Jatkuvatoiminen ioninvaihto ja kompleksoituvien metallien sorptio kloridiympäristössä

Työn tarkoituksena oli tutkia kompleksoituvien metallien erotusta kloridiliuoksesta ioninvaihdolla. Kirjallisessa osassa perehdyttiin metallikompleksien muodostumiseen, ja erityisesti hopean, kalsiumin, magnesiumin, lyijyn ja sinkin muodostamiin komplekseihin kloridin ja nitraatin kanssa. Kirjallisessa osassa käsiteltiin myös metallien erottamista kiintopetikolonneissa jatkuvatoimisilla ioninvaihtomenetelmillä. Tässä työssä jatkuvatoimisen ioninvaihdon prosessivaihtoehdot jaoteltiin pyöriviin ja paikallaan pysyviin kolonneihin, sekä tarkasteltiin eri prosessivaihtoehtoja kolonnien kytkentöjen suhteen. Työn kokeellisessa osassa tutkittiin kahdenarvoisten metallien erottamista yhdenarvoisista metalleista sekä luotiin koedataa vastaavanlaisen erotusprosessin simulointiin. Kokeissa käytettiin anioninvaihtohartsia ja kelatoivaa selektiivistä ioninvaihtohartsia. Kahdenarvoisen kalsiumin, magnesiumin, lyijyn ja sinkin adsorptiota hartseihin tutkittiin tasapaino-, kinetiikka- ja kolonnikokeilla. Anioninvaihtohartsilla tehtyjen tasapaino- ja kolonnikokeiden tulokset osoittivat, että hartsi adsorboi tehokkaasti sinkkiä kloridiliuoksista, koska sinkki muodostaa stabiileja anionisia klorokomplekseja. Muiden tutkittujen kahdenarvoisten metallien adsorptio hartsiin oli huomattavasti vähäisempää. Tulosten perusteella tutkittu anioninvaihtohartsi on hyvä vaihtoehto sinkin erottamiseen muista tutkituista kahdenarvoisista metalleista kloridiympäristössä. Kelatoivalla hartsilla tehdyt tasapaino- ja kolonnikokeet osoittivat, että hartsi adsorboi kloridiliuoksista hyvin kahdenarvoista kalsiumia, magnesiumia, lyijyä ja sinkkiä, mutta ei adsorboi yhdenarvoista hopeaa. Tulosten perusteella kahdenarvoisten metallien erottaminen yhdenarvoisista metalleista voidaan toteuttaa kokeissa käytetyllä kelatoivalla ioninvaihtohartsilla.

Promoting Programming Learning. Engagement, Automatic Assessment with Immediate Feedback in Visualizations

The skill of programming is a key asset for every computer science student. Many studies have shown that this is a hard skill to learn and the outcomes of programming courses have often been substandard. Thus, a range of methods and tools have been developed to assist students’ learning processes. One of the biggest fields in computer science education is the use of visualizations as a learning aid and many visualization based tools have been developed to aid the learning process during last few decades. Studies conducted in this thesis focus on two different visualizationbased tools TRAKLA2 and ViLLE. This thesis includes results from multiple empirical studies about what kind of effects the introduction and usage of these tools have on students’ opinions and performance, and what kind of implications there are from a teacher’s point of view. The results from studies in this thesis show that students preferred to do web-based exercises, and felt that those exercises contributed to their learning. The usage of the tool motivated students to work harder during their course, which was shown in overall course performance and drop-out statistics. We have also shown that visualization-based tools can be used to enhance the learning process, and one of the key factors is the higher and active level of engagement (see. Engagement Taxonomy by Naps et al., 2002). The automatic grading accompanied with immediate feedback helps students to overcome obstacles during the learning process, and to grasp the key element in the learning task. These kinds of tools can help us to cope with the fact that many programming courses are overcrowded with limited teaching resources. These tools allows us to tackle this problem by utilizing automatic assessment in exercises that are most suitable to be done in the web (like tracing and simulation) since its supports students’ independent learning regardless of time and place. In summary, we can use our course’s resources more efficiently to increase the quality of the learning experience of the students and the teaching experience of the teacher, and even increase performance of the students. There are also methodological results from this thesis which contribute to developing insight into the conduct of empirical evaluations of new tools or techniques. When we evaluate a new tool, especially one accompanied with visualization, we need to give a proper introduction to it and to the graphical notation used by tool. The standard procedure should also include capturing the screen with audio to confirm that the participants of the experiment are doing what they are supposed to do. By taken such measures in the study of the learning impact of visualization support for learning, we can avoid drawing false conclusion from our experiments. As computer science educators, we face two important challenges. Firstly, we need to start to deliver the message in our own institution and all over the world about the new – scientifically proven – innovations in teaching like TRAKLA2 and ViLLE. Secondly, we have the relevant experience of conducting teaching related experiment, and thus we can support our colleagues to learn essential know-how of the research based improvement of their teaching. This change can transform academic teaching into publications and by utilizing this approach we can significantly increase the adoption of the new tools and techniques, and overall increase the knowledge of best-practices. In future, we need to combine our forces and tackle these universal and common problems together by creating multi-national and multiinstitutional research projects. We need to create a community and a platform in which we can share these best practices and at the same time conduct multi-national research projects easily.

Improving the calculation of rate of stratification in APROS

APROS (Advanced Process Simulation Environment) is a computer simulation program developed to simulate thermal hydraulic processes in nuclear and conventional power plants. Earlier research at VTT Technological Research Centre of Finland had found the current version of APROS to produce inaccurate simulation results for a certain case of loop seal clearing. The objective of this Master’s thesis is to find and implement an alternative method for calculating the rate of stratification in APROS, which was found to be the reason for the inaccuracies. Brief literature study was performed and a promising candidate for the new method was found. The new method was implemented into APROS and tested against experiments and simulations from two test facilities and the current version of APROS. Simulation results with the new version were partially conflicting; in some cases the new method was more accurate than the current version, in some the current method was better. Overall, the new method can be assessed as an improvement.

Microscopic simulation of pigment coating consolidation

The control of coating layer properties is becoming increasingly important as a result of an emerging demand for novel coated paper-based products and an increasing popularity of new coating application methods. The governing mechanisms of microstructure formation dynamics during consolidation and drying are nevertheless, still poorly understood. Some of the difficulties encountered by experimental methods can be overcome by the utilisation of numerical modelling and simulation-based studies of the consolidation process. The objective of this study was to improve the fundamental understanding of pigment coating consolidation and structure formation mechanisms taking place on the microscopic level. Furthermore, it is aimed to relate the impact of process and suspension properties to the microstructure of the coating layer. A mathematical model based on a modified Stokesian dynamics particle simulation technique was developed and applied in several studies of consolidation-related phenomena. The model includes particle-particle and particle-boundary hydrodynamics, colloidal interactions, Born repulsion, and a steric repulsion model. The Brownian motion and a free surface model were incorporated to enable the specific investigation of consolidation and drying. Filter cake stability was simulated in various particle systems, and subjected to a range of base substrate absorption rates and system temperatures. The stability of the filter cake was primarily affected by the absorption rate and size of particles. Temperature was also shown to have an influence. The consolidation of polydisperse systems, with varying wet coating thicknesses, was studied using imposed pilot trial and model-based drying conditions. The results show that drying methods have a clear influence on the microstructure development, on small particle distributions in the coating layer and also on the mobility of particles during consolidation. It is concluded that colloidal properties can significantly impact coating layer shrinkage as well as the internal solids concentration profile. Visualisations of particle system development in time and comparison of systems at different conditions are useful in illustrating coating layer structure formation mechanisms. The results aid in understanding the underlying mechanisms of pigment coating layer consolidation. Guidance is given regarding the relationship between coating process conditions and internal coating slurry properties and their effects on the microstructure of the coating.

Tutorials for MeVEA Simulation Software

The objective of the thesis was to create three tutorials for MeVEA Simulation Software to instruct the new users to the modeling methodology used in the MeVEA Simulation Software. MeVEA Simulation Software is a real-time simulation software based on multibody dynamics. The simulation software is designed to create simulation models of complete mechatronical system. The thesis begins with a more detail description of the MeVEA Simulation Software and its components. The thesis presents the three simulation models and written theory of the steps of model creation. The first tutorial introduces the basic features which are used in most simulation models. The basic features include bodies, constrains, forces, basic hydraulics and motors. The second tutorial introduces the power transmission components, tyres and user input definitions for the different components in power transmission systems. The third tutorial introduces the definitions of two different types of collisions and collision graphics used in MeVEA Simulation Software.

Methods and Models for Accelerating Dynamic Simulation of Fluid Power Circuits

The objective of this dissertation is to improve the dynamic simulation of fluid power circuits. A fluid power circuit is a typical way to implement power transmission in mobile working machines, e.g. cranes, excavators etc. Dynamic simulation is an essential tool in developing controllability and energy-efficient solutions for mobile machines. Efficient dynamic simulation is the basic requirement for the real-time simulation. In the real-time simulation of fluid power circuits there exist numerical problems due to the software and methods used for modelling and integration. A simulation model of a fluid power circuit is typically created using differential and algebraic equations. Efficient numerical methods are required since differential equations must be solved in real time. Unfortunately, simulation software packages offer only a limited selection of numerical solvers. Numerical problems cause noise to the results, which in many cases leads the simulation run to fail. Mathematically the fluid power circuit models are stiff systems of ordinary differential equations. Numerical solution of the stiff systems can be improved by two alternative approaches. The first is to develop numerical solvers suitable for solving stiff systems. The second is to decrease the model stiffness itself by introducing models and algorithms that either decrease the highest eigenvalues or neglect them by introducing steady-state solutions of the stiff parts of the models. The thesis proposes novel methods using the latter approach. The study aims to develop practical methods usable in dynamic simulation of fluid power circuits using explicit fixed-step integration algorithms. In this thesis, twomechanisms whichmake the systemstiff are studied. These are the pressure drop approaching zero in the turbulent orifice model and the volume approaching zero in the equation of pressure build-up. These are the critical areas to which alternative methods for modelling and numerical simulation are proposed. Generally, in hydraulic power transmission systems the orifice flow is clearly in the turbulent area. The flow becomes laminar as the pressure drop over the orifice approaches zero only in rare situations. These are e.g. when a valve is closed, or an actuator is driven against an end stopper, or external force makes actuator to switch its direction during operation. This means that in terms of accuracy, the description of laminar flow is not necessary. But, unfortunately, when a purely turbulent description of the orifice is used, numerical problems occur when the pressure drop comes close to zero since the first derivative of flow with respect to the pressure drop approaches infinity when the pressure drop approaches zero. Furthermore, the second derivative becomes discontinuous, which causes numerical noise and an infinitely small integration step when a variable step integrator is used. A numerically efficient model for the orifice flow is proposed using a cubic spline function to describe the flow in the laminar and transition areas. Parameters for the cubic spline function are selected such that its first derivative is equal to the first derivative of the pure turbulent orifice flow model in the boundary condition. In the dynamic simulation of fluid power circuits, a tradeoff exists between accuracy and calculation speed. This investigation is made for the two-regime flow orifice model. Especially inside of many types of valves, as well as between them, there exist very small volumes. The integration of pressures in small fluid volumes causes numerical problems in fluid power circuit simulation. Particularly in realtime simulation, these numerical problems are a great weakness. The system stiffness approaches infinity as the fluid volume approaches zero. If fixed step explicit algorithms for solving ordinary differential equations (ODE) are used, the system stability would easily be lost when integrating pressures in small volumes. To solve the problem caused by small fluid volumes, a pseudo-dynamic solver is proposed. Instead of integration of the pressure in a small volume, the pressure is solved as a steady-state pressure created in a separate cascade loop by numerical integration. The hydraulic capacitance V/Be of the parts of the circuit whose pressures are solved by the pseudo-dynamic method should be orders of magnitude smaller than that of those partswhose pressures are integrated. The key advantage of this novel method is that the numerical problems caused by the small volumes are completely avoided. Also, the method is freely applicable regardless of the integration routine applied. The superiority of both above-mentioned methods is that they are suited for use together with the semi-empirical modelling method which necessarily does not require any geometrical data of the valves and actuators to be modelled. In this modelling method, most of the needed component information can be taken from the manufacturer’s nominal graphs. This thesis introduces the methods and shows several numerical examples to demonstrate how the proposed methods improve the dynamic simulation of various hydraulic circuits.

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.

Simulation and optimization of IGCC technique for power generation and hydrogen production by using lignite Thar coal and cotton stalk

The purpose of this study was to simulate and to optimize integrated gasification for combine cycle (IGCC) for power generation and hydrogen (H2) production by using low grade Thar lignite coal and cotton stalk. Lignite coal is abundant of moisture and ash content, the idea of addition of cotton stalk is to increase the mass of combustible material per mass of feed use for the process, to reduce the consumption of coal and to increase the cotton stalk efficiently for IGCC process. Aspen plus software is used to simulate the process with different mass ratios of coal to cotton stalk and for optimization: process efficiencies, net power generation and H2 production etc. are considered while environmental hazard emissions are optimized to acceptance level. With the addition of cotton stalk in feed, process efficiencies started to decline along with the net power production. But for H2 production, it gave positive result at start but after 40% cotton stalk addition, H2 production also started to decline. It also affects negatively on environmental hazard emissions and mass of emissions/ net power production increases linearly with the addition of cotton stalk in feed mixture. In summation with the addition of cotton stalk, overall affects seemed to negative. But the effect is more negative after 40% cotton stalk addition so it is concluded that to get maximum process efficiencies and high production less amount of cotton stalk addition in feed is preferable and the maximum level of addition is estimated to 40%. Gasification temperature should keep lower around 1140 °C and prefer technique for studied feed in IGCC is fluidized bed (ash in dry form) rather than ash slagging gasifier

CFD Modelling of Direct Contact Condensation in Suppression Pools by Applying Condensation Models of Separated Flow

The condensation rate has to be high in the safety pressure suppression pool systems of Boiling Water Reactors (BWR) in order to fulfill their safety function. The phenomena due to such a high direct contact condensation (DCC) rate turn out to be very challenging to be analysed either with experiments or numerical simulations. In this thesis, the suppression pool experiments carried out in the POOLEX facility of Lappeenranta University of Technology were simulated. Two different condensation modes were modelled by using the 2-phase CFD codes NEPTUNE CFD and TransAT. The DCC models applied were the typical ones to be used for separated flows in channels, and their applicability to the rapidly condensing flow in the condensation pool context had not been tested earlier. A low Reynolds number case was the first to be simulated. The POOLEX experiment STB-31 was operated near the conditions between the ’quasi-steady oscillatory interface condensation’ mode and the ’condensation within the blowdown pipe’ mode. The condensation models of Lakehal et al. and Coste & Lavi´eville predicted the condensation rate quite accurately, while the other tested ones overestimated it. It was possible to get the direct phase change solution to settle near to the measured values, but a very high resolution of calculation grid was needed. Secondly, a high Reynolds number case corresponding to the ’chugging’ mode was simulated. The POOLEX experiment STB-28 was chosen, because various standard and highspeed video samples of bubbles were recorded during it. In order to extract numerical information from the video material, a pattern recognition procedure was programmed. The bubble size distributions and the frequencies of chugging were calculated with this procedure. With the statistical data of the bubble sizes and temporal data of the bubble/jet appearance, it was possible to compare the condensation rates between the experiment and the CFD simulations. In the chugging simulations, a spherically curvilinear calculation grid at the blowdown pipe exit improved the convergence and decreased the required cell count. The compressible flow solver with complete steam-tables was beneficial for the numerical success of the simulations. The Hughes-Duffey model and, to some extent, the Coste & Lavi´eville model produced realistic chugging behavior. The initial level of the steam/water interface was an important factor to determine the initiation of the chugging. If the interface was initialized with a water level high enough inside the blowdown pipe, the vigorous penetration of a water plug into the pool created a turbulent wake which invoked the chugging that was self-sustaining. A 3D simulation with a suitable DCC model produced qualitatively very realistic shapes of the chugging bubbles and jets. The comparative FFT analysis of the bubble size data and the pool bottom pressure data gave useful information to distinguish the eigenmodes of chugging, bubbling, and pool structure oscillations.

Software for design of experiments and response modelling of cake ltration applications

Filtration is a widely used unit operation in chemical engineering. The huge variation in the properties of materials to be ltered makes the study of ltration a challenging task. One of the objectives of this thesis was to show that conventional ltration theories are di cult to use when the system to be modelled contains all of the stages and features that are present in a complete solid/liquid separation process. Furthermore, most of the ltration theories require experimental work to be performed in order to obtain critical parameters required by the theoretical models. Creating a good overall understanding of how the variables a ect the nal product in ltration is somewhat impossible on a purely theoretical basis. The complexity of solid/liquid separation processes require experimental work and when tests are needed, it is advisable to use experimental design techniques so that the goals can be achieved. The statistical design of experiments provides the necessary tools for recognising the e ects of variables. It also helps to perform experimental work more economically. Design of experiments is a prerequisite for creating empirical models that can describe how the measured response is related to the changes in the values of the variable. A software package was developed that provides a ltration practitioner with experimental designs and calculates the parameters for linear regression models, along with the graphical representation of the responses. The developed software consists of two software modules. These modules are LTDoE and LTRead. The LTDoE module is used to create experimental designs for di erent lter types. The lter types considered in the software are automatic vertical pressure lter, double-sided vertical pressure lter, horizontal membrane lter press, vacuum belt lter and ceramic capillary action disc lter. It is also possible to create experimental designs for those cases where the variables are totally user de ned, say for a customized ltration cycle or di erent piece of equipment. The LTRead-module is used to read the experimental data gathered from the experiments, to analyse the data and to create models for each of the measured responses. Introducing the structure of the software more in detail and showing some of the practical applications is the main part of this thesis. This approach to the study of cake ltration processes, as presented in this thesis, has been shown to have good practical value when making ltration tests.

Improving Transportation and Warehousing Efficiency with Simulation-Based Decision Support Systems

Transportation and warehousing are large and growing sectors in the society, and their efficiency is of high importance. Transportation also has a large share of global carbondioxide emissions, which are one the leading causes of anthropogenic climate warming. Various countries have agreed to decrease their carbon emissions according to the Kyoto protocol. Transportation is the only sector where emissions have steadily increased since the 1990s, which highlights the importance of transportation efficiency. The efficiency of transportation and warehousing can be improved with the help of simulations, but models alone are not sufficient. This research concentrates on the use of simulations in decision support systems. Three main simulation approaches are used in logistics: discrete-event simulation, systems dynamics, and agent-based modeling. However, individual simulation approaches have weaknesses of their own. Hybridization (combining two or more approaches) can improve the quality of the models, as it allows using a different method to overcome the weakness of one method. It is important to choose the correct approach (or a combination of approaches) when modeling transportation and warehousing issues. If an inappropriate method is chosen (this can occur if the modeler is proficient in only one approach or the model specification is not conducted thoroughly), the simulation model will have an inaccurate structure, which in turn will lead to misleading results. This issue can further escalate, as the decision-maker may assume that the presented simulation model gives the most useful results available, even though the whole model can be based on a poorly chosen structure. In this research it is argued that simulation- based decision support systems need to take various issues into account to make a functioning decision support system. The actual simulation model can be constructed using any (or multiple) approach, it can be combined with different optimization modules, and there needs to be a proper interface between the model and the user. These issues are presented in a framework, which simulation modelers can use when creating decision support systems. In order for decision-makers to fully benefit from the simulations, the user interface needs to clearly separate the model and the user, but at the same time, the user needs to be able to run the appropriate runs in order to analyze the problems correctly. This study recommends that simulation modelers should start to transfer their tacit knowledge to explicit knowledge. This would greatly benefit the whole simulation community and improve the quality of simulation-based decision support systems as well. More studies should also be conducted by using hybrid models and integrating simulations with Graphical Information Systems.

Improving strategic decision-making with simulation based decision support systems

Combating climate change is one of the key tasks of humanity in the 21st century. One of the leading causes is carbon dioxide emissions due to usage of fossil fuels. Renewable energy sources should be used instead of relying on oil, gas, and coal. In Finland a significant amount of energy is produced using wood. The usage of wood chips is expected to increase in the future significantly, over 60 %. The aim of this research is to improve understanding over the costs of wood chip supply chains. This is conducted by utilizing simulation as the main research method. The simulation model utilizes both agent-based modelling and discrete event simulation to imitate the wood chip supply chain. This thesis concentrates on the usage of simulation based decision support systems in strategic decision-making. The simulation model is part of a decision support system, which connects the simulation model to databases but also provides a graphical user interface for the decisionmaker. The main analysis conducted with the decision support system concentrates on comparing a traditional supply chain to a supply chain utilizing specialized containers. According to the analysis, the container supply chain is able to have smaller costs than the traditional supply chain. Also, a container supply chain can be more easily scaled up due to faster emptying operations. Initially the container operations would only supply part of the fuel needs of a power plant and it would complement the current supply chain. The model can be expanded to include intermodal supply chains as due to increased demand in the future there is not enough wood chips located close to current and future power plants.

Simulation methods in the modelling of bioaffinity assays

Computational model-based simulation methods were developed for the modelling of bioaffinity assays. Bioaffinity-based methods are widely used to quantify a biological substance in biological research, development and in routine clinical in vitro diagnostics. Bioaffinity assays are based on the high affinity and structural specificity between the binding biomolecules. The simulation methods developed are based on the mechanistic assay model, which relies on the chemical reaction kinetics and describes the forming of a bound component as a function of time from the initial binding interaction. The simulation methods were focused on studying the behaviour and the reliability of bioaffinity assay and the possibilities the modelling methods of binding reaction kinetics provide, such as predicting assay results even before the binding reaction has reached equilibrium. For example, a rapid quantitative result from a clinical bioaffinity assay sample can be very significant, e.g. even the smallest elevation of a heart muscle marker reveals a cardiac injury. The simulation methods were used to identify critical error factors in rapid bioaffinity assays. A new kinetic calibration method was developed to calibrate a measurement system by kinetic measurement data utilizing only one standard concentration. A nodebased method was developed to model multi-component binding reactions, which have been a challenge to traditional numerical methods. The node-method was also used to model protein adsorption as an example of nonspecific binding of biomolecules. These methods have been compared with the experimental data from practice and can be utilized in in vitro diagnostics, drug discovery and in medical imaging.

Software for design of experiments and response modelling of cake filtration applications

Filtration is a widely used unit operation in chemical engineering. The huge variation in the properties of materials to be ltered makes the study of ltration a challenging task. One of the objectives of this thesis was to show that conventional ltration theories are di cult to use when the system to be modelled contains all of the stages and features that are present in a complete solid/liquid separation process. Furthermore, most of the ltration theories require experimental work to be performed in order to obtain critical parameters required by the theoretical models. Creating a good overall understanding of how the variables a ect the nal product in ltration is somewhat impossible on a purely theoretical basis. The complexity of solid/liquid separation processes require experimental work and when tests are needed, it is advisable to use experimental design techniques so that the goals can be achieved. The statistical design of experiments provides the necessary tools for recognising the e ects of variables. It also helps to perform experimental work more economically. Design of experiments is a prerequisite for creating empirical models that can describe how the measured response is related to the changes in the values of the variable. A software package was developed that provides a ltration practitioner with experimental designs and calculates the parameters for linear regression models, along with the graphical representation of the responses. The developed software consists of two software modules. These modules are LTDoE and LTRead. The LTDoE module is used to create experimental designs for di erent lter types. The lter types considered in the software are automatic vertical pressure lter, double-sided vertical pressure lter, horizontal membrane lter press, vacuum belt lter and ceramic capillary action disc lter. It is also possible to create experimental designs for those cases where the variables are totally user de ned, say for a customized ltration cycle or di erent piece of equipment. The LTRead-module is used to read the experimental data gathered from the experiments, to analyse the data and to create models for each of the measured responses. Introducing the structure of the software more in detail and showing some of the practical applications is the main part of this thesis. This approach to the study of cake ltration processes, as presented in this thesis, has been shown to have good practical value when making ltration tests.