (1:1), ChCl:AA (1:1), menthol:AA (3:1), menthol:BA (3:1), menthol:PA (2:1) and menthol:PA (3:1) were liquid at room temperature. Dissolution studies in PBS led to increased dissolution rates for the APIs when in the form of THEDES, compared to the API alone. The increase in dissolution rate was particularly noticeable for menthol-based THEDES. Antibacterial activity was assessed using both Gram-positive and Gram-negative model organisms. The results show that all the THEDESs retain the antibacterial activity of the API. Overall, our results highlight the great potential of THEDES as dissolution enhancers in the development of novel and more effective drug delivery systems.

Research development of terahertz imaging systems

The electromagnetic radiation at a terahertz frequencies (from 0.1 THz to 10 THz) is situated in the frequency band comprised between the optical band and the radio band. The interest of the scientific community in this frequency band has grown up due to its large capabilities to develop innovative imaging systems. The terahertz waves are able to generate extremely short pulses that achieve good spatial resolution, good penetration capabilities and allow to identify microscopic structures using spectral analysis. The work carried out during the period of the grant has been based on the developement of system working at the aforementioned frequency band. The main system is based on a total power radiometer working at 0.1 THz to perform security imaging. Moreover, the development of this system has been useful to gain knowledge in the behavior of the component systems at this frequency band. Moreover, a vectorial network analyzer has been used to characterize materials and perform active raster imaging. A materials measurement system has been designed and used to measure material properties as permittivity, losses and water concentration. Finally, the design of a terahertz time-domain spectrometer (THz-TDS) system has been started. This system will allow to perform tomographic measurement with very high penetration resolutions while allowing the spectral characterization of the sample material. The application range of this kind of system is very wide: from the identification of cancerous tissues of a skin to the characterization of the thickness of a painted surface of a car.

Overview of coded light projection techniques for automatic 3D profiling

Obtaining automatic 3D profile of objects is one of the most important issues in computer vision. With this information, a large number of applications become feasible: from visual inspection of industrial parts to 3D reconstruction of the environment for mobile robots. In order to achieve 3D data, range finders can be used. Coded structured light approach is one of the most widely used techniques to retrieve 3D information of an unknown surface. An overview of the existing techniques as well as a new classification of patterns for structured light sensors is presented. This kind of systems belong to the group of active triangulation method, which are based on projecting a light pattern and imaging the illuminated scene from one or more points of view. Since the patterns are coded, correspondences between points of the image(s) and points of the projected pattern can be easily found. Once correspondences are found, a classical triangulation strategy between camera(s) and projector device leads to the reconstruction of the surface. Advantages and constraints of the different patterns are discussed

Mission control system for dam inspection with an AUV

This paper presents a complete control architecture that has been designed to fulfill predefined missions with an autonomous underwater vehicle (AUV). The control architecture has three levels of control: mission level, task level and vehicle level. The novelty of the work resides in the mission level, which is built with a Petri network that defines the sequence of tasks that are executed depending on the unpredictable situations that may occur. The task control system is composed of a set of active behaviours and a coordinator that selects the most appropriate vehicle action at each moment. The paper focuses on the design of the mission controller and its interaction with the task controller. Simulations, inspired on an industrial underwater inspection of a dam grate, show the effectiveness of the control architecture

N-dimensional dynamical systems exploiting instabilities in full

We report experimental and numerical results showing how certain N-dimensional dynamical systems are able to exhibit complex time evolutions based on the nonlinear combination of N-1 oscillation modes. The experiments have been done with a family of thermo-optical systems of effective dynamical dimension varying from 1 to 6. The corresponding mathematical model is an N-dimensional vector field based on a scalar-valued nonlinear function of a single variable that is a linear combination of all the dynamic variables. We show how the complex evolutions appear associated with the occurrence of successive Hopf bifurcations in a saddle-node pair of fixed points up to exhaust their instability capabilities in N dimensions. For this reason the observed phenomenon is denoted as the full instability behavior of the dynamical system. The process through which the attractor responsible for the observed time evolution is formed may be rather complex and difficult to characterize. Nevertheless, the well-organized structure of the time signals suggests some generic mechanism of nonlinear mode mixing that we associate with the cluster of invariant sets emerging from the pair of fixed points and with the influence of the neighboring saddle sets on the flow nearby the attractor. The generation of invariant tori is likely during the full instability development and the global process may be considered as a generalized Landau scenario for the emergence of irregular and complex behavior through the nonlinear superposition of oscillatory motions

Optical-geometrical effects on the photoluminescence spectra of Si nanocrystals embedded in SiO2

We demonstrate that thickness, optical constants, and details of the multilayer stack, together with the detection setting, strongly influence the photoluminescence spectra of Si nanocrystals embedded in SiO2. Due to multiple reflections of the visible light against the opaque silicon substrate, an interference pattern is built inside the oxide layer, which is responsible for the modifications in the measured spectra. This interference effect is complicated by the depth dependence of (i) the intensity of the excitation laser and (ii) the concentration of the emitting nanocrystals. These variations can give rise to apparent features in the recorded spectra, such as peak shifts, satellite shoulders, and even splittings, which can be mistaken as intrinsic material features. Thus, they can give rise to an erroneous attribution of optical bands or estimate of the average particle size, while they are only optical-geometrical artifacts. We have analyzed these effects as a function of material composition (Si excess fraction) and thickness, and also evaluated how the geometry of the detection setup affects the measurements. To correct the experimental photoluminescence spectra and extract the true spectral shape of the emission from Si nanocrystals, we have developed an algorithm based on a modulation function, which depends on both the multilayer sequence and the experimental configuration. This procedure can be easily extended to other heterogeneous systems.

Growth, optical characterization, and laser operation of a stoichiometric crystal KYb(WO4)(2)

We present our recent achievements in the growing and optical characterization of KYb(WO4)2 (hereafter KYbW) crystals and demonstrate laser operation in this stoichiometric material. Single crystals of KYbW with optimal crystalline quality have been grown by the top-seeded-solution growth slow-cooling method. The optical anisotropy of this monoclinic crystal has been characterized, locating the tensor of the optical indicatrix and measuring the dispersion of the principal values of the refractive indices as well as the thermo-optic coefficients. Sellmeier equations have been constructed valid in the visible and near-IR spectral range. Raman scattering has been used to determine the phonon energies of KYbW and a simple physical model is applied for classification of the lattice vibration modes. Spectroscopic studies (absorption and emission measurements at room and low temperature) have been carried out in the spectral region near 1 µm characteristic for the ytterbium transition. Energy positions of the Stark sublevels of the ground and the excited state manifolds have been determined and the vibronic substructure has been identified. The intrinsic lifetime of the upper laser level has been measured taking care to suppress the effect of reabsorption and the intrinsic quantum efficiency has been estimated. Lasing has been demonstrated near 1074 nm with 41% slope efficiency at room temperature using a 0.5 mm thin plate of KYbW. This laser material holds great promise for diode pumped high-power lasers, thin disk and waveguide designs as well as for ultrashort (ps/fs) pulse laser systems.

2009 Iowa’s Rail System Background Prepared by the Office of Systems Planning December 2010

Iowa’s Rail Environment Iowa’s rail transportation system provides both freight and passenger service. Rail serves a variety of trips, including those within Iowa and those to other states as well as to foreign markets. While rail competes with other modes, it also cooperates with those modes to provide intermodal services to Iowans. In 2009 Iowa’s rail transportation system could be described as follows: Freight Iowa’s 130,000-mile freight transportation system includes an extensive railroad network, a well-developed highway system, two bordering navigable waterways, and a pipeline network as well as air cargo facilities. While rail accounts for only 3 percent of the freight network, it carries 43 percent of Iowa’s freight tonnage. A great variety of commodities ranging from fresh fish to textiles to optical products are moved by rail. However, most of the Iowa rail shipments consist of bulk commodities, including grain, grain products, coal, ethanol, and fertilizers. The railroad network performs an important role in moving bulk commodities produced and consumed in the state to local processors, livestock feeders, river terminals and ports for foreign export. The railroad’s ability to haul large volumes, long distances at low costs will continue to be a major factor in moving freight and improving the economy of Iowa. Key 2008 Facts • 3,945 miles of track • 18 railroads • 49.5 million tons shipped • 39.7 million tons received • 2 Amtrak routes • 6 Amtrak stations • 66,286 rail passenger rides Key Rail Trends • slightly fewer miles being operated; • railroads serving Iowa has remained the same; • more rail freight traffic; • more tons hauled per car; • higher average rail rates per ton-mile since 2002; • more car and tons hauled per locomotive; and • more ton miles per gallon of fuel consumed. Iowa’s rail system and service has been evolving over time relative to its size, financial conditions, and competition from other modes.

Effect of External Noise Correlation in Optical Coherence Resonance

Coherence resonance occurring in semiconductor lasers with optical feedback is studied via the Lang-Kobayashi model with external nonwhite noise in the pumping current. The temporal correlation and the amplitude of the noise have a highly relevant influence in the system, leading to an optimal coherent response for suitable values of both the noise amplitude and correlation time. This phenomenon is quantitatively characterized by means of several statistical measures.

Ultraviolet optical and microstructural properties of MgF2 and LaF3 coatings deposited by ion-beam sputtering and boat and electron-beam evaporation

Single layers of MgF2 and LaF3 were deposited upon superpolished fused-silica and CaF2 substrates by ion-beam sputtering (IBS) as well as by boat and electron beam (e-beam) evaporation and were characterized by a variety of complementary analytical techniques. Besides undergoing photometric and ellipsometric inspection, the samples were investigated at 193 and 633 nm by an optical scatter measurement facility. The structural properties were assessed with atomic-force microscopy, x-ray diffraction, TEM techniques that involved conventional thinning methods for the layers. For measurement of mechanical stress in the coatings, special silicon substrates were coated and analyzed. The dispersion behavior of both deposition materials, which was determined on the basis of various independent photometric measurements and data reduction techniques, is in good agreement with that published in the literature and with the bulk properties of the materials. The refractive indices of the MgF2 coatings ranged from 1.415 to 1.440 for the wavelength of the ArF excimer laser (193 nm) and from 1.435 to 1.465 for the wavelength of the F2 excimer laser (157 nm). For single layers of LaF3 the refractive indices extended from 1.67 to 1.70 at 193 nm to ~1.80 at 157 nm. The IBS process achieves the best homogeneity and the lowest surface roughness values (close to 1 nmrms) of the processes compared in the joint experiment. In contrast to MgF2 boat and e-beam evaporated coatings, which exhibit tensile mechanical stress ranging from 300 to 400 MPa, IBS coatings exhibit high compressive stress of as much as 910 MPa. A similar tendency was found for coating stress in LaF3 single layers. Experimental results are discussed with respect to the microstructural and compositional properties as well as to the surface topography of the coatings.