Estudo das ligações de hidrogênio para dímeros formados pelas moléculas de H2O, NH3, HF, HCl e HBr através de cálculos baseados em primeiros princípios

Hydrogen bond energies of fifteen dimers were calculated using the large basis set 6-311++G(3df,3pd), at Hartree-Fock (HF) level including Møller-Plesset (MP2) calculations. The procedure for obtaining such energies were based on the dimer's energy rise provoked by increasing in intermolecular distance of the system component units. Deviations from a strictly linear hydrogen bond were investigated and rotational barriers were also computed allowing the calculation of the second order attractive interactions. In order to provide a more objective definition of hydrogen bond, a lower energy limit was proposed in place of the merely empirical parameters employed in the classical definition

Applications and Markets of Linear Motors

A steady increase in practical industrial applications has secured a place for linear motors. They provide high dynamics and high positioning accuracy of the motor, high reliability and durability of all components of the system. Machines with linear motors have very big perspectives in modern industry. This thesis enables to understand what a linear motor is, where they are used and what situation there is on their market nowadays. It can help to understand reasonability of applying linear motors on manufacture and benefits of its application.

Use of experimental design in the optimisation of a solid phase preconcentration system for Cobalt determination by GFAAS

In this work is proposed a solid phase preconcentration system of Co2+ ions and its posterior determination by GFAAS in which fractional factorial design and response surface methodology (RSM) were used for optimization of the variables associated with preconcentration system performance. The method is based on cobalt extraction as a complex Co2+-PAN (1:2) in a mini-column of polyurethane foam (PUF) impregnated with 1-(2-pyridylazo)-naphthol (PAN) followed by elution with HCl solution and its determination by GFAAS. The chemical and flow variables studied were pH, buffer concentration, eluent concentration and preconcentration and elution flow rates. Results obtained from fractional factorial design 2(5-1) showed that only the variables pH, buffer concentration and interaction (pH X buffer concentration) based on analysis of variance (ANOVA) were statistically significant at 95% confidence level. Under optimised conditions, the method provided an enrichment factor of 11.6 fold with limit of detection and quantification of 38 and 130 ng L-1, respectively, and linear range varying from 0.13 to 10 µg L-1. The precision (n = 9) assessed by relative standard deviation (RSD) was respectively 5.18 and 2.87% for 0.3 and 3.0 µg L-1 cobalt concentrations.

Small and Large Scale Dynamics in the Milky Way

This thesis contains dynamical analysis on four different scales: the Solar system, the Sun itself, the Solar neighbourhood, and the central region of the Milky Way galaxy. All of these topics have been handled through methods of potential theory and statistics. The central topic of the thesis is the orbits of stars in the Milky Way. An introduction into the general structure of the Milky Way is presented, with an emphasis on the evolution of the observed value for the scale-length of the Milky Way disc and the observations of two separate bars in the Milky Way. The basics of potential theory are also presented, as well as a developed potential model for the Milky Way. An implementation of the backwards restricted integration method is shown, rounding off the basic principles used in the dynamical studies of this thesis. The thesis looks at the orbit of the Sun, and its impact on the Oort cloud comets (Paper IV), showing that there is a clear link between these two dynamical systems. The statistical atypicalness of the orbit of the Sun is questioned (Paper I), concluding that there is some statistical typicalness to the orbit of the Sun, although it is not very significant. This does depend slightly on whether one includes a bar, or not, as a bar has a clear effect on the dynamical features seen in the Solar neighbourhood (Paper III). This method can be used to find the possible properties of a bar. Finally, we look at the effect of a bar on a statistical system in the Milky Way, seeing that there are not only interesting effects depending on the mass and size of the bar, but also how bars can capture disc stars (Paper II).

Spectrophotometric flow injection system for determination of Zn2+ in ophthalmic formulations using Alizarin red S

A spectrophotometric flow injection method for the determination of Zn(II) in ophthalmic formulations was developed. In this work, Zn(II) ion was complexed with Alizarin red S in borate buffer solution (pH 9.0) and the chromophore produced was monitored at 520 nm. The analytical curve was linear in the Zn(II) concentration range from 6.05 x 10-6 to 1.50 x 10-4 mol L-1 with a detection limit of 3.60 x 10-6 mol L-1. Recoveries ranged from 96.3 to 105 % and a relative standard deviation of 1.2 % (n = 10) for 5.5x10-5 mol L-1 Zn(II) reference solution were obtained. The sampling rate was 60 h-1 and the results obtained of Zn(II) in ophthalmic products using this procedure are in close agreement with those obtained using a comparative spectrophotometric procedure at 95 % confidence level.

A pH optode based on thymol blue: application to determination of CO2 using flow injection analysis system

An optode based on thymol blue (TB), an acid-based indicator, has been constructed and evaluated as a detector in FIA system for CO2 determination. The dye was chemically immobilised on the surface of a bifurcated glass optical fibre bundle, using silanisation in organic media. In FIA system, hydrogen carbonate or carbonate samples are injected in a buffer carrier solution, and then are mixed with phosphoric acid solution to generate CO2, which diffuses through a PTFE membrane, in order to be collected in an acceptor carrier fluid, pumped towards to detection cell, in which the optode was adapted. The proposed system presents two linear response ranges, from 1.0 x 10-3 to 1.0 x 10-2 mol l-1, and from 2.0 x 10-2 to 0.10 mol l-1. The sampling frequency was 11 sample h-1, with good repeatability (R.S.D < 4 %, n = 10). In flow conditions the optode lifetime was 170 h. The system was applied in the analysis of commercial mineral water and the results obtained in the hydrogen carbonate determination did not differ significantly from those obtained by potentiometry, at a confidence level of 95 %.

Centralized Motion Control of a Linear Tooth Belt Drive: Analysis of the Performance and Limitations

A centralized robust position control for an electrical driven tooth belt drive is designed in this doctoral thesis. Both a cascaded control structure and a PID based position controller are discussed. The performance and the limitations of the system are analyzed and design principles for the mechanical structure and the control design are given. These design principles are also suitable for most of the motion control applications, where mechanical resonance frequencies and control loop delays are present. One of the major challenges in the design of a controller for machinery applications is that the values of the parameters in the system model (parameter uncertainty) or the system model it self (non-parametric uncertainty) are seldom known accurately in advance. In this thesis a systematic analysis of the parameter uncertainty of the linear tooth beltdrive model is presented and the effect of the variation of a single parameter on the performance of the total system is shown. The total variation of the model parameters is taken into account in the control design phase using a Quantitative Feedback Theory (QFT). The thesis also introduces a new method to analyze reference feedforward controllers applying the QFT. The performance of the designed controllers is verified by experimentalmeasurements. The measurements confirm the control design principles that are given in this thesis.

IT Financial Management In a Large Industrial Company

IT Service Management plays a key role in many IT organizations today. First IT Service Management principles founded in the early 1980s but the real adaption emerged in the end 2000s. IT Financial Management is one of IT Service Management’s processes. The main purpose of this thesis was study how IT Financial Management approach can be improved in a case company. Budgeting, accounting and charging are IT Financial Management functions. These functions are researched in this thesis. Thesis materials consist of both qualitative and quantitative material. The theoretical part consists mostly of IT Service Management literature while interviews and the case company’s information systems are researched in the empirical part. Thesis also reviews different kind of the systems which supports and automates IT Financial Management functions. The biggest challenge is the cost allocation with the current ERP system in the case company. It is worth to take group based system for allocation in use before there is a holistic system in a market. The case company should also develop its IT service processes forward.

Costs and Benefits of a Shared Digital Long-Term Preservation System

Paper presented at the 40th Annual Conference of LIBER (Ligue des Bibliothèques Européennes de Recherche - Association of European Research Libraries) on July 1st, 2011; with the slides used at the presentation.

Hammashihnajohdeakseleiden liikkeiden synkronointi

Nykyisessä valmistusteollisuudessa erilaisten robottien ja automatisoitujen tuotantovaiheiden rooli on erittäin merkittävä. Tarkasti suunnitellut liikkeet ja toimintavaiheet voidaan nykyisillä järjestelmillä ajoittaa tarkasti toisiinsa nähden, jolloin erilaisten virhetilanteidenkin sattuessa järjestelmä pystyy toimimaan tilanteen edellyttämällä tavalla. Automatisoinnin etuna on myös tuotannon muokkaaminen erilaisten tuotteiden valmistamiseen pienillä muutoksilla, jolloin tuotantokustannukset pysyvät matalina myös pienten valmistuserien tapauksissa. Usean akselin laitteissa eli niin sanotuissa moniakselikäytöissä laitteen toimintatarkkuus riippuu jokaisen liikeakselin tarkkuudesta. Liikkeenohjauksessa on perinteisesti ollut käytössä myötäkytketty paikkakaskadi, jonka virityksessä otetaan huomioon akselilla olevat erilaiset dynaamiset tilat ja käytettävät referenssit. Monissa nykyisissä hajautetuissa järjestelmissä eli moniakselikäytöissä, joissa jokaiselle akselille on oma ohjauslaite, ei yksittäisen akselin paikkavirhettä huomioida muiden akseleiden ohjauksessa. Työssä tutkitaan erilaisia moniakselijärjestelmien ohjausmenetelmiä ja myötäkytketyn paikkakaskadin toimintaa moniakselikäytössä pyritään parantamaan tuomalla paikkasäätimen rinnalle toinen säädin, jonka tulona on akseleiden välinen paikkaero.

Broadband excitation in the system identification of active magnetic bearing rotor systems

One of the targets of the climate and energy package of the European Union is to increase the energy efficiency in order to achieve a 20 percent reduction in primary energy use compared with the projected level by 2020. The energy efficiency can be improved for example by increasing the rotational speed of large electrical drives, because this enables the elimination of gearboxes leading to a compact design with lower losses. The rotational speeds of traditional bearings, such as roller bearings, are limited by mechanical friction. Active magnetic bearings (AMBs), on the other hand, allow very high rotational speeds. Consequently, their use in large medium- and high-speed machines has rapidly increased. An active magnetic bearing rotor system is an inherently unstable, nonlinear multiple-input, multiple-output system. Model-based controller design of AMBs requires an accurate system model. Finite element modeling (FEM) together with the experimental modal analysis provides a very accurate model for the rotor, and a linearized model of the magneticactuators has proven to work well in normal conditions. However, the overall system may suffer from unmodeled dynamics, such as dynamics of foundation or shrink fits. This dynamics can be modeled by system identification. System identification can also be used for on-line diagnostics. In this study, broadband excitation signals are adopted to the identification of an active magnetic bearing rotor system. The broadband excitation enables faster frequency response function measurements when compared with the widely used stepped sine and swept sine excitations. Different broadband excitations are reviewed, and the random phase multisine excitation is chosen for further study. The measurement times using the multisine excitation and the stepped sine excitation are compared. An excitation signal design with an analysis of the harmonics produced by the nonlinear system is presented. The suitability of different frequency response function estimators for an AMB rotor system are also compared. Additionally, analytical modeling of an AMB rotor system, obtaining a parametric model from the nonparametric frequency response functions, and model updating are discussed in brief, as they are key elements in the modeling for a control design. Theoretical methods are tested with a laboratory test rig. The results conclude that an appropriately designed random phase multisine excitation is suitable for the identification of AMB rotor systems.

IFRS 2 Osakeperusteiset maksut – ylimmän johdon osakeperusteisen palkitsemisjärjestelmien käyttöä selittävät tekijät

Työn tarkoituksena on selvittää, mitkä tekijät vaikuttavat IFRS 2 - standardin mukaisen osakeperusteisen palkitsemisen käyttöön ja sen yleisyyteen sekä mitkä tekijät selittävät IFRS 2 -standardin mukaisen osakeperusteisen palkitsemisen osuutta koko henkilöstökuluista tutkimuksessa esiintyvissä OMX-Nordic pörssin listatuissa Suomen ja Ruotsin large cap - yrityksissä. Työn empiirinen tutkimus toteutetaan laadullisella tutkimuksella, jossa lisäksi käytetään hyväksi regressioanalyysin tuloksia vahvistamaan tutkimuksessa muodostettuja ennakko-oletuksia. Tutkimuksesta kävi ilmi, että IFRS 2 -standardin mukaisen osakeperusteisen palkitsemisen käyttöä selittävät toimitusjohtajan ikä, yrityksen koko sekä yrityksen tutkimus- ja kehitystoiminta. Osakeperusteisen palkitsemisen osuutta yrityksen koko henkilöstökuluista puolestaan selittävät yrityksen velkaantuneisuus, palkitsemistapa sekä toimialan riskisyys.

Dispersal and metacommunity dynamics in a soft-sediment benthic system : how well is the seafloor connected?

Connectivity depends on rates of dispersal between communities. For marine soft-sediment communities continued small-scale dispersal as post-larvae and as adults can be equally important in maintaining community composition, as initial recruitment of substrate by pelagic larvae. In this thesis post-larval dispersal strategies of benthic invertebrates, as well as mechanisms by which communities are connected were investigated. Such knowledge on dispersal is scarce, due to the difficulties in actually measuring dispersal directly in nature, and dispersal has not previously been quantified in the Baltic Sea. Different trap-types were used underwater to capture dispersing invertebrates at different sites, while in parallel measuring waves and currents. Local community composition was found to change predictably under varying rates of dispersal and physical connectivity (waves and currents). This response was, however, dependent on dispersal-related traits of taxa. Actively dispersing taxa will be relatively better at maintaining their position, as they are not as dependent on hydrodynamic conditions for dispersal and will be less prone to be passively transported by currents. Taxa also dispersed in relative proportions that were distinctly different from resident community composition and a significant proportion (40 %) of taxa were found to lack a planktonic larval life-stage. Community assembly was re-started in a large-scale manipulative field experiment over one year across several sites, which revealed how patterns of community composition (α-, β- and λ-diversity) change depending on rates of dispersal. Results also demonstrated that in response to small-scale disturbance, initial recruitment was by nearby-dominant species after which other species arrived from successively further away. At later assembly time, the number of coexisting species increased beyond what was expected purely by local niche requirements (species sorting), transferring regional differences in community composition (β-diversity) to the local scale (α-diversity, mass effect). Findings of this thesis complement more theoretical studies in metacommunity ecology by demonstrating that understanding how and when individuals disperse relative to underlying environmental heterogeneity is key to interpreting how patterns of diversity change across different spatial scales. Such information from nature is critical when predicting responses to, for example, different types of disturbances or management actions in conservation.

Secure Bluetooth Audio Transmission System

The growing spread of small but powerful mobile devices (such as PDAs, mobile phone, Internet Tablet, etc.) opens up new scenarios in which users can interact with such devices in many environments in order to access the information at different locations. In this thesis, a ubiquitous computing based system called Secure Bluetooth Audio Transmission System is introduced. This system is situated in a large public place (like airport, festival venues, etc.), where voice messages are conveyed from the system to users' Bluetooth headsets in order to inform users the latest flight schedule and other public information. The reliability of the message is secured by adopting an authorization strategy and ECDSA. In order to assess and evaluate the risks and potential weaknesses of the system, an easy-to-use prototype implementation was written and tested. Other possible uses and further research were also considered.

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.