Influência da quantidade de amônio na síntese de nanopartículas de óxido de ferro por microemulsão

Iron oxide nanoparticles were synthesized in microemulsion systems composed by Triton X-100/hexyl alcohol/cyclohexane/aqueous solution. The nanoparticles were synthesized in microemulsions containing different amounts of ammonium, in order to evaluate the influence of this parameter on the size of the nanoparticles and on the phase transformation after heat treatment. Powder materials were obtained after centrifugation, washing and drying, and they were analyzed as synthesized and after heating at 350, 500 and 1000 °C. It was observed that the higher amount of ammonium induced smaller particles and minor phase transformation, possibly due to a preferential nucleation process.

Validação de método para a determinação de 5-hidroximetilfurfural em mel por cromatografia líquida e sua influência na qualidade do produto

In honey 5-hydroxymethyl-2-furaldehyde (HMF) is one of the most typical products of degradation: it is usually absent in fresh honey, but its concentration tends to rise as a result of heating processes or long-term storage. The validation protocol was performed in terms of detection and quantification limits, precision (by repeatability and intermediate precision), linearity and accuracy (by recovery tests). The method has been tested on 15 honey samples of different ages and geographical origin. HMF correlated highly with the age of the samples has been considered a very important parameter to put these honeys on the market or not and/or to estimate their shelf life.

Cat's claw oxindole alkaloid isomerization induced by common extraction methods

Cat's claw oxindole alkaloids are prone to isomerization in aqueous solution. However, studies on their behavior in extraction processes are scarce. This paper addressed the issue by considering five commonly used extraction processes. Unlike dynamic maceration (DM) and ultrasound-assisted extraction, substantial isomerization was induced by static maceration, turbo-extraction and reflux extraction. After heating under reflux in DM, the kinetic order of isomerization was established and equations were fitted successfully using a four-parameter Weibull model (R² > 0.999). Different isomerization rates and equilibrium constants were verified, revealing a possible matrix effect on alkaloid isomerization.

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.

Heating control of an electrical motor

Electrical motors on a ship attackable to different factors which decrease these lifetimes. One of the main external factors on a ship which usually is a reason of the motor failure is a moisture condensation which decreases the motor winding insulation and increase a probability of the short circuit. Therefore, the protection against moisture is necessary for ship electrical motors. The motor should be protected against moisture all time when it does not operate. The necessity of such protection requires a lot of energy consumption. This master’s thesis is focused on the creation of the electrical motor thermal model and on the different methods of the motor protection against moisture analysis with energy consumption point of view.

Network Structures and Modularity among Biofuel Heating System Manufacturers

The aim of this thesis was to study network structures and modularity among biofuel heating system manufacturers in the Finnish bioenergy sector by utilizing the perspectives of numerous Finnish bioenergy specialists. The study is qualitative due to the fact that the research material was gathered with semi-structured theme interviews during May and June 2010. The research methodology used in the thesis combines conceptual and action-oriented approach. Networks, value nets, and modularity were studied from different perspectives. Three network and platform strategies were discovered and a general network structure was formed. Moreover, benefits and disadvantages of networks and modularity among biofuel heating system manufacturers were illustrated. The analysis provides a comprehensive perception of the industry. The results of the research were constructed by implementing existing theories into practice. Also future recommendations for the biofuel heating system manufacturers were given. The results can be considered to be beneficial because the number of previous studies about the subject is relatively small. The reliability of the study is eminent because the number of the interviews was inclusive.

Utilization of Automatic Meter Reading in the Improvement of a District Heating System

A district heating system comprises production facilities, a distribution network, and heat consumers. The utilization of new energy metering and reading system (AMR) is increasing constantly in district heating systems. This heuristic study shows how the AMR system can be exploited in finding optimization opportunities in district heating system. In this study, the district heating system is mainly considered from the viewpoint of operational optimization. The focus is on the core processes, heat production and distribution. Three objectives were set to this study. The first one was to examine general optimization opportunities in district heating systems. Second, to figure out the benefits of AMR for general optimization opportunities. Finally, to define a methodology for process improvement endeavors. This study shows, through a case study, the usefulness of AMR in specifying current deficiencies in a district heating system. Based on a literature review, the methodology for the improvement of business processes is presented. Additionally, some issues related to future competitiveness of district heating are concerned. As a conclusion, some optimization objectives are considered more desirable than others. Study shows that AMR is useful in the specification of optimization targets in the district heating system. Further steps in optimization process were not examined in detail. That would seem to be interesting topic for further studies.

Spectrometrical Monitoring of Laser Sintering Process of Ceramic Material

This thesis is done as a part of project called FuncMama that is a project between Technical Research Centre of Finland (VTT), Oulu University (OY), Lappeenranta University of Technology (LUT) and Finnish industrial partners. Main goal of the project is to manufacture electric and mechanical components from mixed materials using laser sintering. Aim of this study was to create laser sintered pieces from ceramic material and monitor the sintering event by using spectrometer. Spectrometer is a device which is capable to record intensity of different wavelengths in relation with time. In this study the monitoring of laser sintering was captured with the equipment which consists of Ocean Optics spectrometer, optical fiber and optical lens (detector head). Light from the sintering process hit first to the lens system which guides the light in to the optical fibre. Optical fibre transmits the light from the sintering process to the spectrometer where wavelengths intensity level information is detected. The optical lens of the spectrometer was rigidly set and did not move along with the laser beam. Data which was collected with spectrometer from the laser sintering process was converted with Excel spreadsheet program for result’s evaluation. Laser equipment used was IPG Photonics pulse fibre laser. Laser parameters were kept mainly constant during experimental part and only sintering speed was changed. That way it was possible to find differences in the monitoring results without fear of too many parameters mixing together and affecting to the conclusions. Parts which were sintered had one layer and size of 5 x 5 mm. Material was CT2000 – tape manufactured by Heraeus which was later on post processed to powder. Monitoring of different sintering speeds was tested by using CT2000 reference powder. Moreover tests how different materials effect to the process monitoring were done by adding foreign powder Du Pont 951 which had suffered in re-grinding and which was more reactive than CT2000. By adding foreign material it simulates situation where two materials are accidently mixed together and it was studied if that can be seen with the spectrometer. It was concluded in this study that with the spectrometer it is possible to detect changes between different laser sintering speeds. When the sintering speed is lowered the intensity level of light is higher from the process. This is a result of higher temperature at the sintering spot and that can be noticed with the spectrometer. That indicates it could be possible to use spectrometer as a tool for process observation and support the idea of having system that can help setting up the process parameter window. Also important conclusion was how well the adding of foreign material could be seen with the spectrometer. When second material was added a significant intensity level raise could be noticed in that part where foreign material was mixed. That indicates it is possible to see if there are any variations in the material or if there are more materials mixed together. Spectrometric monitoring of laser sintering could be useful tool for process window observation and temperature controlling of the sintering process. For example if the process window for specific material is experimentally determined to get wanted properties and satisfying sintering speed. It is possible if the data is constantly recorded that the results can show faults in the part texture between layers. Changes between the monitoring data and the experimentally determined values can then indicate changes in the material being generated by material faults or by wrong process parameters. The results of this study show that spectrometer could be one possible tool for monitoring. But to get in that point where this all can be made possible much more researching is needed.

Frequency-Domain and Wide-Pulse Time-Domain Measurements of Lanthanide Luminescence and Lanthanide-Based Resonance Energy Transfer

Resonance energy transfer (RET) is a non-radiative transfer of the excitation energy from the initially excited luminescent donor to an acceptor. The requirements for the resonance energy transfer are: i) the spectral overlap between the donor emission spectrum and the acceptor absorption spectrum, ii) the close proximity of the donor and the acceptor, and iii) the suitable relative orientations of the donor emission and the acceptor absorption transition dipoles. As a result of the RET process the donor luminescence intensity and the donor lifetime are decreased. If the acceptor is luminescent, a sensitized acceptor emission appears. The rate of RET depends strongly on the donor–acceptor distance (r) and is inversely proportional to r6. The distance dependence of RET is utilized in binding assays. The proximity requirement and the selective detection of the RET-modified emission signal allow homogeneous separation free assays. The term lanthanide-based RET is used when luminescent lanthanide compounds are used as donors. The long luminescence lifetimes, the large Stokes’ shifts and the intense, sharply-spiked emission spectra of the lanthanide donors offer advantages over the conventional organic donor molecules. Both the organic lanthanide chelates and the inorganic up-converting phosphor (UCP) particles have been used as donor labels in the RET based binding assays. In the present work lanthanide luminescence and lanthanide-based resonance energy transfer phenomena were studied. Luminescence lifetime measurements had an essential role in the research. Modular frequency-domain and time-domain luminometers were assembled and used successfully in the lifetime measurements. The frequency-domain luminometer operated in the low frequency domain ( 100 kHz) and utilized a novel dual-phase lock-in detection of the luminescence. One of the studied phenomena was the recently discovered non-overlapping fluorescence resonance energy transfer (nFRET). The studied properties were the distance and temperature dependences of nFRET. The distance dependence was found to deviate from the Förster theory and a clear temperature dependence was observed whereas conventional RET was completely independent of the temperature. Based on the experimental results two thermally activated mechanisms were proposed for the nFRET process. The work with the UCP particles involved the measurement of the luminescence properties of the UCP particles synthesized in our laboratory. The goal of the UCP particle research is to develop UCP donor labels for binding assays. In the present work the effect of the dopant concentrations and the core–shell structure on the total up-conversion luminescence intensity, the red–green emission ratio, and the luminescence lifetime was studied. Also the non-radiative nature of the energy transfer from the UCP particle donors to organic acceptors was demonstrated for the first time in aqueous environment and with a controlled donor–acceptor distance.

Test Campaign Parameter Editor for a Graphical TTCN-3 Development Environment

This paper presents the design for a graphical parameter editor for Testing and Test Control Notation 3 (TTCN-3) test suites. This work was done in the context of OpenTTCN IDE, a TTCN-3 development environment built on top of the Eclipse platform. The design presented relies on an additional parameter editing tab added to the launch configurations for test campaigns. This parameter editing tab shows the list of editable parameters and allows opening editing components for the different parameters. Each TTCN-3 primitive type will have a specific editing component providing tools to ease modification of values of that type.

Spatial variability of air dry bulb temperature and black globe humidity index in a broiler house during the heating phase

The air dry-bulb temperature (t db),as well as the black globe humidity index (BGHI), exert great influence on the development of broiler chickens during their heating phase. Therefore, the aim of this study was to analyze the structure and the magnitude of the t db and BGHI spatial variability, using geostatistics tools such as semivariogram analysis and also producing kriging maps. The experiment was conducted in the west mesoregion of the states of Minas Gerais in 2010, in a commercial broiler house with heating system consisting of two furnaces that heat the air indirectly, in the firsts 14 days of the birds' life. The data were registered at intervals of five minutes in the period from 8 a.m. to 10 a.m. The variables were evaluated by variograms fitted by residual maximum likelihood (REML) testing the Spherical and Exponential models. Kriging maps were generated based on the best model used to fit the variogram. It was possible to characterize the variability of the t db and BGHI, which allowed observing the spatial dependence by using geostatistics techniques. In addition, the use of geostatistics and distribution maps made possible to identify problems in the heating system in regions inside the broiler house that may harm the development of chicks.

Evaluation of the heating of broilers in shed by means of gas hoods and underfloor heating

This study was conducted to evaluate and compare the behavior of the heating inside poultry shed through gas hood and underfloor heating. The experiment was conducted in poultry shed belonging to the Federal Institute of Education, Science and Technology of Triângulo Mineiro Region, Uberlândia city – state of Minas Gerais (MG), Brazil. The dimensions of the shed are 24 meters long and 9.6 meters wide and with a ceiling height of 3.2 meters. The temperature was measured with an optical thermometer of Minipa brand, MT 350 model. It was used, to the analysis of temperature behavior, the public domain software FEMM 4.2, which uses finite elements techniques, with data collected from two lots. Underfloor heating is made using hot water flowing through a serpentine type system, which is installed below the bed; this hot water is from solar heaters. An energetic and economic assessment of the warming shed for raising chickens was realized. From the results obtained with the simulations, it may observe that the heating through the floor provides a more homogeneous distribution of temperature when compared with the hood heating. The flow of heat is upwards supplying, thus, the greatest need of heating of the bird, which is the pectoral part.

Solar energy use for water pre-heating in boilers of agro-industries

Energy consumption in the world has been growing every year. The industrial sector represents 27.32% of the world energy demand. Heating systems that use solar energy may contribute with a percentage of the total energy required by industries. This work aimed to study the use of vacuum solar collectors for water pre-heating in boilers. We used four collectors installed according to NBR 15,569; water flow through the tubes was 0.058 L/s, and temperature in the inlet and outlet pipes was measured. Results showed that instantaneous radiation, and inlet fluid and room temperatures are variables that influence the process, reaching water maximum temperature in the solar collector outlet of 97.9 °C, and efficiency of approximately 65% for most experiments. For the financial viability evaluation, the payback study was applied, which resulted in 4; 7 and 5 years, for the respective sources: firewood, LPG (liquefied petroleum gas), and electricity. Regarding the calculation of the annual contribution to the reduction of greenhouse gases, it was, respectively, 2.162 and 356 kg of CO2 per m² of collector tubes, in comparison with firewood and LPG.

Differential Evolution approach and parameter estimation of chaotic

Parameter estimation still remains a challenge in many important applications. There is a need to develop methods that utilize achievements in modern computational systems with growing capabilities. Owing to this fact different kinds of Evolutionary Algorithms are becoming an especially perspective field of research. The main aim of this thesis is to explore theoretical aspects of a specific type of Evolutionary Algorithms class, the Differential Evolution (DE) method, and implement this algorithm as codes capable to solve a large range of problems. Matlab, a numerical computing environment provided by MathWorks inc., has been utilized for this purpose. Our implementation empirically demonstrates the benefits of a stochastic optimizers with respect to deterministic optimizers in case of stochastic and chaotic problems. Furthermore, the advanced features of Differential Evolution are discussed as well as taken into account in the Matlab realization. Test "toycase" examples are presented in order to show advantages and disadvantages caused by additional aspects involved in extensions of the basic algorithm. Another aim of this paper is to apply the DE approach to the parameter estimation problem of the system exhibiting chaotic behavior, where the well-known Lorenz system with specific set of parameter values is taken as an example. Finally, the DE approach for estimation of chaotic dynamics is compared to the Ensemble prediction and parameter estimation system (EPPES) approach which was recently proposed as a possible solution for similar problems.