Carbon prices. Dynamic analysis of European and Californian markets

Dissertação para obtenção do Grau de Doutor em Alterações Climáticas e Políticas de Desenvolvimento Sustentável

Application of NMR RDC’s, relaxation and self-diffusion for the study of dynamic processes of small molecules in solution

Spin-lattice Relaxation, self-Diffusion coefficients and Residual Dipolar Couplings (RDC’s) are the basis of well established Nuclear Magnetic Resonance techniques for the physicochemical study of small molecules (typically organic compounds and natural products with MW < 1000 Da), as they proved to be a powerful and complementary source of information about structural dynamic processes in solution. The work developed in this thesis consists in the application of the earlier-mentioned NMR techniques to explore, analyze and systematize patterns of the molecular dynamic behavior of selected small molecules in particular experimental conditions. Two systems were chosen to investigate molecular dynamic behavior by these techniques: the dynamics of ion-pair formation and ion interaction in ionic liquids (IL) and the dynamics of molecular reorientation when molecules are placed in oriented phases (alignment media). The application of NMR spin-lattice relaxation and self-diffusion measurements was applied to study the rotational and translational molecular dynamics of the IL: 1-butyl-3-methylimidazolium tetrafluoroborate [BMIM][BF4]. The study of the cation-anion dynamics in neat and IL-water mixtures was systematically investigated by a combination of multinuclear NMR relaxation techniques with diffusion data (using by H1, C13 and F19 NMR spectroscopy). Spin-lattice relaxation time (T1), self-diffusion coefficients and nuclear Overhauser effect experiments were combined to determine the conditions that favor the formation of long lived [BMIM][BF4] ion-pairs in water. For this purpose and using the self-diffusion coefficients of cation and anion as a probe, different IL-water compositions were screened (from neat IL to infinite dilution) to find the conditions where both cation and anion present equal diffusion coefficients (8% water fraction at 25 ºC). This condition as well as the neat IL and the infinite dilution were then further studied by 13C NMR relaxation in order to determine correlation times (c) for the molecular reorientational motion using a mathematical iterative procedure and experimental data obtained in a temperature range between 273 and 353 K. The behavior of self-diffusion and relaxation data obtained in our experiments point at the combining parameters of molar fraction 8 % and temperature 298 K as the most favorable condition for the formation of long lived ion-pairs. When molecules are subjected to soft anisotropic motion by being placed in some special media, Residual Dipolar Couplings (RDCs), can be measured, because of the partial alignment induced by this media. RDCs are emerging as a powerful routine tool employed in conformational analysis, as it complements and even outperforms the approaches based on the classical NMR NOE or J3 couplings. In this work, three different alignment media have been characterized and evaluated in terms of integrity using 2H and 1H 1D-NMR spectroscopy, namely the stretched and compressed gel PMMA, and the lyotropic liquid crystals CpCl/n-hexanol/brine and cromolyn/water. The influence that different media and degrees of alignment have on the dynamic properties of several molecules was explored. Different sized sugars were used and their self-diffusion was determined as well as conformation features using RDCs. The results obtained indicate that no influence is felt by the small molecules diffusion and conformational features studied within the alignment degree range studied, which was the 3, 5 and 6 % CpCl/n-hexanol/brine for diffusion, and 5 and 7.5 % CpCl/n-hexanol/brine for conformation. It was also possible to determine that the small molecules diffusion verified in the alignment media presented close values to the ones observed in water, reinforcing the idea of no conditioning of molecular properties in such media.

Dynamic stiffness of the piled foundation of a onshore wind turbine

One of today's biggest concerns is the increase of energetic needs, especially in the developed countries. Among various clean energies, wind energy is one of the technologies that assume greater importance on the sustainable development of humanity. Despite wind turbines had been developed and studied over the years, there are phenomena that haven't been yet fully understood. This work studies the soil-structure interaction that occurs on a wind turbine's foundation composed by a group of piles that is under dynamic loads caused by wind. This problem assumes special importance when the foundation is implemented on locations where safety criteria are very demanding, like the case of a foundation mounted on a dike. To the phenomenon of interaction between two piles and the soil between them it's given the name of pile-soil-pile interaction. It is known that such behavior is frequency dependent, and therefore, on this work evaluation of relevant frequencies for the intended analysis is held. During the development of this thesis, two methods were selected in order to assess pile-soil-pile interaction, being one of analytical nature and the other of numerical origin. The analytical solution was recently developed and its called Generalized pile-soil-pile theory, while for the numerical method the commercial nite element software PLAXIS 3D was used. A study of applicability of the numerical method is also done comparing the given solution by the nite element methods with a rigorous solution widely accepted by the majority of the authors.

Study of the electromyographic signal dynamic behavior in Amyotrophic Lateral Sclerosis (ALS)

Amyotrophic Lateral Sclerosis (ALS) is a neurodegenerative disease characterized by motor neurons degeneration, which reduces muscular force, being very difficult to diagnose. Mathematical methods are used in order to analyze the surface electromiographic signal’s dynamic behavior (Fractal Dimension (FD) and Multiscale Entropy (MSE)), evaluate different muscle group’s synchronization (Coherence and Phase Locking Factor (PLF)) and to evaluate the signal’s complexity (Lempel-Ziv (LZ) techniques and Detrended Fluctuation Analysis (DFA)). Surface electromiographic signal acquisitions were performed in upper limb muscles, being the analysis executed for instants of contraction for ipsilateral acquisitions for patients and control groups. Results from LZ, DFA and MSE analysis present capability to distinguish between the patient group and the control group, whereas coherence, PLF and FD algorithms present results very similar for both groups. LZ, DFA and MSE algorithms appear then to be a good measure of corticospinal pathways integrity. A classification algorithm was applied to the results in combination with extracted features from the surface electromiographic signal, with an accuracy percentage higher than 70% for 118 combinations for at least one classifier. The classification results demonstrate capability to distinguish members between patients and control groups. These results can demonstrate a major importance in the disease diagnose, once surface electromyography (sEMG) may be used as an auxiliary diagnose method.

Storage of water molecules into biomimetic heterostructures: the role of roughness

The development of devices based on heterostructured thin films of biomolecules conveys a huge contribution on biomedical field. However, to achieve high efficiency of these devices, the storage of water molecules into these heterostructures, in order to maintain the biological molecules hydrated, is mandatory. Such hydrated environment may be achieved with lipids molecules which have the ability to rearrange spontaneously into vesicles creating a stable barrier between two aqueous compartments. Yet it is necessary to find conditions that lead to the immobilization of whole vesicles on the heterostructures. In this work, the conditions that govern the deposition of open and closed liposomes of 1.2-dipalmitoyl-sn-Glycero-3-[Phospho-rac-(1-glycerol)] (sodium Salt) (DPPG) onto polyelectrolytes cushions prepared by the layer-by-layer (LbL) method were analyzed. Electronic transitions of DPPG molecules as well as absorption coefficients were obtained by vacuum ultraviolet spectroscopy, while the elemental composition of the heterostructures was characterized by x-ray photoelectron spectroscopy (XPS). The presence of water molecules in the films was inferred by XPS and infrared spectroscopy. Quartz crystal microbalance (QCM) data analysis allowed to conclude that, in certain cases, the DPPG adsorbed amount is dependent of the bilayers number already adsorbed. Moreover, the adsorption kinetics curves of both adsorbed amount and surface roughness allowed to determine the kinetics parameters that are related with adsorption processes namely, electrostatic forces, liposomes diffusion and lipids re-organization on surface. Scaling exponents attained from atomic force microscopy images statistical analysis demonstrate that DPPG vesicles adsorption mechanism is ruled by the diffusion Villain model confirming that adsorption is governed by electrostatic forces. The power spectral density treatment enabled a thorough description of the accessible surface of the samples as well as of its inner structural properties. These outcomes proved that surface roughness influences the adsorption of DPPG liposomes onto surfaces covered by a polyelectrolyte layer. Thus, low roughness was shown to induce liposome rupture creating a lipid bilayer while high roughness allows the adsorption of whole liposomes. In addition, the fraction of open liposomes calculated from the normalized maximum adsorbed amounts decreases with the cushion roughness increase, allowing us to conclude that the surface roughness is a crucial variable that governs the adsorption of open or whole liposomes. This conclusion is fundamental for the development of well-designed sensors based on functional biomolecules incorporated in liposomes. Indeed, LbL films composed of polyelectrolytes and liposomes with and without melanin encapsulated were successfully applied to sensors of olive oil.

40 K Liquid Neon Energy Storage Unit

A thermal Energy Storage Unit (ESU) could be used to attenuate inherent temperature fluctuations of a cold finger, either from a cryocooler working or due to sudden income heat bursts. An ESU directly coupled to the cold source acts as a thermal buffer temporarily increasing its cooling capacity and providing a better thermal stability of the cold finger (“Power Booster mode”). The energy storage units presented here use an enthalpy reservoir based on the high latent heat of the liquid-vapour transition of neon in the temperature range 38 - 44 K to store up to 900 J, and that uses a 6 liters expansion volume at RT in order to work as a closed system. Experimental results in the power booster mode will be described: in this case, the liquid neon cell was directly coupled to the cold finger of the working cryocooler, its volume (12 cm3) allowing it to store 450 J at around 40 K. 10 W heat bursts were applied, leading to liquid evaporation, with quite reduced temperature changes. The liquid neon reservoir can also work as a temporary cold source to be used after stopping the cryocooler, allowing for a vibration-free environment. In this case the enthalpy reservoir implemented (24 cm3) was linked to the cryocooler cold finger through a gas gap heat switch for thermal coupling/decoupling of the cold finger. We will show that, by controlling the enthalpy reservoir’s pressure, 900 J can be stored at a constant temperature of 40 K as in a triple-point ESU.

40 K Neon liquid energy storage unit

Cryocoolers have been progressively replacing the use of the stored cryogens in cryogenic chains used for detector cooling, thanks to their higher and higher reliability. However, the mechanical vibrations, the electromagnetic interferences and the temperature fluctuations inherent to their functioning could reduce the sensor’s sensitivity. In order to minimize this problem, compact thermal energy storage units (ESU) are studied, devices able to store thermal energy without significant temperature increase. These devices can be used as a temporary cold source making it possible to turn the cryocooler OFF providing a proper environment for the sensor. A heat switch is responsible for the thermal decoupling of the ESU from the cryocooler’s temperature that increases when turned OFF. In this work, several prototypes working around 40 K were designed, built and characterized. They consist in a low temperature cell that contains the liquid neon connected to an expansion volume at room temperature for gas storage during the liquid evaporation phase. To turn this system insensitive to the gravity direction, the liquid is retained in the low temperature cell by capillary effect in a porous material. Thanks to pressure regulation of the liquid neon bath, 900 J were stored at 40K. The higher latent heat of the liquid and the inexistence of triple point transitions at 40 K turn the pressure control during the evaporation a versatile and compact alternative to an ESU working at the triple point transitions. A quite compact second prototype ESU directly connected to the cryocooler cold finger was tested as a temperature stabilizer. This device was able to stabilize the cryocooler temperature ((≈ 40K ±1 K) despite sudden heat bursts corresponding to twice the cooling power of the cryocooler. This thesis describes the construction of these devices as well as the tests performed. It is also shown that the thermal model developed to predict the thermal behaviour of these devices, implemented as a software,describes quite well the experimental results. Solutions to improve these devices are also proposed.

Transactions in dynamic reactive environments

Most of today’s systems, especially when related to the Web or to multi-agent systems, are not standalone or independent, but are part of a greater ecosystem, where they need to interact with other entities, react to complex changes in the environment, and act both over its own knowledge base and on the external environment itself. Moreover, these systems are clearly not static, but are constantly evolving due to the execution of self updates or external actions. Whenever actions and updates are possible, the need to ensure properties regarding the outcome of performing such actions emerges. Originally purposed in the context of databases, transactions solve this problem by guaranteeing atomicity, consistency, isolation and durability of a special set of actions. However, current transaction solutions fail to guarantee such properties in dynamic environments, since they cannot combine transaction execution with reactive features, or with the execution of actions over domains that the system does not completely control (thus making rolling back a non-viable proposition). In this thesis, we investigate what and how transaction properties can be ensured over these dynamic environments. To achieve this goal, we provide logic-based solutions, based on Transaction Logic, to precisely model and execute transactions in such environments, and where knowledge bases can be defined by arbitrary logic theories.

40 K neon liquid energy storage unit

Cryocoolers have been progressively replacing the use of the stored cryogens in cryogenic chains used for detector cooling, thanks to their higher and higher reliability. However, the mechanical vibrations, the electromagnetic interferences and the temperature fluctuations inherent to their functioning could reduce the sensor’s sensitivity. In order to minimize this problem, compact thermal energy storage units (ESU) are studied, devices able to store thermal energy without significant temperature increase. These devices can be used as a temporary cold source making it possible to turn the cryocooler OFF providing a proper environment for the sensor. A heat switch is responsible for the thermal decoupling of the ESU from the cryocooler’s temperature that increases when turned OFF. In this work, several prototypes working around 40 K were designed, built and characterized. They consist in a low temperature cell that contains the liquid neon connected to an expansion volume at room temperature for gas storage during the liquid evaporation phase. To turn this system insensitive to the gravity direction, the liquid is retained in the low temperature cell by capillary effect in a porous material. Thanks to pressure regulation of the liquid neon bath, 900 J were stored at 40K. The higher latent heat of the liquid and the inexistence of triple point transitions at 40 K turn the pressure control during the evaporation a versatile and compact alternative to an ESU working at the triple point transitions. A quite compact second prototype ESU directly connected to the cryocooler cold finger was tested as a temperature stabilizer. This device was able to stabilize the cryocooler temperature ((≈ 40K ±1 K) despite sudden heat bursts corresponding to twice the cooling power of the cryocooler. This thesis describes the construction of these devices as well as the tests performed. It is also shown that the thermal model developed to predict the thermal behaviour of these devices,implemented as a software, describes quite well the experimental results. Solutions to improve these devices are also proposed.

Tool for spatial and dynamic representation of artistic performances

This proposal aims to explore the use of available technologies for video representation of sets and performers in order to serve as support for composition processes and artistic performer rehearsals, while focusing in representing the performer’s body and its movements, and its relation with objects belonging to the three-dimensional space of their performances. This project’s main goal is to design and develop a system that can spatially represent the performer and its movements, by means of capturing processes and reconstruction using a camera device, as well as enhance the three-dimensional space where the performance occurs by allowing interaction with virtual objects and by adding a video component, either for documentary purposes, or for live performances effects (for example, using video mapping video techniques in captured video or projection during a performance).

Relatório de estágio na Caixa Geral de Depósitos

This report will describe the activities undertaken during my internship at the Personnel Department (DPE-UPE4.1) in Caixa Geral de Depósitos (CGD), Lisbon, between September 22, 2014, and February 28, 2015. I consider that it is important to note from the outset i) that the subject of my training was suggested by my supervisor in the DPE and accepted by me; and ii) that the internship consisted essentially of carrying out research and information gathering into the different social systems that coexist within the bank and the application of each legal system in solving concrete situations of the CGD employees. The research and analysis of information was important not only for my study but for the CGD itself, as it enables the department to have such an important matter, full of specific characteristics, condensed into a single document, i.e. this report. This is a complex reality. The various welfare systems differ according to the contractual agreement linking the employee to the employer at the date when the labour contract is signed, and also the unique/singular characteristics of the CGD. In the early stage I started by trying to understand the financial institution and its organization and role and the department where I worked. So I analyzed the CGD Statutes and the legal measures that crystallized the scheme for its employees and I also researched its domestic and international operations. The first month was devoted to the research and analysis of such legislation to understand the creation of the CGD and its path to date. In the second and third months I studied the legal social systems that are applied to different groups of CGD workers. This period was quite important to identify and understand the differences between those regimes of CGD employees as well as the procedure inherent in each case. I highlighted the non-implementation of “the social protection regime of convergence” to the workers of this institution; the differences regarding the allocation of sickness subsidies paid to workers who belong to Social Security and CGA contributors, as well as the enforcement of internal rules to all the workers when a work-related accident happens. Then I focused on to assessing and examining external legislation and several internal regulations in order to obtain solutions to questions raised and situations involving by the workers, in order to understand how the DPE solves these situations. Over the last three months of internship, after this more theoretical work, I began the analysis of concrete situations involving employees carrying out their duties in Portugal and abroad. Some of these situations had been received by the department before the beginning of my internship and others over this period. When I was “working” in the DPE I analyzed “cases” that had been solved and some others without a final solution because they were still in courts. As for the last ones (new cases) I was able to follow their assessment and sometimes their outcome. Some of them became study cases for me. Over these five months of my internship, several cases were analyzed and discussed by legal experts of DPE in which I could participate. I always worked hard. I know that this action contributed to elucidate me about the treatment of the issues, and allowed me to have a direct contact with some workers and be part of a dynamic work team. For these reasons, my internship report is not merely descriptive of activities. It consists of an analysis of rules (legislation) and a regulatory framework of activities and it is also a description of several specific situations solved or in a solution process. Through this work I intend to make known the particular reality of a modern Portuguese financial institution not only because of its importance in our country but also such a large number of employees work here (in Portugal and abroad). I should add that throughout my internship I was allowed to attend conferences, within the scope of the bank in order to get a broader view of some issues related to the daily life of the DPE and the CGD. So, I participated in I Jornadas Bancárias and the Conferência Internacional do Contrato a Termo, given that the CGD is a bank and the DPE deals with legal and labour relations.

DYNAMOD – A dynamic agent based modelling framework for digital businesses

Digital Businesses have become a major driver for economic growth and have seen an explosion of new startups. At the same time, it also includes mature enterprises that have become global giants in a relatively short period of time. Digital Businesses have unique characteristics that make the running and management of a Digital Business much different from traditional offline businesses. Digital businesses respond to online users who are highly interconnected and networked. This enables a rapid flow of word of mouth, at a pace far greater than ever envisioned when dealing with traditional products and services. The relatively low cost of incremental user addition has led to a variety of innovation in pricing of digital products, including various forms of free and freemium pricing models. This thesis explores the unique characteristics and complexities of Digital Businesses and its implications on the design of Digital Business Models and Revenue Models. The thesis proposes an Agent Based Modeling Framework that can be used to develop Simulation Models that simulate the complex dynamics of Digital Businesses and the user interactions between users of a digital product. Such Simulation models can be used for a variety of purposes such as simple forecasting, analysing the impact of market disturbances, analysing the impact of changes in pricing models and optimising the pricing for maximum revenue generation or a balance between growth in usage and revenue generation. These models can be developed for a mature enterprise with a large historical record of user growth rate as well as for early stage enterprises without much historical data. Through three case studies, the thesis demonstrates the applicability of the Framework and its potential applications.

Dynamic delta hedging of autocallables under a discrete rebalancing context

This work tests different delta hedging strategies for two products issued by Banco de Investimento Global in 2012. The work studies the behaviour of the delta and gamma of autocallables and their impact on the results when delta hedging with different rebalancing periods. Given its discontinuous payoff and path dependency, it is suggested the hedging portfolio is rebalanced on a daily basis to better follow market changes. Moreover, a mixed strategy is analysed where time to maturity is used as a criterion to change the rebalancing frequency.

Nestle's dynamic forecasting process: Anticipating risks and opportunities

Nestlé’s Dynamic Forecasting Process: Anticipating Risks and Opportunities This Work Project discusses the Nestlé’s Dynamic Forecasting Process, implemented within the organization as a way of reengineering its performance management concept and processes, so as to make it more flexible and capable to react to volatile business conditions. When stressing the importance of demand planning to reallocate resources and enhance performance, Nescafé Dolce Gusto comes as way of seeking improvements on this forecasts’ accuracy and it is thus, by providing a more accurate model on its capsules’ sales, as well as recommending adequate implementations that positively contribute to the referred Planning Process, that value is brought to the Project

Historic and potential technology transition paths of grid battery storage: Co-evolution of energy grid, electric mobility and batteries

Scarcity of fuels, changes in environmental policy and in society increased the interest in generating electric energy from renewable energy sources (RES) for a sustainable energy supply in the future. The main problem of RES as solar and wind energy, which represent a main pillar of this transition, is that they cannot supply constant power output. This results inter alia in an increased demand of backup technologies as batteries to assure electricity system safety. The diffusion of energy storage technologies is highly dependent on the energy system and transport transition pathways which might lead to a replacement or reconfiguration of embedded socio-technical practices and regimes (by creating new standards or dominant designs, changing regulations, infrastructure and user patterns). The success of this technology is dependent on hardly predictable future technical advances, actor preferences, development of competing technologies and designs, diverging interests of actors, future cost efficiencies, environmental performance, the evolution of market demand and design and evolution of our society.