Preparação, caracterização e modificação de adsorventes para remoção de pesticidas de águas

O objectivo principal deste trabalho de mestrado consistiu em avaliar a potencial utilização de materiais adsorventes, nomeadamente, de carvões activados (AC) preparados por activação química com KOH, a partir de PET reciclado, e de materiais com estrutura mesoporosa ordenada, do tipo MCM-41 e SBA-15, na remoção de ácido 4 - cloro - 2 - metilfenoxiacético (MCPA) e de azul de metileno (MB), presentes nas águas. Nesta tese apresentam-se estudos de preparação e caracterização de materiais micro e mesoporosos e também estudos de avaliação da capacidade adsortiva em fase líquida. Prepararam-se três materiais microporosos, nomeadamente, PET-2-700, PET-2-700ox (AC oxidado) e PET-2-700red (AC reduzido), dois materiais constituídos exclusivamente por mesoporos, Si-MCM-41 e Ti-MCM-41-50 e dois materiais contendo maioritariamente mesoporos, mas que também possuem alguma microporosidade, tais corno, Si-SBA-15 e Ti-SBA-15-50. A caracterização textural dos adsorventes foi inferida por adsorção de azoto a 77K e por de difracção de raios X. Recorreu-se a três métodos de análise das isotérmicas, nomeadamente, Dubinin-Radushkevich, Brunauer-Ernrnett-Teller e alfa-s (as). A caracterização química dos AC foi realizada recorrendo-se a técnicas de análise elementar (AE) e espectroscopia de infravermelho com transformadas de Fourier (FTIR) e à determinação do ponto de carga zero. Os três carvões activados possuem valores de área superficial externa idênticos, o PET-2-700 possui o maior volume microporoso e o PET-2-700ox exibe o maior diâmetro de poros. Por outro lado, o PET-2-700ox possui um carácter fortemente ácido, o PET-2-700 exibe carácter ligeiramente ácido e o PET-2-700red apresenta propriedades ligeiramente alcalinas. Com base na AE, todas as amostras possuem percentagens de carbono elevadas, sendo que o PET-2-700red apresenta o valor mais elevado. Os resultados obtidos para a caracterização estrutural dos revelaram a obtenção de materiais mesoporosos de alta qualidade, definida pela elevada regularidade e uniformidade da estrutura porosa. A análise dos parâmetros de caracterização textura! permitiu inferir que os quatro materiais mesoporosos possuem valores de área superficial elevados, e que os materiais SBA-15 apresentam valores de volume poroso total e de tamanho de poros superiores aos manifestados pelos MCM-41. A incorporação de titânio não conduziu a uma perda significativa de qualidade dos materiais substituídos em relação às correspondentes amostras de sílica. Efectuaram-se estudos de adsorção em fase líquida de forma a avaliar a possível aplicação dos vários adsorventes na remoção de MCPA e de MB de efluentes líquidos. concluiu-se que o tempo de equilíbrio de 72 horas seria adequado e que a capacidade de adsorção dos vários AC era superior em meio ácido. Com base nas isotérmicas de adsorção do MCPA e do MB e na aplicação da representação de Langmuir e de Freundlich, foi possível concluir que o PET-2-700 possui a maior capacidade de adsorção do MCPA, 1.42 mmol/g, enquanto que o PET-2-700ox revelou a maior capacidade de adsorção do MB, 1.43 mmol/g. Na realidade, os materiais microporosos estudados apresentaram percentagens de remoção elevadas, tanto do MCPA como do MB. Relativamente aos materiais mesoporosos ordenados preparados neste trabalho, a percentagem de remoção de para os poluentes em estudo foi relativamente baixa, constatando-se que nesta fase dos estudos não constituem uma alternativa viável à utilização dos AC. No entanto, uma funcionalização criteriosa dos mesmos pode eventualmente proporcionar um aumento da capacidade adsortiva. ABSTRACT: The work presented in this master thesis, consisted of evaluating the potential use of different adsorbents materials, like activated carbon (AC) prepared by chemical activation with KOH, from recycled poly (ethylene terephthalate) (PET) and materials with ordered mesoporous structure such as MCM-41 and SBA-15, for removing acid 4-chlorine-2-metilfenoxiacétic and methylene blue from aqueous phase. We had prepared three microporous materials, PET-200-700, PET-2-700ox (AC oxidized) and PET-2-700red (reduced AC), two materials consisting exclusively of mesopores, Si-MCM-41 and Ti-MCM-41-50 and two materials containing mainly mesopores, but also having some microporosity, such as Si-SBA-15 and Ti-SBA-15-50. The textural characterization of the adsorbents was inferred by nitrogen adsorption at 77K and X-ray diffraction. Three methods were used to analyse the isotherms, namely, Dubinin-Radushkevich, Brunauer-Emmett-Teller and alpha-s (as). The chemical characterization of AC was performed using the elementary analysis, Fourier transform infrared spectroscopy (FTIR) and determination of the point of zero charge. Concerning the AC, the three present almost the same externa! surface area, PET-2-700 has a high micropore volume and PET-2-700ox shows the largest pore size diameter. On the other hand, PET-2-700ox had a strong acid character, PET-2-700 exhibits just a slightly acid character and PET-2-700red presents alkaline properties. The AE analysis allows confirming the high carbon content of theses AC, with PET-2-700red exhibiting the highest carbon proportion. The results from the structural characterization of the mesoporous materials, had disclosed the attainment of materials with high quality, defined by the raised regularity and uniformity of the porous structure. The analysis of the textural parameters allowed inferring that the four studied mesoporous materials possess high superficial area. The SBA-15 type materials present higher values of total porous volume and pores size diameter as the MCM-41. Also, the titanium incorporation did not lead to a significant loss of quality of the materials substituted in relation to the corresponding silica samples. The adsorption studies in liquid phase allow evaluating the possibility of using the different adsorbents for the MCPA and the MB removal. The kinetic studies had allowed to state the equilibrium time as 72 hours and a higher adsorption capacity was achieved in an acid medium. The influence of the pH of the medium, on the MCPA adsorption was evaluated. The MCPA and MB isotherms were analysed based on the Langmuir and Freundlich equation, the representations presented an excellent linearity, indicating the applicability of these equations to these systems. Also, it allows concluded that PET-2-700 had a higher adsorption capacity for MCPA, 1.42 mmol/g, and PET-2-700ox had a higher adsorption capacity for MB, 1.43 mmol/g. The AC used presented high removal percentages for MCPA and MB. Concerning the mesoporous materials prepared in this work, the percentage removal for the pollutants in study was relatively low, and evidencing that at the moment these mesoporous materials do not constitute a viable alternative to the AC. However, an astute funcionalisation of the same ones can, eventually provide an increase of the adsorption capacity.

Typed behavioural equivalences in the Pi-Calculus

In this thesis, I study the notion of program equivalences, i.e. proving that two programs can be used interchangeably without altering the overall observable behaviour. This definition is highly dependent on the contexts in which these programs can be used; does the context have exceptions, parallelism, etc... So proofs also need to be adapted according to the expressiveness of those contexts. This thesis presents on the pi-calculus – a concurrent programming language – under various typing constraints. Types allows us to impose different disciplines like forcing a sequential execution, or ensuring linearity, meaning an object can be used once. In each case, the bisimulation, a standard proof technique for the pi-calculus, needs to be adapted accordingly to obtain a suitable equivalence. We then test how using the modified bisimulations can be used to reason about a language with higher-order functions and references, which once translated into the pi-calculus satisfies the typing constraints.

PCM-based in-memory computing: architectures, circuits and applications

Analog In-memory Computing (AIMC) has been proposed in the context of Beyond Von Neumann architectures as a valid strategy to reduce internal data transfers energy consumption and latency, and to improve compute efficiency. The aim of AIMC is to perform computations within the memory unit, typically leveraging the physical features of memory devices. Among resistive Non-volatile Memories (NVMs), Phase-change Memory (PCM) has become a promising technology due to its intrinsic capability to store multilevel data. Hence, PCM technology is currently investigated to enhance the possibilities and the applications of AIMC. This thesis aims at exploring the potential of new PCM-based architectures as in-memory computational accelerators. In a first step, a preliminar experimental characterization of PCM devices has been carried out in an AIMC perspective. PCM cells non-idealities, such as time-drift, noise, and non-linearity have been studied to develop a dedicated multilevel programming algorithm. Measurement-based simulations have been then employed to evaluate the feasibility of PCM-based operations in the fields of Deep Neural Networks (DNNs) and Structural Health Monitoring (SHM). Moreover, a first testchip has been designed and tested to evaluate the hardware implementation of Multiply-and-Accumulate (MAC) operations employing PCM cells. This prototype experimentally demonstrates the possibility to reach a 95% MAC accuracy with a circuit-level compensation of cells time drift and non-linearity. Finally, empirical circuit behavior models have been included in simulations to assess the use of this technology in specific DNN applications, and to enhance the potentiality of this innovative computation approach.

Identification of sunflower genotypes suitable for organic agriculture and development of analytical tools for their traceability

Thanks to the development and combination of molecular markers for the genetic traceability of sunflower varieties and a gas chromatographic method for the determination of the FAs composition of sunflower oil, it was possible to implement an experimental method for the verification of both the traceability and the variety of organic sunflower marketed by Agricola Grains S.p.A. The experimental activity focused on two objectives: the implementation of molecular markers for the routine control of raw material deliveries for oil extraction and the improvement and validation of a gas chromatographic method for the determination of the FAs composition of sunflower oil. With regard to variety verification and traceability, the marker systems evaluated were the following: SSR markers (12) arranged in two multiplex sets and SCAR markers for the verification of cytoplasmic male sterility (Pet1) and fertility. In addition, two objectives were pursued in order to enable a routine application in the industrial field: the development of a suitable protocol for DNA extraction from single seeds and the implementation of a semi-automatic capillary electrophoresis system for the analysis of marker fragments. The development and validation of a new GC/FID analytical method for the determination of fatty acids (FAME) in sunflower achenes to improve the quality and efficiency of the analytical flow in the control of raw and refined materials entering the Agricola Grains S.p.A. production chain. The analytical performances being validated by the newly implemented method are: linearity of response, limit of quantification, specificity, precision, intra-laboratory precision, robustness, BIAS. These parameters are used to compare the newly developed method with the one considered as reference - Commission Regulation No. 2568/91 and Commission Implementing Regulation No. 2015/1833. Using the combination of the analytical methods mentioned above, the documentary traceability of the product can be confirmed experimentally, providing relevant information for subsequent marketing.

Dal sacrificio alla preghiera. La distruzione del Secondo Tempio di Gerusalemme e le trasformazioni cultuali della religione giudaica

La distruzione del Secondo Tempio di Gerusalemme nel 70 e.v. rappresenta un momento cruciale nell’evoluzione storica e teologica della religione giudaica. Prima della catastrofe, l’intero sistema cultuale si fondava sulle ritualità sacrificali, che si concentravano esclusivamente nel santuario gerosolimitano. Con la caduta di quest’ultimo e il venir meno delle sue prassi, il giudaismo dovette ripensare totalmente la propria religiosità, la quale andò gradualmente a imperniarsi sulla preghiera e su atti di devozione non cruenti, in una prospettiva più aperta, mobile e orizzontale. Pertanto, questa ricerca si pone lo scopo di analizzare, in una prospettiva fortemente votata all’antropologia, alla storia e alla sociologia della religione, il senso profondo di tale trasformazione. A questo fine, è stato studiato il culto sacrificale e liturgico giudaico precedente e successivo al 70 e.v., indagando in particolare alcuni aspetti specifici, quali la spazialità sacra, la gestualità rituale e l’uso della musica. In questo modo, è stato possibile delineare alcune logiche fondamentali che costituiscono la struttura dell’intero sistema religioso. Confrontando quelle del periodo del Secondo Tempio con quelle posteriori a esso, è dunque emersa una certa linearità, ma anche una forte discontinuità nella percezione del sacro e dei suoi rituali, fornendo così una nuova interpretazione del significato di una trasformazione di così vasta portata.

Black holes as quantum bound states

We present a new quantum description for the Oppenheimer-Snyder model of gravitational collapse of a ball of dust. Starting from the geodesic equation for dust in spherical symmetry, we introduce a time-independent Schrödinger equation for the radius of the ball. The resulting spectrum is similar to that of the Hydrogen atom and Newtonian gravity. However, the non-linearity of General Relativity implies that the ground state is characterised by a principal quantum number proportional to the square of the ADM mass of the dust. For a ball with ADM mass much larger than the Planck scale, the collapse is therefore expected to end in a macroscopically large core and the singularity predicted by General Relativity is avoided. Mathematical properties of the spectrum are investigated and the ground state is found to have support essentially inside the gravitational radius, which makes it a quantum model for the matter core of Black Holes. In fact, the scaling of the ADM mass with the principal quantum number agrees with the Bekenstein area law and the corpuscular model of Black Holes. Finally, the uncertainty on the size of the ground state is interpreted within the framework of an Uncertainty Principle.

Design for uncertainty of aerospace structures

The aim of this work is to present a general overview of state-of-the-art related to design for uncertainty with a focus on aerospace structures. In particular, a simulation on a FCCZ lattice cell and on the profile shape of a nozzle will be performed. Optimization under uncertainty is characterized by the need to make decisions without complete knowledge of the problem data. When dealing with a complex problem, non-linearity, or optimization, two main issues are raised: the uncertainty of the feasibility of the solution and the uncertainty of the objective value of the function. In the first part, the Design Of Experiments (DOE) methodologies, Uncertainty Quantification (UQ), and then Uncertainty optimization will be deepened. The second part will show an application of the previous theories on through a commercial software. Nowadays multiobjective optimization on high non-linear problem can be a powerful tool to approach new concept solutions or to develop cutting-edge design. In this thesis an effective improvement have been reached on a rocket nozzle. Future work could include the introduction of multi scale modelling, multiphysics approach and every strategy useful to simulate as much possible real operative condition of the studied design.

Lipschitz regularity for weak solutions of parabolic p-Laplacian type equations in certain subriemannian structures

The main aim of the thesis is to prove the local Lipschitz regularity of the weak solutions to a class of parabolic PDEs modeled on the parabolic p-Laplacian. This result is well known in the Euclidean case and recently has been extended in the Heisenberg group, while higher regularity results are not known in subriemannian parabolic setting. In this thesis we will consider vector fields more general than those in the Heisenberg setting, introducing some technical difficulties. To obtain our main result we will use a Moser-like iteration. Due to the non linearity of the equation, we replace the usual parabolic cylinders with new ones, whose dimension also depends on the L^p norm of the solution. In addition, we deeply simplify the iterative procedure, using the standard Sobolev inequality, instead of the parabolic one.

Low Power instrument Transformer: technologies and applications

Instrument transformers serve an important role in the protection and isolation of AC electrical systems for measurements of different electrical parameters like voltage, current, power factor, frequency, and energy. As suggested by name these transformers are used in connection with suitable measuring instruments like an ammeter, wattmeter, voltmeter, and energy meters. We have seen how higher voltages and currents are transformed into lower magnitudes to provide isolation between power networks, relays, and other instruments. Reducing transient, suppressing electrical noises in sensitive devices, standardization of instruments and relays up to a few volts and current. Transformer performance directly affects the accuracy of power system measurements and the reliability of relay protection. We classified transformers in terms of purpose, insulating medium, Voltage ranges, temperature ranges, humidity or environmental effect, indoor and outdoor use, performance, Features, specification, efficiency, cost analysis, application, benefits, and limitations which enabled us to comprehend their correct use and selection criteria based on our desired requirements. We also discussed modern Low power instrument transformer products that are recently launched or offered by renowned companies like Schneider Electric, Siemens, ABB, ZIV, G&W etc. These new products are innovations and problem solvers in the domain of measurement, protection, digital communication, advance, and commercial energy metering. Since there is always some space for improvements to explore new advantages of Low power instrument transformers in the domain of their wide linearity, high-frequency range, miniaturization, structural and technological modification, integration, smart frequency modeling, and output prediction of low-power voltage transformers.