Phase diagram and complex patterns in the modeling of the bromate-oxalic acid-Ce-acetone oscillating reaction

Simulations have been carried out on the bromate - oxalic acid - Ce(IV) - acetone oscillating reaction, under flow conditions, using Field and Boyd's model (J. Phys. Chem. 1985, 89, 3707). Many different complex dynamic behaviors were found, including simple periodic oscillations, complex periodic oscillations, quasiperiodicity and chaos. Some of these complex oscillations can be understood as belonging to a Farey sequence. The many different behaviors were systematized in a phase diagram which shows that some regions of complex patterns were nested with one inside the other. The existence of almost all known dynamic behavior for this system allows the suggestion that it can be used as a model for some very complex phenomena that occur in biological systems.

Full instability behavior of N-dimensional dynamical systems with a one-directional nonlinear vector field

We show how certain N-dimensional dynamical systems are able to exploit the full instability capabilities of their fixed points to do Hopf bifurcations and how such a behavior produces complex time evolutions based on the nonlinear combination of the oscillation modes that emerged from these bifurcations. For really different oscillation frequencies, the evolutions describe robust wave form structures, usually periodic, in which selfsimilarity with respect to both the time scale and system dimension is clearly appreciated. For closer frequencies, the evolution signals usually appear irregular but are still based on the repetition of complex wave form structures. The study is developed by considering vector fields with a scalar-valued nonlinear function of a single variable that is a linear combination of the N dynamical variables. In this case, the linear stability analysis can be used to design N-dimensional systems in which the fixed points of a saddle-node pair experience up to N21 Hopf bifurcations with preselected oscillation frequencies. The secondary processes occurring in the phase region where the variety of limit cycles appear may be rather complex and difficult to characterize, but they produce the nonlinear mixing of oscillation modes with relatively generic features

QSAR modeling: um novo pacote computacional open source para gerar e validar modelos QSAR

QSAR modeling is a novel computer program developed to generate and validate QSAR or QSPR (quantitative structure- activity or property relationships) models. With QSAR modeling, users can build partial least squares (PLS) regression models, perform variable selection with the ordered predictors selection (OPS) algorithm, and validate models by using y-randomization and leave-N-out cross validation. An additional new feature is outlier detection carried out by simultaneous comparison of sample leverage with the respective Studentized residuals. The program was developed using Java version 6, and runs on any operating system that supports Java Runtime Environment version 6. The use of the program is illustrated. This program is available for download at lqta.iqm.unicamp.br.

Modeling and developing a customer-oriented configuration process in a mass customization environment

In this thesis the main objective is to examine and model configuration system and related processes. When and where configuration information is created in product development process and how it is utilized in order-delivery process? These two processes are the essential part of the whole configuration system from the information point of view. Empirical part of the work was done as a constructive research inside a company that follows a mass customization approach. Data models and documentation are created for different development stages of the configuration system. A base data model already existed for new structures and relations between these structures. This model was used as the basis for the later data modeling work. Data models include different data structures, their key objects and attributes, and relations between. Representation of configuration rules for the to-be configuration system was defined as one of the key focus point. Further, it is examined how the customer needs and requirements information can be integrated into the product development process. Requirements hierarchy and classification system is presented. It is shown how individual requirement specifications can be connected for physical design structure via features by developing the existing base data model further.

Molecular modeling of asymmetric induction in heterogeneously catalyzed hydrogenation of the C=O bond

Modifiering av metallytor med starkt adsorberade kirala organiska molekyler är eventuellt den mest relevanta teknik man vet i dag för att skapa kirala ytor. Den kan utnyttjas i katalytisk produktion av enantiomeriskt rena kirala föreningar som behövs t.ex. som läkemedel och aromkemikalier. Trots många fördelar av asymmetrisk heterogen katalys jämfört med andra sätt för att få kirala föreningar, har den ändå inte blivit ett allmänt verktyg för storskaliga tillämpningar. Detta beror t.ex. på brist på djupare kunskaper i katalytiska reaktionsmekanismer och ursprunget för asymmetrisk induktion. I denna studie användes molekylmodelleringstekniker för att studera asymmetriska, heterogena katalytiska system, speciellt hydrering av prokirala karbonylföreningar till motsvarande kirala alkoholer på cinchona-alkaloidmodifierade Pt-katalysatorer. 1-Fenyl-1,2-propandion (PPD) och några andra föreningar, som innehåller en prokiral C=O-grupp, användes som reaktanter. Konformationer av reaktanter och cinchona-alkaloider (som kallas modifierare) samt vätebundna 1:1-komplex mellan dem studerades i gas- och lösningsfas med metoder som baserar sig på vågfunktionsteori och täthetsfunktionalteori (DFT). För beräkningen av protonaffiniteter användes också högst noggranna kombinationsmetoder såsom G2(MP2). Den relativa populationen av modifierarnas konformationer varierade som funktion av modifieraren, dess protonering och lösningsmedlet. Flera reaktant–modifierareinteraktionsgeometrier beaktades. Slutsatserna på riktning av stereoselektivitet baserade sig på den relativa termodynamiska stabiliteten av de diastereomeriska reaktant–modifierare-komplexen samt energierna hos π- och π*-orbitalerna i den reaktiva karbonylgruppen. Adsorption och reaktioner på Pt(111)-ytan betraktades med DFT. Regioselektivitet i hydreringen av PPD och 2,3-hexandion kunde förklaras med molekyl–yta-interaktioner. Storleken och formen av klustret använt för att beskriva Pt-ytan inverkade inte bara på adsorptionsenergierna utan också på de relativa stabiliteterna av olika adsorptionsstrukturer av en molekyl. Populationerna av modifierarnas konformationer i gas- och lösningsfas korrelerade inte med populationerna på Pt-ytan eller med enantioselektiviteten i hydreringen av PPD på Pt–cinchona-katalysatorer. Vissa modifierares konformationer och reaktant–modifierare-interaktionsgeometrier var stabila bara på metallytan. Teoretiskt beräknade potentialenergiprofiler för hydrering av kirala α-hydroxiketoner på Pt implicerade preferens för parvis additionsmekanism för väte och selektiviteter i harmoni med experimenten. De uppnådda resultaten ökar uppfattningen om kirala heterogena katalytiska system och kunde därför utnyttjas i utvecklingen av nya, mera aktiva och selektiva kirala katalysatorer.

Metallien kompleksinmuodostus liuosfaasissa

Liuoksessa metallit muodostavat erilaisia koordinatioyhdisteitä epäorgaanisten ja orgaanisten anionien ja neutraalien molekyylien kanssa. Erityisesti siirtymämetalleilla on voimakas taipumus kompleksiyhdisteiden muodostamiseen elektroneja sisältävien 3-, 4-, ja 5d orbitaaliensa johdosta. Samassa liuoksessa voi samanaikaisesti esiintyä useita erilaisia, mutta samoista lähtöaineista muodostuneita, kompleksiyhdisteitä. Kompleksinmuodostusreaktiot ovat tasapainoreaktioita. Usein tasapainovakiot on esitetty termodynaamisina tasapainovakioina eli ne ovat päteviä standarditilassa. Standarditilan tasapainovakioista voidaan johtaa missä tahansa liuoksessa pätevät vakiot erilaisten Debye-Hückel-teoriasta johdettujen laskentamenetelmien avulla. Metalli-ligandiparin jakautuminen erilaisiksi kompleksiyhdisteiksi voidaan mallintaa kun tunnetaan muodostumisreaktioiden tasapainovakiot. Muodostumisreaktioiden tasapainovakioiden yhtälöistä voidaan johtaa epälineaarinen yhtälöryhmä, joka voidaan ratkaista jollakin numeerisella ratkaisimella. Esimerkiksi Matlab-ohjelmiston sisältämä fsolve-ratkaisin soveltuu tällaiseen tehtävään. Osana tätä työtä on kirjoitettu Matlab-sovellus, jolla voidaan mallintaa kationi-ligandiparin jakautumista koordinaatioyhdisteiksi tunnettujen tasapainovakioiden perusteella.

Charge transport in disordered materials : simulations, theory, and numerical modeling of hopping transport and electron-hole recombination

Min avhandling behandlar hur oordnade material leder elektrisk ström. Bland materialen som studeras finns ledande polymerer, d.v.s. plaster som leder ström, och mer allmänt organiska halvledare. Av de här materialen har man kunnat bygga elektroniska komponenter, och man hoppas på att kunna trycka hela kretsar av organiska material. För de här tillämpningarna är det viktigt att förstå hur materialen själva leder elektrisk ström. Termen oordnade material syftar på material som saknar kristallstruktur. Oordningen gör att elektronernas tillstånd blir lokaliserade i rummet, så att en elektron i ett visst tillstånd är begränsad t.ex. till en molekyl eller ett segment av en polymer. Det här kan jämföras med kristallina material, där ett elektrontillstånd är utspritt över hela kristallen (men i stället har en väldefinierad rörelsemängd). Elektronerna (eller hålen) i det oordnade materialet kan röra sig genom att tunnelera mellan de lokaliserade tillstånden. Utgående från egenskaperna för den här tunneleringsprocessen, kan man bestämma transportegenskaperna för hela materialet. Det här är utgångspunkten för den så kallade hopptransportmodellen, som jag har använt mig av. Hopptransportmodellen innehåller flera drastiska förenklingar. Till exempel betraktas elektrontillstånden som punktformiga, så att tunneleringssannolikheten mellan två tillstånd endast beror på avståndet mellan dem, och inte på deras relativa orientation. En annan förenkling är att behandla det kvantmekaniska tunneleringsproblemet som en klassisk process, en slumpvandring. Trots de här grova approximationerna visar hopptransportmodellen ändå många av de fenomen som uppträder i de verkliga materialen som man vill modellera. Man kan kanske säga att hopptransportmodellen är den enklaste modell för oordnade material som fortfarande är intressant att studera. Man har inte hittat exakta analytiska lösningar för hopptransportmodellen, därför använder man approximationer och numeriska metoder, ofta i form av datorberäkningar. Vi har använt både analytiska metoder och numeriska beräkningar för att studera olika aspekter av hopptransportmodellen. En viktig del av artiklarna som min avhandling baserar sig på är att jämföra analytiska och numeriska resultat. Min andel av arbetet har främst varit att utveckla de numeriska metoderna och applicera dem på hopptransportmodellen. Därför fokuserar jag på den här delen av arbetet i avhandlingens introduktionsdel. Ett sätt att studera hopptransportmodellen numeriskt är att direkt utföra en slumpvandringsprocess med ett datorprogram. Genom att föra statisik över slumpvandringen kan man beräkna olika transportegenskaper i modellen. Det här är en så kallad Monte Carlo-metod, eftersom själva beräkningen är en slumpmässig process. I stället för att följa rörelsebanan för enskilda elektroner, kan man beräkna sannolikheten vid jämvikt för att hitta en elektron i olika tillstånd. Man ställer upp ett system av ekvationer, som relaterar sannolikheterna för att hitta elektronen i olika tillstånd i systemet med flödet, strömmen, mellan de olika tillstånden. Genom att lösa ekvationssystemet fås sannolikhetsfördelningen för elektronerna. Från sannolikhetsfördelningen kan sedan strömmen och materialets transportegenskaper beräknas. En aspekt av hopptransportmodellen som vi studerat är elektronernas diffusion, d.v.s. deras slumpmässiga rörelse. Om man betraktar en samling elektroner, så sprider den med tiden ut sig över ett större område. Det är känt att diffusionshastigheten beror av elfältet, så att elektronerna sprider sig fortare om de påverkas av ett elektriskt fält. Vi har undersökt den här processen, och visat att beteendet är väldigt olika i endimensionella system, jämfört med två- och tredimensionella. I två och tre dimensioner beror diffusionskoefficienten kvadratiskt av elfältet, medan beroendet i en dimension är linjärt. En annan aspekt vi studerat är negativ differentiell konduktivitet, d.v.s. att strömmen i ett material minskar då man ökar spänningen över det. Eftersom det här fenomenet har uppmätts i organiska minnesceller, ville vi undersöka om fenomenet också kan uppstå i hopptransportmodellen. Det visade sig att det i modellen finns två olika mekanismer som kan ge upphov till negativ differentiell konduktivitet. Dels kan elektronerna fastna i fällor, återvändsgränder i systemet, som är sådana att det är svårare att ta sig ur dem då elfältet är stort. Då kan elektronernas medelhastighet och därmed strömmen i materialet minska med ökande elfält. Elektrisk växelverkan mellan elektronerna kan också leda till samma beteende, genom en så kallad coulombblockad. En coulombblockad kan uppstå om antalet ledningselektroner i materialet ökar med ökande spänning. Elektronerna repellerar varandra och ett större antal elektroner kan leda till att transporten blir långsammare, d.v.s. att strömmen minskar.

Use data from permanent sampling points in growth and yield modeling

This study was carried to evaluate the efficiency of the Bitterlich method in growth and yield modeling of the even-aged Eucalyptus stands. 25 plots were setup in Eucalyptus grandis cropped under a high bole system in the Central Western Region of Minas Gerais, Brazil. The sampling points were setup in the center of each plot. The data of four annual mesurements were colleted and used to adjust the three model types using the age, the site index and the basal area as independent variables. The growths models were fitted for volume and mass of trees. The efficiency of the Bitterlich method was confirmed for generating the data for growth and yield modeling.

Novel force control methods in a teleoperation system of a hydraulic slider

The objective of the this research project is to develop a novel force control scheme for the teleoperation of a hydraulically driven manipulator, and to implement an ideal transparent mapping between human and machine interaction, and machine and task environment interaction. This master‘s thesis provides a preparatory study for the present research project. The research is limited into a single degree of freedom hydraulic slider with 6-DOF Phantom haptic device. The key contribution of the thesis is to set up the experimental rig including electromechanical haptic device, hydraulic servo and 6-DOF force sensor. The slider is firstly tested as a position servo by using previously developed intelligent switching control algorithm. Subsequently the teleoperated system is set up and the preliminary experiments are carried out. In addition to development of the single DOF experimental set up, methods such as passivity control in teleoperation are reviewed. The thesis also contains review of modeling of the servo slider in particular reference to the servo valve. Markov Chain Monte Carlo method is utilized in developing the robustness of the model in presence of noise.

Modeling of electrolyte sorption – from phase equilibria to dynamic separation systems

In this thesis, general approach is devised to model electrolyte sorption from aqueous solutions on solid materials. Electrolyte sorption is often considered as unwanted phenomenon in ion exchange and its potential as an independent separation method has not been fully explored. The solid sorbents studied here are porous and non-porous organic or inorganic materials with or without specific functional groups attached on the solid matrix. Accordingly, the sorption mechanisms include physical adsorption, chemisorption on the functional groups and partition restricted by electrostatic or steric factors. The model is tested in four Cases Studies dealing with chelating adsorption of transition metal mixtures, physical adsorption of metal and metalloid complexes from chloride solutions, size exclusion of electrolytes in nano-porous materials and electrolyte exclusion of electrolyte/non-electrolyte mixtures. The model parameters are estimated using experimental data from equilibrium and batch kinetic measurements, and they are used to simulate actual single-column fixed-bed separations. Phase equilibrium between the solution and solid phases is described using thermodynamic Gibbs-Donnan model and various adsorption models depending on the properties of the sorbent. The 3-dimensional thermodynamic approach is used for volume sorption in gel-type ion exchangers and in nano-porous adsorbents, and satisfactory correlation is obtained provided that both mixing and exclusion effects are adequately taken into account. 2-Dimensional surface adsorption models are successfully applied to physical adsorption of complex species and to chelating adsorption of transition metal salts. In the latter case, comparison is also made with complex formation models. Results of the mass transport studies show that uptake rates even in a competitive high-affinity system can be described by constant diffusion coefficients, when the adsorbent structure and the phase equilibrium conditions are adequately included in the model. Furthermore, a simplified solution based on the linear driving force approximation and the shrinking-core model is developed for very non-linear adsorption systems. In each Case Study, the actual separation is carried out batch-wise in fixed-beds and the experimental data are simulated/correlated using the parameters derived from equilibrium and kinetic data. Good agreement between the calculated and experimental break-through curves is usually obtained indicating that the proposed approach is useful in systems, which at first sight are very different. For example, the important improvement in copper separation from concentrated zinc sulfate solution at elevated temperatures can be correctly predicted by the model. In some cases, however, re-adjustment of model parameters is needed due to e.g. high solution viscosity.

MODELING A COMPUTER APPLICATION FOR MANAGEMENT OF MAINTENANCE ACTIVITIES OF UNPAVED ROADS

ABSTRACTThis study presents a contribution to the modeling of a computer application employing a method of serviceability performance for unpaved roads, aiming the management of maintenance/restoration activities of the primary surface layer. The proposed methodology consisted of field inspections during dry (April to September) and rainy (October to March) periods, during which objective evaluations were performed to survey of defects and their densities and degrees of severity. To aid the functional classification of analyzed road sections and the determination of the defect with major influence on the serviceability of these roads, the method of serviceability performance proposed by Silva (2009)was implemented in the Visual Basic for Applications (VBA) language in Microsoft Excel software. With the use of the computer application proposed it was possible to identify among the defects analyzed in field, through the index of serviceability of the sampling unit per defect type (ISUdef), which one had the greatest influence on determining the relative serviceability index per road section (IST). The results allow us to conclude that the computer application Road achieved satisfactory results, since the objective evaluation criteria applied to road sections denotes consistency regarding their serviceability.

ALLOMETRIC MODELS FOR ESTIMATING ABOVEGROUND BIOMASS AND BIOMASS ALLOCATION OF CAPIXINGUI TREES (Croton floribundus Spreng.) IN AN AGRISILVICULTURAL SYSTEM

ABSTRACT The objective of this study was to select allometric models to estimate total and pooled aboveground biomass of 4.5-year-old capixingui trees established in an agrisilvicultural system. Aboveground biomass distribution of capixingui was also evaluated. Single- (diameter at breast height [DBH] or crown diameter or stem diameter as the independent variable) and double-entry (DBH or crown diameter or stem diameter and total height as independent variables) models were studied. The estimated total biomass was 17.3 t.ha-1, corresponding to 86.6 kg per tree. All models showed a good fit to the data (R2ad > 0.85) for bole, branches, and total biomass. DBH-based models presented the best residual distribution. Model lnW = b0 + b1* lnDBH can be recommended for aboveground biomass estimation. Lower coefficients were obtained for leaves (R2ad > 82%). Biomass distribution followed the order: bole>branches>leaves. Bole biomass percentage decreased with increasing DBH of the trees, whereas branch biomass increased.

A decision support system for cost determination in grain storage facility operations

Many research works have being carried out on analyzing grain storage facility costs; however a few of them had taken into account the analysis of factors associated to all pre-processing and storage steps. The objective of this work was to develop a decision support system for determining the grain storage facility costs and utilization fees in grain storage facilities. The data of a CONAB storage facility located in Ponta Grossa - PR, Brazil, was used as input of the system developed to analyze its specific characteristics, such as amount of product received and stored throughout the year, hourly capacity of drying, cleaning, and receiving, and dispatch. By applying the decision support system, it was observed that the reception and expedition costs were exponentially reduced as the turnover rate of the storage increased. The cleaning and drying costs increased linearly with grain initial moisture. The storage cost increased exponentially as the occupancy rate of the storage facility decreased.

Warning system based on theoretical-experimental study of dispersion of soluble pollutants in rivers

Information about capacity of transport and dispersion of soluble pollutants in natural streams are important in the management of water resources, especially in planning preventive measures to minimize the problems caused by accidental or intentional waste, in public health and economic activities that depend on the use of water. Considering this importance, this study aimed to develop a warning system for rivers, based on experimental techniques using tracers and analytical equations of one-dimensional transport of soluble pollutants conservative, to subsidizing the decision-making in the management of water resources. The system was development in JAVA programming language and MySQL database can predict the travel time of pollutants clouds from a point of eviction and graphically displays the temporal distribution of concentrations of passage clouds, in a particular location, downstream from the point of its launch.

Power cycling lifetime estimation of IGBT power modules based on chip temperature modeling

In this doctoral thesis, methods to estimate the expected power cycling life of power semiconductor modules based on chip temperature modeling are developed. Frequency converters operate under dynamic loads in most electric drives. The varying loads cause thermal expansion and contraction, which stresses the internal boundaries between the material layers in the power module. Eventually, the stress wears out the semiconductor modules. The wear-out cannot be detected by traditional temperature or current measurements inside the frequency converter. Therefore, it is important to develop a method to predict the end of the converter lifetime. The thesis concentrates on power-cycling-related failures of insulated gate bipolar transistors. Two types of power modules are discussed: a direct bonded copper (DBC) sandwich structure with and without a baseplate. Most common failure mechanisms are reviewed, and methods to improve the power cycling lifetime of the power modules are presented. Power cycling curves are determined for a module with a lead-free solder by accelerated power cycling tests. A lifetime model is selected and the parameters are updated based on the power cycling test results. According to the measurements, the factor of improvement in the power cycling lifetime of modern IGBT power modules is greater than 10 during the last decade. Also, it is noticed that a 10 C increase in the chip temperature cycle amplitude decreases the lifetime by 40%. A thermal model for the chip temperature estimation is developed. The model is based on power loss estimation of the chip from the output current of the frequency converter. The model is verified with a purpose-built test equipment, which allows simultaneous measurement and simulation of the chip temperature with an arbitrary load waveform. The measurement system is shown to be convenient for studying the thermal behavior of the chip. It is found that the thermal model has a 5 C accuracy in the temperature estimation. The temperature cycles that the power semiconductor chip has experienced are counted by the rainflow algorithm. The counted cycles are compared with the experimentally verified power cycling curves to estimate the life consumption based on the mission profile of the drive. The methods are validated by the lifetime estimation of a power module in a direct-driven wind turbine. The estimated lifetime of the IGBT power module in a direct-driven wind turbine is 15 000 years, if the turbine is located in south-eastern Finland.