A primeira lei da termodinâmica dos processos homogêneos

Thermodynamics of homogeneous processes, which corresponds to the very special situation in thermodynamics of continuous media, is used to discuss the first law. An important part of this work is the exposition of some typical mathematical errors, frequently found in the traditional presentation of thermodynamics. The concepts of state and process functions are discussed, as well as reverse and reversible processes, temporality and its implications on thermodynamics, energy reservoirs and symmetry. Our proposal is to present the first law by using a time dependent viewpoint coherent with mechanics and the foundations of that viewpoint.

A Equação-Mestra: atingindo o equilíbrio

In the last years, a great interest in nonequilibrium systems has been witnessed. Although the Master Equations are one of the most common methods used to describe these systems, the literature about these equations is not straightforward due to the mathematical framework used in their derivations. The goals of this work are to present the physical concepts behind the Master Equations development and to discuss their basic proprieties via a matrix approach. It is also shown how the Master Equations can be used to model typical nonequilibrium processes like multi-wells chemical reactions and radiation absorption processes.

Diesel/biodiesel soot oxidation with ceo2 and ceo2-zro2-modified cordierites: a facile way of accounting for their catalytic ability in fuel combustion processes

CeO2 and mixed CeO2-ZrO2 nanopowders were synthesized and efficiently deposited onto cordierite substrates, with the evaluation of their morphologic and structural properties through XRD, SEM, and FTIR. The modified substrates were employed as outer heterogeneous catalysts for reducing the soot originated from the diesel and diesel/biodiesel blends incomplete combustion. Their activity was evaluated in a diesel stationary motor, and a comparative analysis of the soot emission was carried out through diffuse reflectance spectroscopy. The analyses have shown that the catalyst-impregnated cordierite samples are very efficient for soot oxidation, being capable of reducing the soot emission in more than 60%.

COMPREENSÃO MATEMÁTICA DA DIFUSÃO NO CONTEXTO ELETROQUÍMICO

The aim of this study was to explain in detail the mathematical methods used to deal with diffusion equations, mainly for students and researchers interested in electrochemistry and related areas. Emphasis was placed on the deduction and resolution of diffusion equations, as well as addressing cartesian, spherical and cylindrical coordinates. Different aspects of mass transfer processes were discussed including the importance of the resolution of Fick's laws equations to understand and derive parameters of the electroactive species (e.g., diffusion coefficients, formal electrode potentials) from the electrochemical techniques. As an example, the resolution of diffusion equations for a reversible reduction process of soluble oxidized species was presented for the chronopotentiometry technique. This study is envisaged to broaden the understanding of these frequently used methods, in which mathematical deductions are not always completely understood.

Wet oxidation of recalcitrant lignin waters: Experimental and kinetic studies

The dissertation is based on four articles dealing with recalcitrant lignin water purification. Lignin, a complicated substance and recalcitrant to most treatment technologies, inhibits seriously pulp and paper industry waste management. Therefore, lignin is studied, using WO as a process method for its degradation. A special attention is paid to the improvement in biodegradability and the reduction of lignin content, since they have special importance for any following biological treatment. In most cases wet oxidation is not used as a complete ' mineralization method but as a pre treatment in order to eliminate toxic components and to reduce the high level of organics produced. The combination of wet oxidation with a biological treatment can be a good option due to its effectiveness and its relatively low technology cost. The literature part gives an overview of Advanced Oxidation Processes (AOPs). A hot oxidation process, wet oxidation (WO), is investigated in detail and is the AOP process used in the research. The background and main principles of wet oxidation, its industrial applications, the combination of wet oxidation with other water treatment technologies, principal reactions in WO, and key aspects of modelling and reaction kinetics are presented. There is also given a wood composition and lignin characterization (chemical composition, structure and origin), lignin containing waters, lignin degradation and reuse possibilities, and purification practices for lignin containing waters. The aim of the research was to investigate the effect of the operating conditions of WO, such as temperature, partial pressure of oxygen, pH and initial concentration of wastewater, on the efficiency, and to enhance the process and estimate optimal conditions for WO of recalcitrant lignin waters. Two different waters are studied (a lignin water model solution and debarking water from paper industry) to give as appropriate conditions as possible. Due to the great importance of re using and minimizing the residues of industries, further research is carried out using residual ash of an Estonian power plant as a catalyst in wet oxidation of lignin-containing water. Developing a kinetic model that includes in the prediction such parameters as TOC gives the opportunity to estimate the amount of emerging inorganic substances (degradation rate of waste) and not only the decrease of COD and BOD. The degradation target compound, lignin is included into the model through its COD value (CODligning). Such a kinetic model can be valuable in developing WO treatment processes for lignin containing waters, or other wastewaters containing one or more target compounds. In the first article, wet oxidation of "pure" lignin water was investigated as a model case with the aim of degrading lignin and enhancing water biodegradability. The experiments were performed at various temperatures (110 -190°C), partial oxygen pressures (0.5 -1.5 MPa) and pH (5, 9 and 12). The experiments showed that increasing the temperature notably improved the processes efficiency. 75% lignin reduction was detected at the lowest temperature tested and lignin removal improved to 100% at 190°C. The effect of temperature on the COD removal rate was lower, but clearly detectable. 53% of organics were oxidized at 190°C. The effect of pH occurred mostly on lignin removal. Increasing the pH enhanced the lignin removal efficiency from 60% to nearly 100%. A good biodegradability ratio (over 0.5) was generally achieved. The aim of the second article was to develop a mathematical model for "pure" lignin wet oxidation using lumped characteristics of water (COD, BOD, TOC) and lignin concentration. The model agreed well with the experimental data (R2 = 0.93 at pH 5 and 12) and concentration changes during wet oxidation followed adequately the experimental results. The model also showed correctly the trend of biodegradability (BOD/COD) changes. In the third article, the purpose of the research was to estimate optimal conditions for wet oxidation (WO) of debarking water from the paper industry. The WO experiments were' performed at various temperatures, partial oxygen pressures and pH. The experiments showed that lignin degradation and organics removal are affected remarkably by temperature and pH. 78-97% lignin reduction was detected at different WO conditions. Initial pH 12 caused faster removal of tannins/lignin content; but initial pH 5 was more effective for removal of total organics, represented by COD and TOC. Most of the decrease in organic substances concentrations occurred in the first 60 minutes. The aim of the fourth article was to compare the behaviour of two reaction kinetic models, based on experiments of wet oxidation of industrial debarking water under different conditions. The simpler model took into account only the changes in COD, BOD and TOC; the advanced model was similar to the model used in the second article. Comparing the results of the models, the second model was found to be more suitable for describing the kinetics of wet oxidation of debarking water. The significance of the reactions involved was compared on the basis of the model: for instance, lignin degraded first to other chemically oxidizable compounds rather than directly to biodegradable products. Catalytic wet oxidation of lignin containing waters is briefly presented at the end of the dissertation. Two completely different catalysts were used: a commercial Pt catalyst and waste power plant ash. CWO showed good performance using 1 g/L of residual ash gave lignin removal of 86% and COD removal of 39% at 150°C (a lower temperature and pressure than with WO). It was noted that the ash catalyst caused a remarkable removal rate for lignin degradation already during the pre heating for `zero' time, 58% of lignin was degraded. In general, wet oxidation is not recommended for use as a complete mineralization method, but as a pre treatment phase to eliminate toxic or difficultly biodegradable components and to reduce the high level of organics. Biological treatment is an appropriate post treatment method since easily biodegradable organic matter remains after the WO process. The combination of wet oxidation with subsequent biological treatment can be an effective option for the treatment of lignin containing waters.

Potentials of process intensification in the Finnish petrochemical industry

This research was motivated by the need to examine the potential application areas of process intensification technologies in Neste Oil Oyj. According to the company’s interest membrane reactor technology was chosen and applicability of this technology in refining industry was investigated. Moreover, Neste Oil suggested a project which is related to the CO2 capture from FCC unit flue gas stream. The flowrate of the flue gas is 180t/h and consist of approximately 14% by volume CO2. Membrane based absorption process (membrane contactor) was chosen as a potential technique to model CO2 capture from fluid catalytic cracking (FCC) unit effluent. In the design of membrane contactor, a mathematical model was developed to describe CO2 absorption from a gas mixture using monoethanole amine (MEA) aqueous solution. According to the results of literature survey, in the hollow fiber contactor for laminar flow conditions approximately 99 % percent of CO2 can be removed by using a 20 cm in length polyvinylidene fluoride (PDVF) membrane. Furthermore, the design of whole process was performed by using PRO/II simulation software and the CO2 removal efficiency of the whole process obtained as 97 %. The technical and economical comparisons among existing MEA absorption processes were performed to determine the advantages and disadvantages of membrane contactor technology.

Microwave Processes in Ferrite-ferroelectric Layered Structure

This work is devoted to investigation of wave processes in new hybrid ferrite/ferroelectric structures. Spin wave devices based on ferrite films have disadvanteges. And their applications are limited. Investigated structures allow to overcome disadvantages. This investigation helps to create new class of devices. Electromagnetic analysis of hybrid spin-electromagnetic waves in ferrite/ferroelectric structures were done. As a result dispersion relation was found. Numerical solution of this dispersion relation gave us follow results. These structures can be effectively tuned by external electric and magnetic field. Methods to increase tuning range were suggested. It was found that such structures have one basic disadvantage which is connected with presence of thick ferroelectric layer. To solve this problem is to use thin ferroelectric films. But this decreases tuning range. It was confirmed by experiment that this structures can be effectively tuned by electric and magnetic fields. Resonance characteristics of ferrite/ferroelectric resonator were succesfully tuned by magnetic and electric field.

Quality and analysis of administration processes in server operations

IT outsourcing refers to the way companies focus on their core competencies and buy the supporting functions from other companies specialized in that area. Service is the total outcome of numerous of activities by employees and other resources to provide solutions to customers' problems. Outsourcing and service business have their unique characteristics. Service Level Agreements quantify the minimum acceptable service to the user. The service quality has to be objectively quantified so that its achievement or non-achievement of it can be monitored. Usually offshoring refers to the transferring of tasks to low-cost nations. Offshoring presents a lot of challenges that require special attention and they need to be assessed thoroughly. IT Infrastructure management refers to installation and basic usability assistance of operating systems, network and server tools and utilities. ITIL defines the industry best practices for organizing IT processes. This thesis did an analysis of server operations service and the customers’ perception of the quality of daily operations. The agreed workflows and processes should be followed better. Service providers’ processes are thoroughly defined but both the customer and the service provider might disobey them. Service provider should review the workflows regarding customer functions. Customer facing functions require persistent skill development, as they communicate the quality to the customer. Service provider needs to provide better organized communication and knowledge exchange methods between the specialists in different geographical locations.

Finnair Technical Procurement’s Processes and Service Quality

As primary objective, this thesis examines Finnair Technical Procurement’s service quality with its underlying process. As an internal unit, Technical Procurement serves as a link between external suppliers and internal customers. It is argued that external service quality requires a certain quality level within an organization. At the same time, aircraft maintenance business is subject to economic restraints. Therefore, a methodology was developed with a modified House of Quality that assists management in analyzing and evaluating Technical Procurement’s service level and connected process steps. It could be shown that qualitative and quantitative objectives do not exclude each other per se.

Evaluation of the dioxin and furan formation thermodynamics in combustion processes of urban solid wastes

Specific combustion programs (Gaseq, Chemical equilibria in perfect gases, Chris Morley) are used to model dioxin and formation in the incineration processes of urban solid wastes. Thanks to these programs, it is possible to establish correlations with the formation mechanisms postulated in literature on the subject. It was found that minimum oxygen quantities are required to obtain a significant formation of these compounds and that more furans than dioxins are formed. Likewise, dioxin and furan formation is related to the presence of carbon monoxide, and dioxin and furan distribution among its different compounds depends on the chlorine and hydrogen relative composition. This is due to the fact that an increased chlorine availability leads to the formation of compounds bearing a higher chlorine concentration (penta-, hexa-, hepta-, and octachlorides), whereas an increased hydrogen availability leads to the formation of compounds bearing a lower chlorine number (mono, di-, tri-, and tetrachlorides).

Mathematical equation correction to spectral and transport interferences in high-resolution continuum source flame atomic absorption spectrometry: determination of lead in phosphoric acid

In this work, a new mathematical equation correction approach for overcoming spectral and transport interferences was proposed. The proposal was applied to eliminate spectral interference caused by PO molecules at the 217.0005 nm Pb line, and the transport interference caused by variations in phosphoric acid concentrations. Correction may be necessary at 217.0005 nm to account for the contribution of PO, since Atotal217.0005 nm = A Pb217.0005 nm + A PO217.0005 nm. This may be easily done by measuring other PO wavelengths (e.g. 217.0458 nm) and calculating the relative contribution of PO absorbance (A PO) to the total absorbance (Atotal) at 217.0005 nm: A Pb217.0005 nm = Atotal217.0005 nm - A PO217.0005 nm = Atotal217.0005 nm - k (A PO217.0458 nm). The correction factor k is calculated from slopes of calibration curves built up for phosphorous (P) standard solutions measured at 217.0005 and 217.0458 nm, i.e. k = (slope217.0005 nm/slope217.0458 nm). For wavelength integrated absorbance of 3 pixels, sample aspiration rate of 5.0 ml min-1, analytical curves in the 0.1 - 1.0 mg L-1 Pb range with linearity better than 0.9990 were consistently obtained. Calibration curves for P at 217.0005 and 217.0458 nm with linearity better than 0.998 were obtained. Relative standard deviations (RSD) of measurements (n = 12) in the range of 1.4 - 4.3% and 2.0 - 6.0% without and with mathematical equation correction approach were obtained respectively. The limit of detection calculated to analytical line at 217.0005 nm was 10 µg L-1 Pb. Recoveries for Pb spikes were in the 97.5 - 100% and 105 - 230% intervals with and without mathematical equation correction approach, respectively.

Development of chemical looping combustion process

Chemical looping combustion (CLC) provides a promising technology to help cut carbon dioxide emissions. CLC is based on separated oxidation and reduction processes. Oxygen carrier, which is made from metal and supporting material, is in continuous recirculation between the air and fuel reactors. The CLC process does not require separation unit for carbon dioxide. The fuel reactor can produce an almost pure carbon dioxide feed which decrease costs of carbon capture and storage (CCS). The CLC method is one of the most promising ones for energy efficient carbon capture. A large amount of literature was examined for this study and from it the most promising methods and designs were chosen. These methods and designs were combined as reactor system design which was then sized during the making of this thesis. Sizing was done with a mathematical model that was further improved during the study.

Understanding change processes in business networks : a study of convergence in Finnish telecommunications 1985-2005

Aktörer inom telekommunikationsbranschen i Finland har genomgått en intensiv förändring under de senaste 25 åren, från 1980-talets självständiga företag till företag beroende av varandra, och även av aktörer inom närliggande branscher. I dag skapas telekommunikationsmarknaden inte endast av operatörerna, utan också av mediebolag (t.ex. MTV Media) och IT-företag (t.ex. TietoEnator). Gränserna mellan olika industrier håller därmed på att suddas ut - ett fenomen som allmänt benämns som teknologisk konvergens. Konvergens innebär att någonting integreras; det kan handla om t.ex. teknologier (telefoni och Internet), företag (AOL och Time Warner), industrier (telekom, media och IT-branscherna), tjänster (mobilt TV), produkter (PDA) osv. Detta innebär att ytterst få telekomaktörer ensamma kan vidareutveckla marknaden och tekniska lösningar. Samarbete mellan aktörer krävs; mobiltelefontillverkare, innehållsproducenter, operatörer osv. bör intesifiera sitt samarbete för att kunna erbjuda attraktiva tjänster och produkter till kunder och slutanvändare. Avhandlingen fokuserar speciellt på affärsnätverk och samarbetsmönster mellan nätverksaktörer som medel för att få tillgång till resurser som krävs i en konvergenskarakteriserad affärsomgivning. Avhandlingen lyfter fram vad den teknologiska konvergensen har inneburit för telekomaktörer, dvs. att företag tvingats förändra sina strategier och verksamhetsmodeller. För många företag i branschen har anpassningen till konvergenstänkande varit utmanande, och i vissa fall kan man till och med tala om att företagen upplevt en identitetskris. Den utförda forskningen visar att konvergens uppfattas på marknaden som en pågående förändringsprocess, där varje telekomaktör är tvungen att utvärdera sin roll och position i relation till andra aktörer inom branschen. Konvergensprocesser forsätter i framtiden med ökad intensitet. Aktörerna skapar medvetet sin omgivning genom att agera i olika roller, som kan sträcka sig över industrigränser. Avhandlingen påvisar även att externa händelser och industrikontexten påverkar dynamiken i ett affärsnätverk.

Usability of laser–arc hybrid welding processes in industrial applications

Metal industries producing thick sections have shown increasing interest in the laser–arc hybrid welding process because of its clear advantages compared with the individual processes of autogenous laser welding and arc welding. One major benefit of laser–arc hybrid welding is that joints with larger gaps can be welded with acceptable quality compared to autogenous laser welding. The laser-arc hybrid welding process has good potential to extend the field of applications of laser technology, and provide significant improvements in weld quality and process efficiency in manufacturing applications. The objective of this research is to present a parameter set-up for laser–arc hybrid welding processes, introduce a methodical comparison of the chosen parameters, and discuss how this technology may be adopted in industrial applications. The research describes the principles, means and applications of different types of laser–arc hybrid welding processes. Conducted experiment processing variables are presented and compared using an analytical model which can also be used for predictive simulations. The main argument in this thesis is that profound understanding of the advanced technology of laser-arc hybrid welding will help improve the productivity of welding in industrial applications. Based on a review of the current knowledge base, important areas for further research are also identified. This thesis consists of two parts. The first part introduces the research topic and discusses laser–arc hybrid welding by characterizing its mechanism and most important variables. The second part comprises four research papers elaborating on the performance of laser– arc hybrid welding in the joining of metals. The study uses quantitative and qualitative research methods which include in-depth, interpretive analyses of results from a number of research groups. In the interpretive analysis, the emphasis is placed on the relevance and usefulness of the investigative results drawn from other research publications. The results of this study contribute to research on laser–arc hybrid welding by increasing understanding of how old and new perspectives on laser–arc hybrid welding are evidenced in industry. The research methodology applied permits continued exploration of how laser–arc hybrid welding and various process factors influence the overall quality of the weld. Thestudy provides a good foundation for future research, creates improved awareness of the laser–arc hybrid welding process, and assists the metal industry to maximize welding productivity.