A topologia molecular QTAIM e a descrição mecânico-quântica de ligações de hidrogênio e ligações de di-hidrogênio

Hydrogen bonds formed through the interaction between a high electronic density center (lone electron pairs, π or pseudo-π bonds) and proton donors cause important electronic and vibrational phenomena in many systems. However, it was demonstrated that proton donors interact with hydrides, such as alkali and alkaline earth metals (BeH2, MgH2, LiH and NaH), what yields a new type of interaction so-called dihydrogen bonds. The characterization of these interactions has been performed at light of the Quantum Theory of Atoms in Molecules (QTAIM), by which the electronic densities ρ are quantified and the intermolecular regions are characterized as closed-shell interactions through the analysis of the Laplacian field ∇2ρ.

A study of combustion phenomena in circulating fluidized beds by developing and applying experimental and modelling methods for laboratory-scale reactors

The results shown in this thesis are based on selected publications of the 2000s decade. The work was carried out in several national and EC funded public research projects and in close cooperation with industrial partners. The main objective of the thesis was to study and quantify the most important phenomena of circulating fluidized bed combustors by developing and applying proper experimental and modelling methods using laboratory scale equipments. An understanding of the phenomena plays an essential role in the development of combustion and emission performance, and the availability and controls of CFB boilers. Experimental procedures to study fuel combustion behaviour under CFB conditions are presented in the thesis. Steady state and dynamic measurements under well controlled conditions were carried out to produce the data needed for the development of high efficiency, utility scale CFB technology. The importance of combustion control and furnace dynamics is emphasized when CFB boilers are scaled up with a once through steam cycle. Qualitative information on fuel combustion characteristics was obtained directly by comparing flue gas oxygen responses during the impulse change experiments with fuel feed. A one-dimensional, time dependent model was developed to analyse the measurement data Emission formation was studied combined with fuel combustion behaviour. Correlations were developed for NO, N2O, CO and char loading, as a function of temperature and oxygen concentration in the bed area. An online method to characterize char loading under CFB conditions was developed and validated with the pilot scale CFB tests. Finally, a new method to control air and fuel feeds in CFB combustion was introduced. The method is based on models and an analysis of the fluctuation of the flue gas oxygen concentration. The effect of high oxygen concentrations on fuel combustion behaviour was also studied to evaluate the potential of CFB boilers to apply oxygenfiring technology to CCS. In future studies, it will be necessary to go through the whole scale up chain from laboratory phenomena devices through pilot scale test rigs to large scale, commercial boilers in order to validate the applicability and scalability of the, results. This thesis shows the chain between the laboratory scale phenomena test rig (bench scale) and the CFB process test rig (pilot). CFB technology has been scaled up successfully from an industrial scale to a utility scale during the last decade. The work shown in the thesis, for its part, has supported the development by producing new detailed information on combustion under CFB conditions.

Dialogue in the crisis of representation : realism and antirealism in the context of the conversation between theologians and quantum physicists in Göttingen 1949-1961

The aim of this study is to analyse the content of the interdisciplinary conversations in Göttingen between 1949 and 1961. The task is to compare models for describing reality presented by quantum physicists and theologians. Descriptions of reality indifferent disciplines are conditioned by the development of the concept of reality in philosophy, physics and theology. Our basic problem is stated in the question: How is it possible for the intramental image to match the external object?Cartesian knowledge presupposes clear and distinct ideas in the mind prior to observation resulting in a true correspondence between the observed object and the cogitative observing subject. The Kantian synthesis between rationalism and empiricism emphasises an extended character of representation. The human mind is not a passive receiver of external information, but is actively construing intramental representations of external reality in the epistemological process. Heidegger's aim was to reach a more primordial mode of understanding reality than what is possible in the Cartesian Subject-Object distinction. In Heidegger's philosophy, ontology as being-in-the-world is prior to knowledge concerning being. Ontology can be grasped only in the totality of being (Dasein), not only as an object of reflection and perception. According to Bohr, quantum mechanics introduces an irreducible loss in representation, which classically understood is a deficiency in knowledge. The conflicting aspects (particle and wave pictures) in our comprehension of physical reality, cannot be completely accommodated into an entire and coherent model of reality. What Bohr rejects is not realism, but the classical Einsteinian version of it. By the use of complementary descriptions, Bohr tries to save a fundamentally realistic position. The fundamental question in Barthian theology is the problem of God as an object of theological discourse. Dialectics is Barth¿s way to express knowledge of God avoiding a speculative theology and a human-centred religious self-consciousness. In Barthian theology, the human capacity for knowledge, independently of revelation, is insufficient to comprehend the being of God. Our knowledge of God is real knowledge in revelation and our words are made to correspond with the divine reality in an analogy of faith. The point of the Bultmannian demythologising programme was to claim the real existence of God beyond our faculties. We cannot simply define God as a human ideal of existence or a focus of values. The theological programme of Bultmann emphasised the notion that we can talk meaningfully of God only insofar as we have existential experience of his intervention. Common to all these twentieth century philosophical, physical and theological positions, is a form of anti-Cartesianism. Consequently, in regard to their epistemology, they can be labelled antirealist. This common insight also made it possible to find a common meeting point between the different disciplines. In this study, the different standpoints from all three areas and the conversations in Göttingen are analysed in the frameworkof realism/antirealism. One of the first tasks in the Göttingen conversations was to analyse the nature of the likeness between the complementary structures inquantum physics introduced by Niels Bohr and the dialectical forms in the Barthian doctrine of God. The reaction against epistemological Cartesianism, metaphysics of substance and deterministic description of reality was the common point of departure for theologians and physicists in the Göttingen discussions. In his complementarity, Bohr anticipated the crossing of traditional epistemic boundaries and the generalisation of epistemological strategies by introducing interpretative procedures across various disciplines.

Trustworthy context dependency in ubiquitous systems

The modern society is getting increasingly dependent on software applications. These run on processors, use memory and account for controlling functionalities that are often taken for granted. Typically, applications adjust the functionality in response to a certain context that is provided or derived from the informal environment with various qualities. To rigorously model the dependence of an application on a context, the details of the context are abstracted and the environment is assumed stable and fixed. However, in a context-aware ubiquitous computing environment populated by autonomous agents, a context and its quality parameters may change at any time. This raises the need to derive the current context and its qualities at runtime. It also implies that a context is never certain and may be subjective, issues captured by the context’s quality parameter of experience-based trustworthiness. Given this, the research question of this thesis is: In what logical topology and by what means may context provided by autonomous agents be derived and formally modelled to serve the context-awareness requirements of an application? This research question also stipulates that the context derivation needs to incorporate the quality of the context. In this thesis, we focus on the quality of context parameter of trustworthiness based on experiences having a level of certainty and referral experiences, thus making trustworthiness reputation based. Hence, in this thesis we seek a basis on which to reason and analyse the inherently inaccurate context derived by autonomous agents populating a ubiquitous computing environment in order to formally model context-awareness. More specifically, the contribution of this thesis is threefold: (i) we propose a logical topology of context derivation and a method of calculating its trustworthiness, (ii) we provide a general model for storing experiences and (iii) we formalise the dependence between the logical topology of context derivation and its experience-based trustworthiness. These contributions enable abstraction of a context and its quality parameters to a Boolean decision at runtime that may be formally reasoned with. We employ the Action Systems framework for modelling this. The thesis is a compendium of the author’s scientific papers, which are republished in Part II. Part I introduces the field of research by providing the mending elements for the thesis to be a coherent introduction for addressing the research question. In Part I we also review a significant body of related literature in order to better illustrate our contributions to the research field.

Structural and operational optimisation : applications in energy systems

In this work mathematical programming models for structural and operational optimisation of energy systems are developed and applied to a selection of energy technology problems. The studied cases are taken from industrial processes and from large regional energy distribution systems. The models are based on Mixed Integer Linear Programming (MILP), Mixed Integer Non-Linear Programming (MINLP) and on a hybrid approach of a combination of Non-Linear Programming (NLP) and Genetic Algorithms (GA). The optimisation of the structure and operation of energy systems in urban regions is treated in the work. Firstly, distributed energy systems (DES) with different energy conversion units and annual variations of consumer heating and electricity demands are considered. Secondly, district cooling systems (DCS) with cooling demands for a large number of consumers are studied, with respect to a long term planning perspective regarding to given predictions of the consumer cooling demand development in a region. The work comprises also the development of applications for heat recovery systems (HRS), where paper machine dryer section HRS is taken as an illustrative example. The heat sources in these systems are moist air streams. Models are developed for different types of equipment price functions. The approach is based on partitioning of the overall temperature range of the system into a number of temperature intervals in order to take into account the strong nonlinearities due to condensation in the heat recovery exchangers. The influence of parameter variations on the solutions of heat recovery systems is analysed firstly by varying cost factors and secondly by varying process parameters. Point-optimal solutions by a fixed parameter approach are compared to robust solutions with given parameter variation ranges. In the work enhanced utilisation of excess heat in heat recovery systems with impingement drying, electricity generation with low grade excess heat and the use of absorption heat transformers to elevate a stream temperature above the excess heat temperature are also studied.

Thermal radiation in combustion systems

A numerical procedure for solving the nongray radiative transfer equation (RTE) in two-dimensional cylindrical participating media is presented. Nongray effects are treated by using a narrow-band approach. Radiative emission from CO, CO2, H2O, CH4 and soot is considered. The solution procedure is applied to study radiative heat transfer in a premixed CH4-O2, laminar, flame. Temperature, soot and IR-active species molar fraction distributions are allowed to vary in the axial direction of the flame. From the obtained results it is possible to quantify the radiative loss in the flame, as well as the importance of soot radiation as compared to gaseous radiation. Since the solution procedure is developed for a two-dimensional cylindrical geometry, it can be applied to other combustion systems such as furnaces, internal combustion engines, liquid and solid propellant combustion.

Using passive techniques for vibration damping in mechanical systems

This paper examines two passive techniques for vibration reduction in mechanical systems: the first one is based on dynamic vibration absorbers (DVAs) and the second uses resonant circuit shunted (RCS) piezoceramics. Genetic algorithms are used to determine the optimal design parameters with respect to performance indexes, which are associated with the dynamical behavior of the system over selected frequency bands. The calculation of the frequency response functions (FRFs) of the composite structure (primary system + DVAs) is performed through a substructure coupling technique. A modal technique is used to determine the frequency response function of the structure containing shunted piezoceramics which are bonded to the primary structure. The use of both techniques simultaneously on the same structure is investigated. The methodology developed is illustrated by numerical applications in which the primary structure is represented by simple Euler-Bernoulli beams. However, the design aspects of vibration control devices presented in this paper can be extended to more complex structures.

Accuracy of modelling and identification of malfunctions in rotor systems: experimental results

The accuracy of modelling of rotor systems composed of rotors, oil film bearings and a flexible foundation, is evaluated and discussed in this paper. The model validation of different models has been done by comparing experimental results with numerical results by means. The experimental data have been obtained with a fully instrumented four oil film bearing, two shafts test rig. The fault models are then used in the frame of a model based malfunction identification procedure, based on a least square fitting approach applied in the frequency domain. The capability of distinguishing different malfunctions has been investigated, even if they can create similar effects (such as unbalance, rotor bow, coupling misalignment and others) from shaft vibrations measured in correspondence of the bearings.

Instabilities in electrochemical systems with a rotating disc electrode

Polarization curves experimentally obtained in the electro-dissolution of iron in a 1 M H2SO4 solution using a rotating disc as the working electrode present a current instability region within the range of applied voltage in which the current is controlled by mass transport in the electrolyte. According to the literature (Barcia et. al., 1992) the electro-dissolution process leads to the existence of a viscosity gradient in the interface metal-solution, which leads to a velocity field quantitatively different form the one developed in uniform viscosity conditions and may affect the stability of the hydrodynamic field. The purpose of this work is to investigate whether a steady viscosity profile, depending on the distance to the electrode surface, affects the stability properties of the classic velocity field near a rotating disc. Two classes of perturbations are considered: perturbations monotonically varying along the radial direction, and perturbations periodically modulated along the radial direction. The results show that the hydrodynamic field is always stable with respect to the first class of perturbations and that the neutral stability curves are modified by the presence of a viscosity gradient in the second case, in the sense of reducing the critical Reynolds number beyond which perturbations are amplified. This result supports the hypothesis that the current oscillations observed in the polarization curve may originate from a hydrodynamic instability.

On state and parameter estimation in chaotic systems

State-of-the-art predictions of atmospheric states rely on large-scale numerical models of chaotic systems. This dissertation studies numerical methods for state and parameter estimation in such systems. The motivation comes from weather and climate models and a methodological perspective is adopted. The dissertation comprises three sections: state estimation, parameter estimation and chemical data assimilation with real atmospheric satellite data. In the state estimation part of this dissertation, a new filtering technique based on a combination of ensemble and variational Kalman filtering approaches, is presented, experimented and discussed. This new filter is developed for large-scale Kalman filtering applications. In the parameter estimation part, three different techniques for parameter estimation in chaotic systems are considered. The methods are studied using the parameterized Lorenz 95 system, which is a benchmark model for data assimilation. In addition, a dilemma related to the uniqueness of weather and climate model closure parameters is discussed. In the data-oriented part of this dissertation, data from the Global Ozone Monitoring by Occultation of Stars (GOMOS) satellite instrument are considered and an alternative algorithm to retrieve atmospheric parameters from the measurements is presented. The validation study presents first global comparisons between two unique satellite-borne datasets of vertical profiles of nitrogen trioxide (NO3), retrieved using GOMOS and Stratospheric Aerosol and Gas Experiment III (SAGE III) satellite instruments. The GOMOS NO3 observations are also considered in a chemical state estimation study in order to retrieve stratospheric temperature profiles. The main result of this dissertation is the consideration of likelihood calculations via Kalman filtering outputs. The concept has previously been used together with stochastic differential equations and in time series analysis. In this work, the concept is applied to chaotic dynamical systems and used together with Markov chain Monte Carlo (MCMC) methods for statistical analysis. In particular, this methodology is advocated for use in numerical weather prediction (NWP) and climate model applications. In addition, the concept is shown to be useful in estimating the filter-specific parameters related, e.g., to model error covariance matrix parameters.

SELECTION OF HERBICIDES TARGETING THE USE IN CROP SYSTEMS CULTIVATED WITH SHOWY CROTALARIA

ABSTRACT The increase in the area planted with Crotalaria spectabilishas occurred by several factors, highlighting the potential to reduce the nematodes, nitrogen fixation and the high production of biomass. By becoming a species sown as a crop, it is necessary to control the weeds that coexist with showy crotalaria. This change in the use of this crop creates the possibility of this specie becoming a weed. The aim of this study was to assess the potential use of herbicides applied in preemergence and postemergence of C.spectabilisfor different purposes (control of volunteer and selectivity plants). Three experiments were installed in a greenhouse (two with herbicides applied in preemergence - in soils with distinct textural categories; and one experiment with herbicides applied in postemergence). The results of the experiments with herbicides applied in preemergence showed that: amicarbazone, atrazine, diuron, metribuzin, prometryn, fomesafen and sulfentrazone showed effectiveness for control of C.spectabilis in clayey soil. Besides these, flumioxazin and isoxaflutole also showed potential to be used in the control of showy crotalaria in soils with loam texture. In relation to the postemergence herbicides, atrazine, diuron, prometryn, flumioxazin, fomesafen, lactofen, saflufenacil, amonio-glufosinate and glyphosate can be used aiming the chemical control of C.spectabilis. Herbicides chlorimuron-ethyl, diclosulan, imazethapyr, pyrithiobac-sodium, trifloxysulfuron-sodium, clomazone, pendimethalin, S-metolachlor and trifluralin applied in preemergence, and imazethapyr, pyrithiobac-sodium, flumiclorac, bentazon and clethodim applied in postemergence caused low levels of injury to C.spectabilis plants, making necessary the development of new searches to ensure the selectivity of these products.

Influence of surface functionalization on the behavior of silica nanoparticles in biological systems

Personalized nanomedicine has been shown to provide advantages over traditional clinical imaging, diagnosis, and conventional medical treatment. Using nanoparticles can enhance and clarify the clinical targeting and imaging, and lead them exactly to the place in the body that is the goal of treatment. At the same time, one can reduce the side effects that usually occur in the parts of the body that are not targets for treatment. Nanoparticles are of a size that can penetrate into cells. Their surface functionalization offers a way to increase their sensitivity when detecting target molecules. In addition, it increases the potential for flexibility in particle design, their therapeutic function, and variation possibilities in diagnostics. Mesoporous nanoparticles of amorphous silica have attractive physical and chemical characteristics such as particle morphology, controllable pore size, and high surface area and pore volume. Additionally, the surface functionalization of silica nanoparticles is relatively straightforward, which enables optimization of the interaction between the particles and the biological system. The main goal of this study was to prepare traceable and targetable silica nanoparticles for medical applications with a special focus on particle dispersion stability, biocompatibility, and targeting capabilities. Nanoparticle properties are highly particle-size dependent and a good dispersion stability is a prerequisite for active therapeutic and diagnostic agents. In the study it was shown that traceable streptavidin-conjugated silica nanoparticles which exhibit a good dispersibility could be obtained by the suitable choice of a proper surface functionalization route. Theranostic nanoparticles should exhibit sufficient hydrolytic stability to effectively carry the medicine to the target cells after which they should disintegrate and dissolve. Furthermore, the surface groups should stay at the particle surface until the particle has been internalized by the cell in order to optimize cell specificity. Model particles with fluorescently-labeled regions were tested in vitro using light microscopy and image processing technology, which allowed a detailed study of the disintegration and dissolution process. The study showed that nanoparticles degrade more slowly outside, as compared to inside the cell. The main advantage of theranostic agents is their successful targeting in vitro and in vivo. Non-porous nanoparticles using monoclonal antibodies as guiding ligands were tested in vitro in order to follow their targeting ability and internalization. In addition to the targeting that was found successful, a specific internalization route for the particles could be detected. In the last part of the study, the objective was to clarify the feasibility of traceable mesoporous silica nanoparticles, loaded with a hydrophobic cancer drug, being applied for targeted drug delivery in vitro and in vivo. Particles were provided with a small molecular targeting ligand. In the study a significantly higher therapeutic effect could be achieved with nanoparticles compared to free drug. The nanoparticles were biocompatible and stayed in the tumor for a longer time than a free medicine did, before being eliminated by renal excretion. Overall, the results showed that mesoporous silica nanoparticles are biocompatible, biodegradable drug carriers and that cell specificity can be achieved both in vitro and in vivo.

Decision making and decision support in service systems

This thesis is a literature study that develops a conceptual model of decision making and decision support in service systems. The study is related to the Ä-Logi, Intelligent Service Logic for Welfare Sector Services research project, and the objective of the study is to develop the necessary theoretical framework to enable further research based on the research project results and material. The study first examines the concepts of service and service systems, focusing on understanding the characteristics of service systems and their implications for decision making and decision support to provide the basis for the development of the conceptual model. Based on the identified service system characteristics, an integrated model of service systems is proposed that views service systems through a number of interrelated perspectives that each offer different, but complementary, implications on the nature of decision making and the requirements for decision support in service systems. Based on the model, it is proposed that different types of decision making contexts can be identified in service systems that may be dominated by different types of decision making processes and where different types of decision support may be required, depending on the characteristics of the decision making context and its decision making processes. The proposed conceptual model of decision making and decision support in service systems examines the characteristics of decision making contexts and processes in service systems, and their typical requirements for decision support. First, a characterization of different types of decision making contexts in service systems is proposed based on the Cynefin framework and the identified service system characteristics. Second, the nature of decision making processes in service systems is proposed to be dual, with both rational and naturalistic decision making processes existing in service systems, and having an important and complementary role in decision making in service systems. Finally, a characterization of typical requirements for decision support in service systems is proposed that examines the decision support requirements associated with different types of decision making processes in characteristically different types of decision making contexts. It is proposed that decision support for the decision making processes that are based on rational decision making can be based on organizational decision support models, while decision support for the decision making processes that are based on naturalistic decision making should be based on supporting the decision makers’ situation awareness and facilitating the development of their tacit knowledge of the system and its tasks. Based on the proposed conceptual model a further research process is proposed. The study additionally provides a number of new perspectives on the characteristics of service systems, and the nature of decision making and requirements for decision support in service systems that can potentially provide a basis for further discussion and research, and support the practice alike.

Motor Types Comparison Determining Efficiency in Pumping Systems

Pumping, fan and compressor systems consume most of the motor electricity power in both the industrial and services sectors. A variable speed drive brings relevant improvements in a fluid system leading to energy saving that further on can be translated into Mtons reduction of CO 2 emissions. Standards and regulations are being adopted for fluid handling systems to limit the less efficiency pumps out of the European market on the coming years and a greater potential in energy savings is dictated by the Energy Efficiency Index (EEI) requirements for the whole pumping system and integrated pumps. Electric motors also have an International Efficiency (IE) classification in order to introduce higher efficiency motors into the market. In this thesis, the applicability of mid-size common electric motor types to industrial pumping system took place comparing the motor efficiency characteristics with each other and by analyzing the effect of motor dimensioning on the pumping system and its impact in the energy consumption.

Study of the application of the high performance liquid chromatography-particle beam interface-mass spectrometry technique on some pesiticides and the reduction phenomena in the system

This work includes two major parts. The first part of the work concentrated on the studies of the application of the highperfonnance liquid chromatography-particle beam interface-mass spectrometry system of some pesticides. Factors that have effects on the detection sensitivity were studied. The linearity ranges and detection limits of ten pesticides are also given in this work. The second part of the work concentrated on the studies of the reduction phenomena of nitro compounds in the HPLC-PB-MS system. Direct probe mass spectrometry and gas chromatography-mass spectrometry techniques were also used in the work. Factors that have effects on the reduction of the nitro compounds were studied, and the possible explanation is proposed. The final part of this work included the studies of reduction behavior of some other compounds in the HPLC-PB-MS system, included in them are: quinones, sulfoxides, and sulfones.