Effects of Fin Parameters on Gas-Side Heat Transfer Performance of H-Type Finned Tube Bundle in a Waste Heat Recovery Boiler

Alfa Laval Aalborg Oy designs and manufactures waste heat recovery systems utilizing extended surfaces. The waste heat recovery boiler considered in this thesis is a water-tube boiler where exhaust gas is used as the convective heat transfer medium and water or steam flowing inside the tubes is subject to cross-flow. This thesis aims to contribute to the design of waste heat recovery boiler unit by developing a numerical model of the H-type finned tube bundle currently used by Alfa Laval Aalborg Oy to evaluate the gas-side heat transfer performance. The main objective is to identify weaknesses and potential areas of development in the current H-type finned tube design. In addition, numerical simulations for a total of 15 cases with varying geometric parameters are conducted to investigate the heat transfer and pressure drop performance dependent on H-type fin geometry. The investigated geometric parameters include fin width and height, fin spacing, and fin thickness. Comparison between single and double tube type configuration is also conducted. Based on the simulation results, the local heat transfer and flow behaviour of the H-type finned tube is presented including boundary layer development between the fins, the formation of recirculation zone behind the tubes, and the local variations of flow velocity and temperature within the tube bundle and on the fin surface. Moreover, an evaluation of the effects of various fin parameters on heat transfer and pressure drop performance of H-type finned tube bundle has been provided. It was concluded that from the studied parameters fin spacing and fin width had the most significant effect on tube bundle performance and the effect of fin thickness was the least important. Furthermore, the results suggested that the heat transfer performance would increase due to enhanced turbulence if the current double tube configuration is replaced with single tube configuration, but further investigation and experimental measurements are required in order to validate the results.

Two-dimensional drift-diffusion simulation of organic solar cells

The aim of this master's thesis is to develop a two-dimensional drift-di usion model, which describes charge transport in organic solar cells. The main bene t of a two-dimensional model compared to a one-dimensional one is the inclusion of the nanoscale morphology of the active layer of a bulk heterojunction solar cell. The developed model was used to study recombination dynamics at the donor-acceptor interface. In some cases, it was possible to determine e ective parameters, which reproduce the results of the two-dimensional model in the one-dimensional case. A summary of the theory of charge transport in semiconductors was presented and discussed in the context of organic materials. Additionally, the normalization and discretization procedures required to nd a numerical solution to the charge transport problem were outlined. The charge transport problem was solved by implementing an iterative scheme called successive over-relaxation. The obtained solution is given as position-dependent electric potential, free charge carrier concentrations and current densities in the active layer. An interfacial layer, separating the pure phases, was introduced in order to describe charge dynamics occurring at the interface between the donor and acceptor. For simplicity, an e ective generation of free charge carriers in the interfacial layer was implemented. The pure phases simply act as transport layers for the photogenerated charges. Langevin recombination was assumed in the two-dimensional model and an analysis of the apparent recombination rate in the one-dimensional case is presented. The recombination rate in a two-dimensional model is seen to e ectively look like reduced Langevin recombination at open circuit. Replicating the J-U curves obtained in the two-dimensional model is, however, not possible by introducing a constant reduction factor in the Langevin recombination rate. The impact of an acceptor domain in the pure donor phase was investigated. Two cases were considered, one where the acceptor domain is isolated and another where it is connected to the bulk of the acceptor. A comparison to the case where no isolated domains exist was done in order to quantify the observed reduction in the photocurrent. The results show that all charges generated at the isolated domain are lost to recombination, but the domain does not have a major impact on charge transport. Trap-assisted recombination at interfacial trap states was investigated, as well as the surface dipole caused by the trapped charges. A theoretical expression for the ideality factor n_id as a function of generation was derived and shown to agree with simulation data. When the theoretical expression was fitted to simulation data, no interface dipole was observed.

A novel procedure for establishing clinching parameters for high strength steel sheet

The building industry has a particular interest in using clinching as a joining method for frame constructions of light-frame housing. Normally many clinch joints are required in joining of frames.In order to maximise the strength of the complete assembly, each clinch joint must be as sound as possible. Experimental testing is the main means of optimising a particular clinch joint. This includes shear strength testing and visual observation of joint cross-sections. The manufacturers of clinching equipment normally perform such experimental trials. Finite element analysis can also be used to optimise the tool geometry and the process parameter, X, which represents the thickness of the base of the joint. However, such procedures require dedicated software, a skilled operator, and test specimens in order to verify the finite element model. In addition, when using current technology several hours' computing time may be necessary. The objective of the study was to develop a simple calculation procedure for rapidly establishing an optimum value for the parameter X for a given tool combination. It should be possible to use the procedure on a daily basis, without stringent demands on the skill of the operator or the equipment. It is also desirable that the procedure would significantly decrease thenumber of shear strength tests required for verification. The experimental workinvolved tests in order to obtain an understanding of the behaviour of the sheets during clinching. The most notable observation concerned the stage of the process in which the upper sheet was initially bent, after which the deformation mechanism changed to shearing and elongation. The amount of deformation was measured relative to the original location of the upper sheet, and characterised as the C-measure. By understanding in detail the behaviour of the upper sheet, it waspossible to estimate a bending line function for the surface of the upper sheet. A procedure was developed, which makes it possible to estimate the process parameter X for each tool combination with a fixed die. The procedure is based on equating the volume of material on the punch side with the volume of the die. Detailed information concerning the behaviour of material on the punch side is required, assuming that the volume of die does not change during the process. The procedure was applied to shear strength testing of a sample material. The sample material was continuously hot-dip zinc-coated high-strength constructional steel,with a nominal thickness of 1.0 mm. The minimum Rp0.2 proof stress was 637 N/mm2. Such material has not yet been used extensively in light-frame housing, and little has been published on clinching of the material. The performance of the material is therefore of particular interest. Companies that use clinching on a daily basis stand to gain the greatest benefit from the procedure. By understanding the behaviour of sheets in different cases, it is possible to use data at an early stage for adjusting and optimising the process. In particular, the functionality of common tools can be increased since it is possible to characterise the complete range of existing tools. The study increases and broadens the amount ofbasic information concerning the clinching process. New approaches and points of view are presented and used for generating new knowledge.

Modeling of non-isothermalvapor membrane separation with thermodynamic models and generalized mass transfer equations

A rigorous unit operation model is developed for vapor membrane separation. The new model is able to describe temperature, pressure, and concentration dependent permeation as wellreal fluid effects in vapor and gas separation with hydrocarbon selective rubbery polymeric membranes. The permeation through the membrane is described by a separate treatment of sorption and diffusion within the membrane. The chemical engineering thermodynamics is used to describe the equilibrium sorption of vapors and gases in rubbery membranes with equation of state models for polymeric systems. Also a new modification of the UNIFAC model is proposed for this purpose. Various thermodynamic models are extensively compared in order to verify the models' ability to predict and correlate experimental vapor-liquid equilibrium data. The penetrant transport through the selective layer of the membrane is described with the generalized Maxwell-Stefan equations, which are able to account for thebulk flux contribution as well as the diffusive coupling effect. A method is described to compute and correlate binary penetrant¿membrane diffusion coefficients from the experimental permeability coefficients at different temperatures and pressures. A fluid flow model for spiral-wound modules is derived from the conservation equation of mass, momentum, and energy. The conservation equations are presented in a discretized form by using the control volume approach. A combination of the permeation model and the fluid flow model yields the desired rigorous model for vapor membrane separation. The model is implemented into an inhouse process simulator and so vapor membrane separation may be evaluated as an integralpart of a process flowsheet.

Gas-liquid mass transfer in bubbly flow: Estimation of mass transfer, bubble size and reactor performance in various applications

Gas-liquid mass transfer is an important issue in the design and operation of many chemical unit operations. Despite its importance, the evaluation of gas-liquid mass transfer is not straightforward due to the complex nature of the phenomena involved. In this thesis gas-liquid mass transfer was evaluated in three different gas-liquid reactors in a traditional way by measuring the volumetric mass transfer coefficient (kLa). The studied reactors were a bubble column with a T-junction two-phase nozzle for gas dispersion, an industrial scale bubble column reactor for the oxidation of tetrahydroanthrahydroquinone and a concurrent downflow structured bed.The main drawback of this approach is that the obtained correlations give only the average volumetric mass transfer coefficient, which is dependent on average conditions. Moreover, the obtained correlations are valid only for the studied geometry and for the chemical system used in the measurements. In principle, a more fundamental approach is to estimate the interfacial area available for mass transfer from bubble size distributions obtained by solution of population balance equations. This approach has been used in this thesis by developing a population balance model for a bubble column together with phenomenological models for bubble breakage and coalescence. The parameters of the bubble breakage rate and coalescence rate models were estimated by comparing the measured and calculated bubble sizes. The coalescence models always have at least one experimental parameter. This is because the bubble coalescence depends on liquid composition in a way which is difficult to evaluate using known physical properties. The coalescence properties of some model solutions were evaluated by measuring the time that a bubble rests at the free liquid-gas interface before coalescing (the so-calledpersistence time or rest time). The measured persistence times range from 10 msup to 15 s depending on the solution. The coalescence was never found to be instantaneous. The bubble oscillates up and down at the interface at least a coupleof times before coalescence takes place. The measured persistence times were compared to coalescence times obtained by parameter fitting using measured bubble size distributions in a bubble column and a bubble column population balance model. For short persistence times, the persistence and coalescence times are in good agreement. For longer persistence times, however, the persistence times are at least an order of magnitude longer than the corresponding coalescence times from parameter fitting. This discrepancy may be attributed to the uncertainties concerning the estimation of energy dissipation rates, collision rates and mechanisms and contact times of the bubbles.

Development of a Ceramic Membrane Filtration Equipment and Its Applicability for Different Wastewaters

In this thesis the membrane filtration equipment for plate type ceramic membranes was developed based on filtration results achieved with different kinds of wastewaters. The experiments were mainly made with pulp and board mill wastewaters, but some experiments were also made with a bore well water and a stone cutting mine wastewater. The ceramicmembranes used were alpha-alumina membranes with a pore size of 100 nm. Some ofthe membranes were coated with a gamma-alumina layer to reduce the membrane pore size to 10 nm, and some of them were modified with different metal oxides in order to change the surface properties of the membranes. The effects of operationparameters, such as cross-flow velocity, filtration pressure and backflushing on filtration performance were studied. The measured parameters were the permeateflux, the quality of the permeate, as well as the fouling tendency of the membrane. A dynamic membrane or a cake layer forming on top of the membrane was observed to decrease the flux and increase separa-tion of certain substances, especially at low cross-flow velocities. When the cross-flow velocities were increased the membrane properties became more important. Backflushing could also be used to decrease the thickness of the cake layer and thus it improved the permeate flux. However, backflushing can lead to a reduction of retentions in cases where the cake layer is improving them. The wastewater quality was important for the thickness of the dynamic membrane and the membrane pore size influenced the permeate flux. In general, the optimization of operation conditions is very important for the successful operation of a membrane filtration system. The filtration equipment with a reasonable range of operational conditions is necessary, especiallywhen different kinds of wastewaters are treated. This should be taken into account already in the development stage of a filtration equipment.

Kuluttajapakkauskartonkien laserleikattavuuden karakterisointi

Tämän diplomityön tarkoituksena oli karakterisoida kuluttajapakkauskartonkien laserleikattavuutta. Kirjallisuusosassa perehdyttiin asiaa käsittelevään kirjallisuuteen ja tutkimuksiin ja kokeellisessa osassa käsiteltiin kuitumateriaalien laserleikkausta erilaisin leikkausparametrein. Leikattujen näytteiden leikkausrailosta otetuista mikroskooppikuvista määritettiin leikkausrailon uraleveys, purseen ja mustumisen määrä. Työssä tutkitut materiaalit olivat koivu- ja mäntysellu, CTMP, päällystämätön ja päällystetty sellukartonki sekä päällystämätön CTMP-runkoinen nestepakkauskartonki. Työssä havaittiin, että tutkitut kuitumateriaalit soveltuivat erinomaisesti laserleikkaukseen. Leikattujen kuitumateriaalinäytteiden leikkausrailo oli hyvälaatuinen eli leikkausrailo oli kapea, täydellisesti näytteen lävitse, tasainen reunoiltaan, väriltään vaalea ( ei hiiltynyt ) ja ei sisältänyt railon reunassa pystyssä olevia katkenneita kuituja ( pursetta ). Työssä todettiin myös, että kuitumateriaaleja laserleikatessa leikkausnopeus ja laserteho riippuivat lineaarisesti toisistaan. Leikkausnopeuden kasvaessa tarvittiin enemmän lasertehoa hyvälaatuisen leikkausrailon saavuttamiseksi. Tällöin leikkausuran leveys pysyi lähes vakiona. Lisäksi huomattiin, että optimisijainti polttopisteelle olisi 0.1-0.4 mm materiaalin pinnan yläpuolella, vaikka kirjallisuudesta löydettiin suosituksia sijoittaa polttopiste materiaalin pinnan alapuolelle. Näillä polttopisteen sijainnin arvoilla saavutettiin suurimmat leikkausnopeudet ja kapeimmat urat.

Fraktiointikerrostuksen vaikutus paperin laatuun

Työn tavoitteena oli kehittää prosessia fraktioinnista monikerrosperälaatikolle painopaperilajeilla. Tarkoituksena oli selvittää koeajojen avulla sihti- ja pyörrepuhdistusfraktioinnin soveltuvuutta paperin kerrostuksen kannalta. Työssä vertailtiin keskenään fraktiointimenetelmiä ja niiden yhdistelmiä. Tehtävänä oli prosessikonseptin kehittäminen eri prosessikytkennöistä ja –ratkaisuista simuloinnin avulla. Kirjallisuusosassa tutustuttiin analysoiden kirjallisuusviitteiden perusteella massan fraktiointiin ja paperin kerrostamiseen sekä fraktiointikerrostetun rainan karakterisointiin. Tavoitteiden saavuttamiseksi esikokeena suoritettiin pilotkoeajo hienopaperimassalla, jossa tutkittiin pääasiassa fraktiointitulosta. Toinen koeajo suoritettiin LWC-paperilla, jossa koekonekonsepti oli optimaalisempi kerrostuksen kannalta ja fraktiointitulos voitiin linkittää paperin laatusuureisiin. LWC-koeajossa fraktioidulla massalla tehtiin laboratoriomittakaavassa monikerrosarkkimuottikokeita, joiden tuloksilla pyrittiin vahvistamaan koeajosta saatuja tuloksia ja fraktioinnnin potentialia. Prosessikonseptin kehittämiseksi rakennettiin seitsemän simulointimallia eri kytkennöistä. Malleja verrattiin keskenään täyteaine- ja kuitujakeiden fraktiointikyvyn perusteella. Koeajojen avulla selvitettiin fraktioinnin kannalta optimaaliset prosessimuuttujat. Fraktiointikerrostuksella parannettiin paperin z-suuntaista lujuutta ja etenkin pyörrepuhdistinfraktioinnilla pintojen sileyttä. Fraktiointikerrostuksella voitiin parantaa paperin täyteainejakaumaa. Kokeiden perusteella huomattiin, että kukin paperilaji tarvitsee erilaisen fraktiointijärjestelyn riippuen käytetystä massasta ja täyteaineesta.

Modeling the transport phenomena within arterial wall: porous media approach

The transport of macromolecules, such as low-density lipoprotein (LDL), and their accumulation in the layers of the arterial wall play a critical role in the creation and development of atherosclerosis. Atherosclerosis is a disease of large arteries e.g., the aorta, coronary, carotid, and other proximal arteries that involves a distinctive accumulation of LDL and other lipid-bearing materials in the arterial wall. Over time, plaque hardens and narrows the arteries. The flow of oxygen-rich blood to organs and other parts of the body is reduced. This can lead to serious problems, including heart attack, stroke, or even death. It has been proven that the accumulation of macromolecules in the arterial wall depends not only on the ease with which materials enter the wall, but also on the hindrance to the passage of materials out of the wall posed by underlying layers. Therefore, attention was drawn to the fact that the wall structure of large arteries is different than other vessels which are disease-resistant. Atherosclerosis tends to be localized in regions of curvature and branching in arteries where fluid shear stress (shear rate) and other fluid mechanical characteristics deviate from their normal spatial and temporal distribution patterns in straight vessels. On the other hand, the smooth muscle cells (SMCs) residing in the media layer of the arterial wall respond to mechanical stimuli, such as shear stress. Shear stress may affect SMC proliferation and migration from the media layer to intima. This occurs in atherosclerosis and intimal hyperplasia. The study of blood flow and other body fluids and of heat transport through the arterial wall is one of the advanced applications of porous media in recent years. The arterial wall may be modeled in both macroscopic (as a continuous porous medium) and microscopic scales (as a heterogeneous porous medium). In the present study, the governing equations of mass, heat and momentum transport have been solved for different species and interstitial fluid within the arterial wall by means of computational fluid dynamics (CFD). Simulation models are based on the finite element (FE) and finite volume (FV) methods. The wall structure has been modeled by assuming the wall layers as porous media with different properties. In order to study the heat transport through human tissues, the simulations have been carried out for a non-homogeneous model of porous media. The tissue is composed of blood vessels, cells, and an interstitium. The interstitium consists of interstitial fluid and extracellular fibers. Numerical simulations are performed in a two-dimensional (2D) model to realize the effect of the shape and configuration of the discrete phase on the convective and conductive features of heat transfer, e.g. the interstitium of biological tissues. On the other hand, the governing equations of momentum and mass transport have been solved in the heterogeneous porous media model of the media layer, which has a major role in the transport and accumulation of solutes across the arterial wall. The transport of Adenosine 5´-triphosphate (ATP) is simulated across the media layer as a benchmark to observe how SMCs affect on the species mass transport. In addition, the transport of interstitial fluid has been simulated while the deformation of the media layer (due to high blood pressure) and its constituents such as SMCs are also involved in the model. In this context, the effect of pressure variation on shear stress is investigated over SMCs induced by the interstitial flow both in 2D and three-dimensional (3D) geometries for the media layer. The influence of hypertension (high pressure) on the transport of lowdensity lipoprotein (LDL) through deformable arterial wall layers is also studied. This is due to the pressure-driven convective flow across the arterial wall. The intima and media layers are assumed as homogeneous porous media. The results of the present study reveal that ATP concentration over the surface of SMCs and within the bulk of the media layer is significantly dependent on the distribution of cells. Moreover, the shear stress magnitude and distribution over the SMC surface are affected by transmural pressure and the deformation of the media layer of the aorta wall. This work reflects the fact that the second or even subsequent layers of SMCs may bear shear stresses of the same order of magnitude as the first layer does if cells are arranged in an arbitrary manner. This study has brought new insights into the simulation of the arterial wall, as the previous simplifications have been ignored. The configurations of SMCs used here with elliptic cross sections of SMCs closely resemble the physiological conditions of cells. Moreover, the deformation of SMCs with high transmural pressure which follows the media layer compaction has been studied for the first time. On the other hand, results demonstrate that LDL concentration through the intima and media layers changes significantly as wall layers compress with transmural pressure. It was also noticed that the fraction of leaky junctions across the endothelial cells and the area fraction of fenestral pores over the internal elastic lamina affect the LDL distribution dramatically through the thoracic aorta wall. The simulation techniques introduced in this work can also trigger new ideas for simulating porous media involved in any biomedical, biomechanical, chemical, and environmental engineering applications.

Päivittäistavaravaraston keräystyön simulointi

Varastotuotannon keskeinen osa on keräystyö, joka edustaa joissain tapauksissa jopa 50 % logistiikan kustannuksista. Jo pienelläkin tehostamisella päästään huomattaviin säästöihin. Keräystyö on kuitenkin yksinkertaisesta perusajatuksesta huolimatta usein monimutkaisen prosessin osa, joka on vahvasti riippuvainen tietojärjestelmistä ja toimintamalleista. Tässä diplomityössä rakennetaan kaupan alan logistiikkapalvelujen tuottajalle simulaatio-ohjelmisto, jolla on mahdollista tutkia tietojärjestelmän tiettyjen parametrien ja varaston layoutin ja artikkelinsijoittelun vaikutuksia keräystyöhön. Työssä tarkastellaan myös tilaajayrityksen varaston uudelleen organisoinnin yhteydessä tehtyjen simulaatioiden tuloksia ja verrataan niitä käytännön toteutuneeseen tilanteeseen. Varaston uudelleen organisoinnin yhteydessä tehdyt simulaatiot osoittavat, että simulaatio-ohjelmistolla voidaan simuloida tilaajayrityksen varaston keräyseriä ja -lenkkejä kohtalaisen tarkasti, kun varaston artikkeleja siirretään keräysalueelta toiselle. Simulaattorilla oli mahdollista arvioida keräyserien tunnuslukujen muutosta ja keräysmatkojen muutoksia. Työn tilaajayrityksessä tehtiin simulaation tuottamien keräyserän rakenteiden ja suoritteiden muutosten pohjalta päätös kahden eri artikkelisijoittelu vaihtoehdon välillä. Muutoksen jälkeen mitatut tulokset osoittautuivat keräysaluekohtaisesti hyvin samansuuntaisiksi, kuin simulaattorin tuottamat tulokset.

On Transmission System Design for Wireless Broadcasting

This thesis considers aspects related to the design and standardisation of transmission systems for wireless broadcasting, comprising terrestrial and mobile reception. The purpose is to identify which factors influence the technical decisions and what issues could be better considered in the design process in order to assess different use cases, service scenarios and end-user quality. Further, the necessity of cross-layer optimisation for efficient data transmission is emphasised and means to take this into consideration are suggested. The work is mainly related terrestrial and mobile digital video broadcasting systems but many of the findings can be generalised also to other transmission systems and design processes. The work has led to three main conclusions. First, it is discovered that there are no sufficiently accurate error criteria for measuring the subjective perceived audiovisual quality that could be utilised in transmission system design. Means for designing new error criteria for mobile TV (television) services are suggested and similar work related to other services is recommended. Second, it is suggested that in addition to commercial requirements there should be technical requirements setting the frame work for the design process of a new transmission system. The technical requirements should include the assessed reception conditions, technical quality of service and service functionalities. Reception conditions comprise radio channel models, receiver types and antenna types. Technical quality of service consists of bandwidth, timeliness and reliability. Of these, the thesis focuses on radio channel models and errorcriteria (reliability) as two of the most important design challenges and provides means to optimise transmission parameters based on these. Third, the thesis argues that the most favourable development for wireless broadcasting would be a single system suitable for all scenarios of wireless broadcasting. It is claimed that there are no major technical obstacles to achieve this and that the recently published second generation digital terrestrial television broadcasting system provides a good basis. The challenges and opportunities of a universal wireless broadcasting system are discussed mainly from technical but briefly also from commercial and regulatory aspect

Automated, adaptive methods for forest inventory

Forest inventories are used to estimate forest characteristics and the condition of forest for many different applications: operational tree logging for forest industry, forest health state estimation, carbon balance estimation, land-cover and land use analysis in order to avoid forest degradation etc. Recent inventory methods are strongly based on remote sensing data combined with field sample measurements, which are used to define estimates covering the whole area of interest. Remote sensing data from satellites, aerial photographs or aerial laser scannings are used, depending on the scale of inventory. To be applicable in operational use, forest inventory methods need to be easily adjusted to local conditions of the study area at hand. All the data handling and parameter tuning should be objective and automated as much as possible. The methods also need to be robust when applied to different forest types. Since there generally are no extensive direct physical models connecting the remote sensing data from different sources to the forest parameters that are estimated, mathematical estimation models are of "black-box" type, connecting the independent auxiliary data to dependent response data with linear or nonlinear arbitrary models. To avoid redundant complexity and over-fitting of the model, which is based on up to hundreds of possibly collinear variables extracted from the auxiliary data, variable selection is needed. To connect the auxiliary data to the inventory parameters that are estimated, field work must be performed. In larger study areas with dense forests, field work is expensive, and should therefore be minimized. To get cost-efficient inventories, field work could partly be replaced with information from formerly measured sites, databases. The work in this thesis is devoted to the development of automated, adaptive computation methods for aerial forest inventory. The mathematical model parameter definition steps are automated, and the cost-efficiency is improved by setting up a procedure that utilizes databases in the estimation of new area characteristics.

Recovery and refining of manganese as by-product from hydrometallurgical processes

The consumption of manganese is increasing, but huge amounts of manganese still end up in waste in hydrometallurgical processes. The recovery of manganese from multi-metal solutions at low concentrations may not be economical. In addition, poor iron control typically prevents the production of high purity manganese. Separation of iron from manganese can be done with chemical precipitation or solvent extraction methods. Combined carbonate precipitation with air oxidation is a feasible method to separate iron and manganese due to the fast kinetics, good controllability and economical reagents. In addition the leaching of manganese carbonate is easier and less acid consuming than that of hydroxide or sulfide precipitates. Selective iron removal with great efficiency from MnSO4 solution is achieved by combined oxygen or air oxidation and CaCO3 precipitation at pH > 5.8 and at a redox potential of > 200 mV. In order to avoid gypsum formation, soda ash should be used instead of limestone. In such case, however, extra attention needs to be paid on the reagents mole ratios in order to avoid manganese coprecipitation. After iron removal, pure MnSO4 solution was obtained by solvent extraction using organophosphorus reagents, di-(2-ethylhexyl)phosphoric acid (D2EHPA) and bis(2,4,4- trimethylpentyl)phosphinic acid (CYANEX 272). The Mn/Ca and Mn/Mg selectivities can be increased by decreasing the temperature from the commonly used temperatures (40 –60oC) to 5oC. The extraction order of D2EHPA (Ca before Mn) at low temperature remains unchanged but the lowering of temperature causes an increase in viscosity and slower phase separation. Of these regents, CYANEX 272 is selective for Mn over Ca and, therefore, it would be the better choice if there is Ca present in solution. A three-stage Mn extraction followed by a two-stage scrubbing and two-stage sulfuric acid stripping is an effective method of producing a very pure MnSO4 intermediate solution for further processing. From the intermediate MnSO4 some special Mn- products for ion exchange applications were synthesized and studied. Three types of octahedrally coordinated manganese oxide materials as an alternative final product for manganese were chosen for synthesis: layer structured Nabirnessite, tunnel structured Mg-todorokite and K-kryptomelane. As an alternative source of pure MnSO4 intermediate, kryptomelane was synthesized by using a synthetic hydrometallurgical tailings. The results show that the studied OMS materials adsorb selectively Cu, Ni, Cd and K in the presence of Ca and Mg. It was also found that the exchange rates were reasonably high due to the small particle dimensions. Materials are stable in the studied conditions and their maximum Cu uptake capacity was 1.3 mmol/g. Competitive uptake of metals and acid was studied using equilibrium, batch kinetic and fixed-bed measurements. The experimental data was correlated with a dynamic model, which also accounts for the dissolution of the framework manganese. Manganese oxide micro-crystals were also bound onto silica to prepare a composite material having a particle size large enough to be used in column separation experiments. The MnOx/SiO2 ratio was found to affect significantly the properties of the composite. The higher the ratio, the lower is the specific surface area, the pore volume and the pore size. On the other hand, higher amount of silica binder gives composites better mechanical properties. Birnesite and todorokite can be aggregated successfully with colloidal silica at pH 4 and with MnO2/SiO2 weight ratio of 0.7. The best gelation and drying temperature was 110oC and sufficiently strong composites were obtained by additional heat-treatment at 250oC for 2 h. The results show that silica–supported MnO2 materials can be utilized to separate copper from nickel and cadmium. The behavior of the composites can be explained reasonably well with the presented model and the parameters estimated from the data of the unsupported oxides. The metal uptake capacities of the prepared materials were quite small. For example, the final copper loading was 0.14 mmol/gMnO2. According to the results the special MnO2 materials are potential for a specific environmental application to uptake harmful metal ions.

Trustworthy context dependency in ubiquitous systems

The modern society is getting increasingly dependent on software applications. These run on processors, use memory and account for controlling functionalities that are often taken for granted. Typically, applications adjust the functionality in response to a certain context that is provided or derived from the informal environment with various qualities. To rigorously model the dependence of an application on a context, the details of the context are abstracted and the environment is assumed stable and fixed. However, in a context-aware ubiquitous computing environment populated by autonomous agents, a context and its quality parameters may change at any time. This raises the need to derive the current context and its qualities at runtime. It also implies that a context is never certain and may be subjective, issues captured by the context’s quality parameter of experience-based trustworthiness. Given this, the research question of this thesis is: In what logical topology and by what means may context provided by autonomous agents be derived and formally modelled to serve the context-awareness requirements of an application? This research question also stipulates that the context derivation needs to incorporate the quality of the context. In this thesis, we focus on the quality of context parameter of trustworthiness based on experiences having a level of certainty and referral experiences, thus making trustworthiness reputation based. Hence, in this thesis we seek a basis on which to reason and analyse the inherently inaccurate context derived by autonomous agents populating a ubiquitous computing environment in order to formally model context-awareness. More specifically, the contribution of this thesis is threefold: (i) we propose a logical topology of context derivation and a method of calculating its trustworthiness, (ii) we provide a general model for storing experiences and (iii) we formalise the dependence between the logical topology of context derivation and its experience-based trustworthiness. These contributions enable abstraction of a context and its quality parameters to a Boolean decision at runtime that may be formally reasoned with. We employ the Action Systems framework for modelling this. The thesis is a compendium of the author’s scientific papers, which are republished in Part II. Part I introduces the field of research by providing the mending elements for the thesis to be a coherent introduction for addressing the research question. In Part I we also review a significant body of related literature in order to better illustrate our contributions to the research field.

Acidic dissolution of iron oxides and regeneration of a ceramic filter medium

The dewatering of iron ore concentrates requires large capacity in addition to producing a cake with low moisture content. Such large processes are commonly energy intensive and means to lower the specific energy consumption are needed. Ceramic capillary action disc filters incorporate a novel filter medium enabling the harnessing of capillary action, which results in decreased energy consumption in comparison to traditional filtration technologies. As another benefit, the filter medium is mechanically and chemically more durable than, for example, filter cloths and can, thus, withstand harsh operating conditions and possible regeneration better than other types of filter media. In iron ore dewatering, the regeneration of the filter medium is done through a combination of several techniques: (1) backwashing, (2) ultrasonic cleaning, and (3) acid regeneration. Although it is commonly acknowledged that the filter medium is affected by slurry particles and extraneous compounds, published research, especially in the field of dewatering of mineral concentrates, is scarce. Whereas the regenerative effect of backwashing and ultrasound are more or less mechanical, regeneration with acids is based on chemistry. The chemistry behind the acid regeneration is, naturally, dissolution. The dissolution of iron oxide particles has been extensively studied over several decades but those studies may not necessarily be directly applicable in the regeneration of the filter medium which has undergone interactions with the slurry components. The aim of this thesis was to investigate if free particle dissolution indeed correlates with the regeneration of the filter medium. For this purpose, both free particle dissolution and dissolution of surface adhered particles were studied. The focus was on acidic dissolution of iron oxide particles and on the study of the ceramic filter medium used in the dewatering of iron ore concentrates. The free particle dissolution experiments show that the solubility of synthetic fine grained iron oxide particles in oxalic acid could be explained through linear models accounting for the effects of temperature and acid concentration, whereas the dissolution of a natural magnetite is not so easily explained by such models. In addition, the kinetic experiments performed both support and contradict the work of previous authors: the suitable kinetic model here supports previous research suggesting solid state reduction to be the reaction mechanism of hematite dissolution but the formation of a stable iron oxalate is not supported by the results of this research. Several other dissolution mechanisms have also been suggested for iron oxide dissolution in oxalic acid, indicating that the details of oxalate promoted reductive dissolution are not yet agreed and, in this respect, this research offers added value to the community. The results of the regeneration experiments with the ceramic filter media show that oxalic acid is highly effective in removing iron oxide particles from the surface of the filter medium. The dissolution of those particles did not, however, exhibit the expected behaviour, i.e. complete dissolution. The results of this thesis show that although the regeneration of the ceramic filter medium with acids incorporates the dissolution of slurry particles from the surface of the filter medium, the regeneration cannot be assessed purely based upon free particle dissolution. A steady state, dependent on temperature and on the acid concentration, was observed in the dissolution of particles from the surface even though the limit of solubility of free iron oxide particles had not been reached. Both the regeneration capacity and efficiency, with regards to the removal of iron oxide particles, was found to be temperature dependent, but was not affected by the acid concentration. This observation further suggests that the removal of the surface adhered particles does not follow the dissolution of free particles, which do exhibit a dependency on the acid concentration. In addition, changes in the permeability and in the pore structure of the filter medium were still observed after the bulk concentration of dissolved iron had reached a steady state. Consequently, the regeneration of the filter medium continued after the dissolution of particles from the surface had ceased. This observation suggests that internal changes take place at the final stages of regeneration. The regeneration process could, in theory, be divided into two, possibly overlapping, stages: (1) dissolution of surface-adhered particles, and (2) dissolution of extraneous compounds from within the pore structure. In addition to the fundamental knowledge generated during this thesis, tools to assess the effects of parameters on the regeneration of the ceramic filter medium are needed. It has become clear that the same tools used to estimate the dissolution of free particles cannot be used to estimate the regeneration of a filter medium unless only a robust characterisation of the order of regeneration efficiency is needed.