Utilization of steelmaking waste materials for production of calcium carbonate (CaCO3)

The steel industry produces, besides steel, also solid mineral by-products or slags, while it emits large quantities of carbon dioxide (CO2). Slags consist of various silicates and oxides which are formed in chemical reactions between the iron ore and the fluxing agents during the high temperature processing at the steel plant. Currently, these materials are recycled in the ironmaking processes, used as aggregates in construction, or landfilled as waste. The utilization rate of the steel slags can be increased by selectively extracting components from the mineral matrix. As an example, aqueous solutions of ammonium salts such as ammonium acetate, chloride and nitrate extract calcium quite selectively already at ambient temperature and pressure conditions. After the residual solids have been separated from the solution, calcium carbonate can be precipitated by feeding a CO2 flow through the solution. Precipitated calcium carbonate (PCC) is used in different applications as a filler material. Its largest consumer is the papermaking industry, which utilizes PCC because it enhances the optical properties of paper at a relatively low cost. Traditionally, PCC is manufactured from limestone, which is first calcined to calcium oxide, then slaked with water to calcium hydroxide and finally carbonated to PCC. This process emits large amounts of CO2, mainly because of the energy-intensive calcination step. This thesis presents research work on the scale-up of the above-mentioned ammonium salt based calcium extraction and carbonation method, named Slag2PCC. Extending the scope of the earlier studies, it is now shown that the parameters which mainly affect the calcium utilization efficiency are the solid-to-liquid ratio of steel slag and the ammonium salt solvent solution during extraction, the mean diameter of the slag particles, and the slag composition, especially the fractions of total calcium, silicon, vanadium and iron as well as the fraction of free calcium oxide. Regarding extraction kinetics, slag particle size, solid-to-liquid ratio and molar concentration of the solvent solution have the largest effect on the reaction rate. Solvent solution concentrations above 1 mol/L NH4Cl cause leaching of other elements besides calcium. Some of these such as iron and manganese result in solution coloring, which can be disadvantageous for the quality of the PCC product. Based on chemical composition analysis of the produced PCC samples, however, the product quality is mainly similar as in commercial products. Increasing the novelty of the work, other important parameters related to assessment of the PCC quality, such as particle size distribution and crystal morphology are studied as well. As in traditional PCC precipitation process, the ratio of calcium and carbonate ions controls the particle shape; a higher value for [Ca2+]/[CO32-] prefers precipitation of calcite polymorph, while vaterite forms when carbon species are present in excess. The third main polymorph, aragonite, is only formed at elevated temperatures, above 40-50 °C. In general, longer precipitation times cause transformation of vaterite to calcite or aragonite, but also result in particle agglomeration. The chemical equilibrium of ammonium and calcium ions and dissolved ammonia controlling the solution pH affects the particle sizes, too. Initial pH of 12-13 during the carbonation favors nonagglomerated particles with a diameter of 1 μm and smaller, while pH values of 9-10 generate more agglomerates of 10-20 μm. As a part of the research work, these findings are implemented in demonstrationscale experimental process setups. For the first time, the Slag2PCC technology is tested in scale of ~70 liters instead of laboratory scale only. Additionally, design of a setup of several hundreds of liters is discussed. For these purposes various process units such as inclined settlers and filters for solids separation, pumps and stirrers for material transfer and mixing as well as gas feeding equipment are dimensioned and developed. Overall emissions reduction of the current industrial processes and good product quality as the main targets, based on the performed partial life cycle assessment (LCA), it is most beneficial to utilize low concentration ammonium salt solutions for the Slag2PCC process. In this manner the post-treatment of the products does not require extensive use of washing and drying equipment, otherwise increasing the CO2 emissions of the process. The low solvent concentration Slag2PCC process causes negative CO2 emissions; thus, it can be seen as a carbon capture and utilization (CCU) method, which actually reduces the anthropogenic CO2 emissions compared to the alternative of not using the technology. Even if the amount of steel slag is too small for any substantial mitigation of global warming, the process can have both financial and environmental significance for individual steel manufacturers as a means to reduce the amounts of emitted CO2 and landfilled steel slag. Alternatively, it is possible to introduce the carbon dioxide directly into the mixture of steel slag and ammonium salt solution. The process would generate a 60-75% pure calcium carbonate mixture, the remaining 25-40% consisting of the residual steel slag. This calcium-rich material could be re-used in ironmaking as a fluxing agent instead of natural limestone. Even though this process option would require less process equipment compared to the Slag2PCC process, it still needs further studies regarding the practical usefulness of the products. Nevertheless, compared to several other CO2 emission reduction methods studied around the world, the within this thesis developed and studied processes have the advantage of existing markets for the produced materials, thus giving also a financial incentive for applying the technology in practice.

The Optimization of Flotation Process Parameters in the Deinking Plant

Tämän diplomityön tavoitteena oli sekundäärisen esiflotaation optimointi Stora Enso Sachsen GmbH:n tehtaalla. Optimoinnin muuttujana käytettiin vaahdon määrää ja optimointiparametreinä ISO-vaaleutta, saantoja sekä tuhkapitoisuutta. Lisäksi tutkittiin flotaatiosakeuden vaikutusta myös muihin tehtaan flotaatioprosesseihin. Kirjallisuusosassa tarkasteltiin flotaatiotapahtumaa, poistettavien partikkeleiden ja ilmakuplien kontaktia, vaahdon muodostumista sekä tärkeimpiä käytössä olevia siistausflotaattoreiden laiteratkaisuja. Kokeellisessa osassa tutkittiin flotaatiosakeuden pienetämisen vaikutuksia tehtaan flotaatioprosesseihin tuhkapitoisuuden, ISO-vaaleuden, valon sironta- ja valon absorpiokerrointen kannalta. Sekundäärisen esiflotaation optimonti suoritettiin muuttamalla vaahdon määrää kolmella erilaisella injektorin koolla, (8 mm, 10 mm ja 13 mm), joista keskimmäinen kasvattaa 30 % massan tilavuusvirtaa ilmapitoisuuden muodossa. Optimonnin tarkoituksena oli kasvattaa hyväksytyn massajakeen ISO-vaaleutta, sekä kasvattaa kuitu- ja kokonaissaantoa sekundäärisessä esiflotaatiossa. Flotaatiosakeuden pienentämisellä oli edullisia vaikutuksia ISO-vaaleuteen ja valon sirontakertoimeen kussakin flotaatiossa. Tuhkapitoisuus pieneni sekundäärisissä flotaatioissa enemmän sakeuden ollessa pienempi, kun taas primäärisissä flotaatiossa vaikutus oli päinvastainen. Valon absorptiokerroin parani jälkiflotaatioissa alhaisemmalla sakeudella, kun taas esiflotaatioissa vaikutus oli päinvastainen. Sekundäärisen esiflotaation optimoinnin tuloksena oli lähes 5 % parempi ISO-vaaleus hyväksytyssä massajakeessa. Kokonaissaanto parani optimoinnin myötä 5 % ja kuitusaanto 2 %. Saantojen nousu tuottaa vuosittaisia säästöjä siistauslaitoksen tuotantokapasiteetin noustessa 0,5 %. Tämän lisäksi sekundäärisessä esiflotaatiossa rejektoituvan massavirran pienentyminen tuottaa lisäsäästöjä tehtaan voimalaitoksella.

Novel Proteins Involved in Dynamics of The Photosynthetic Apparatus

During the past few years, a considerable number of research articles have been published relating to the structure and function of the major photosynthetic protein complexes, photosystem (PS) I, PSII, cytochrome (Cyt) b6f, and adenosine triphosphate (ATP) synthase. Sequencing of the Arabidopsis thaliana (Arabidopsis) genome together with several high-quality proteomics studies has, however, revealed that the thylakoid membrane network of plant chloroplasts still contains a number of functionally unknown proteins. These proteins may have a role as auxiliary proteins guiding the assembly, maintenance, and turnover of the thylakoid protein complexes, or they may be as yet unknown subunits of the photosynthetic complexes. Novel subunits are most likely to be found in the NAD(P)H dehydrogenase (NDH) complex, the structure and function of which have remained obscure in the absence of detailed crystallographic data, thus making this thylakoid protein complex a particularly interesting target of investigation. In this thesis, several novel thylakoid-associated proteins were identified by proteomics-based methods. The major goal of characterization of the stroma thylakoid associated polysome-nascent chain complexes was to determine the proteins that guide the dynamic life cycle of PSII. In addition, a large protein complex of ≥ 1,000 kDa, residing in the stroma thylakoid, was characterized in greater depth and it was found to be a supercomplex composed of the PSI and NDH complexes. A set of newly identified proteins from Arabidopsis thylakoids was subjected to detailed characterization using the reverse genetics approach and extensive biochemical and biophysical analysis. The role of the novel proteins, either as auxiliary proteins or subunits of the photosynthetic protein complexes, was revealed. Two novel thylakoid lumen proteins, TLP18.3 and AtCYP38, function as auxiliary proteins assisting specific steps of the assembly/repair of PSII. The role of the 10-kDa thylakoid lumen protein PsbR is related to the optimization of oxygen evolution of PSII by assisting the assembly of the PsbP protein. Two integral thylakoid membrane proteins, NDH45 and NDH48, are novel subunits of the chloroplast NDH complex. Finally, the thylakoid lumen immunophilin AtCYP20-2 is suggested to interact with the NDH complex, instead of PSII as was hypothesized earlier.

Novel Robot Solutions for Carrying out Field Joint Welding and Machining in the Assembly of the Vacuum Vessel of ITER

It is necessary to use highly specialized robots in ITER (International Thermonuclear Experimental Reactor) both in the manufacturing and maintenance of the reactor due to a demanding environment. The sectors of the ITER vacuum vessel (VV) require more stringent tolerances than normally expected for the size of the structure involved. VV consists of nine sectors that are to be welded together. The vacuum vessel has a toroidal chamber structure. The task of the designed robot is to carry the welding apparatus along a path with a stringent tolerance during the assembly operation. In addition to the initial vacuum vessel assembly, after a limited running period, sectors need to be replaced for repair. Mechanisms with closed-loop kinematic chains are used in the design of robots in this work. One version is a purely parallel manipulator and another is a hybrid manipulator where the parallel and serial structures are combined. Traditional industrial robots that generally have the links actuated in series are inherently not very rigid and have poor dynamic performance in high speed and high dynamic loading conditions. Compared with open chain manipulators, parallel manipulators have high stiffness, high accuracy and a high force/torque capacity in a reduced workspace. Parallel manipulators have a mechanical architecture where all of the links are connected to the base and to the end-effector of the robot. The purpose of this thesis is to develop special parallel robots for the assembly, machining and repairing of the VV of the ITER. The process of the assembly and machining of the vacuum vessel needs a special robot. By studying the structure of the vacuum vessel, two novel parallel robots were designed and built; they have six and ten degrees of freedom driven by hydraulic cylinders and electrical servo motors. Kinematic models for the proposed robots were defined and two prototypes built. Experiments for machine cutting and laser welding with the 6-DOF robot were carried out. It was demonstrated that the parallel robots are capable of holding all necessary machining tools and welding end-effectors in all positions accurately and stably inside the vacuum vessel sector. The kinematic models appeared to be complex especially in the case of the 10-DOF robot because of its redundant structure. Multibody dynamics simulations were carried out, ensuring sufficient stiffness during the robot motion. The entire design and testing processes of the robots appeared to be complex tasks due to the high specialization of the manufacturing technology needed in the ITER reactor, while the results demonstrate the applicability of the proposed solutions quite well. The results offer not only devices but also a methodology for the assembly and repair of ITER by means of parallel robots.

Supersaturation-controlled crystallization

Identification of product requirements and quality, together with the management of production are key issues in chemical engineering. Quality control of crystalline products is part of the quality of many industrially manufactured products like paper, paintings, medicines and fertilizers. In most crystallization cases, quality is described with the size, polymorph, shape and purity of the crystal. The chemical composition, hydrodynamics and driving force, together with the operating temperature are in a key position when the properties of a crystalline product are controlled with the crystallization process. This study concentrates on managing the identified properties of a crystalline product with the control of a driving force. The controlling of the driving force can be based on the change of solubility or the change of concentration. Solubility can be changed with temperature, pressure and an antisolvent. The concentration of crystallizing compound, the solute can be changed with the evaporation of the solvent and with the addition of a reagent. The present study focuses on reagent addition and temperature change as methods of changing the level of the driving force. Three control structures for direct control of supersaturation are built, one for cooling crystallization and two for reactive crystallization. Closed loop feedback control structures are based on the measurement of the solute concentration with attenuated total reflection - Fourier transform infrared spectrometer. The details of the reagent feed are analyzed with experimental studies and with results of computational fluid dynamic simulations of the inert particle pulse in the premixer and inert particle injection to the mixing tank. Nucleation in conditions of controlled reactive crystallization is analyzed with Nielsen’s equation of homogeneous nucleation. The resulting control systems, based on regulation of supersaturation, can be used to produce the desired polymorph of an organic product. The polymorph composition of product crystals is controlled repeatably with the decision of a set value of supersaturation level.

Spectroscopic monitoring during laser welding of aluminium alloy

The mechanical properties of aluminium alloys are strongly influenced by the alloying elements and their concentration. In the case of aluminium alloy EN AW-6060 the main alloying elements are magnesium and silicon. The first goal of this thesis was to determine stability, repeatability and sensitivity as figures of merit of the in-situ melt identification technique. In this study the emissions from the laser welding process were monitored with a spectrometer. With the information produced by the spectrometer, quantitative analysis was conducted to determine the figures of merit. The quantitative analysis concentrated on magnesium and aluminium emissions and their relation. The results showed that the stability of absolute intensities was low, but the normalized magnesium emissions were quite stable. The repeatability of monitoring magnesium emissions was high (about 90 %). Sensitivity of the in-situ melt identification technique was also high. As small as 0.5 % change in magnesium content was detected by the spectrometer. The second goal of this study was to determine the loss of mass during deep penetration laser welding. The amount of magnesium in the material was measured before and after laser welding to determine the loss of magnesium. This study was conducted for aluminium alloy with nominal magnesium content of 0-10 % and for standard material EN AW-6060 that was welded with filler wire AlMg5. It was found that while the magnesium concentration in the material changed, the loss of magnesium remained fairly even. Also by feeding filler wire, the behaviour was similar. Thirdly, the reason why silicon had not been detected in the emission spectrum needed to be explained. Literature research showed that the amount of energy required for silicon to excite is considerably higher compared to magnesium. The energy input in the used welding process is insufficient to excite the silicon atoms.

The value of digitalization of services in the new service development

The purpose of this thesis is to study factors that have an impact on the company’s capabilities to identify and analyze the value of digitalization of services during the early stages of service development process and evaluate them from the perspective of a case company. The research problem was defined: “How digitalization of services affects delivering the services of the future?” The research method of this thesis was based on the qualitative case study which aimed to study both company’s and customer’s set of values. The study included a literature review and a development study. The empirical research part consisted of analyzing three existing services, specifying a new digital service concept and its feasibility analysis as part of a business requirement phase. To understand the set of values, 10 stakeholder interviews were conducted and earlier customer surveys were utilized, and additionally, a number of meetings were conducted with the case company representatives to develop service concept, and evaluate the findings. The impact of the early stages of service development process discovered to reflect directly in the capabilities of the case company to identify and create customer value were related to the themes presented in the literature review. In order to specify the value achieved from the digitalization the following areas of strategic background elements were deepened during the study: Innovations, customer understanding and business service. Based on the findings, the study aims to enhance the case company’s capability to identify and evaluate the impact of the digitalization in delivering services of the future. Recognizing the value of digital service before the beginning of the development project is important to the businesses of both customer and provider. By exploring the various levels of digitalization one can get the overall picture of the value gained from utilizing digital opportunities. From the development perspective, the process of reviewing and discovering the most promising opportunities and solutions is the key step in order to deliver superior services. Ultimately, a company should understand the value outcome determination of the individual services as well as their digital counterparts.

Novel Methods for Error Modeling and Parameter Identification of a Redundant Serial-Parallel Hybrid Robot

To obtain the desirable accuracy of a robot, there are two techniques available. The first option would be to make the robot match the nominal mathematic model. In other words, the manufacturing and assembling tolerances of every part would be extremely tight so that all of the various parameters would match the “design” or “nominal” values as closely as possible. This method can satisfy most of the accuracy requirements， but the cost would increase dramatically as the accuracy requirement increases. Alternatively, a more cost-effective solution is to build a manipulator with relaxed manufacturing and assembling tolerances. By modifying the mathematical model in the controller, the actual errors of the robot can be compensated. This is the essence of robot calibration. Simply put, robot calibration is the process of defining an appropriate error model and then identifying the various parameter errors that make the error model match the robot as closely as possible. This work focuses on kinematic calibration of a 10 degree-of-freedom (DOF) redundant serial-parallel hybrid robot. The robot consists of a 4-DOF serial mechanism and a 6-DOF hexapod parallel manipulator. The redundant 4-DOF serial structure is used to enlarge workspace and the 6-DOF hexapod manipulator is used to provide high load capabilities and stiffness for the whole structure. The main objective of the study is to develop a suitable calibration method to improve the accuracy of the redundant serial-parallel hybrid robot. To this end, a Denavit–Hartenberg (DH) hybrid error model and a Product-of-Exponential (POE) error model are developed for error modeling of the proposed robot. Furthermore, two kinds of global optimization methods, i.e. the differential-evolution (DE) algorithm and the Markov Chain Monte Carlo (MCMC) algorithm, are employed to identify the parameter errors of the derived error model. A measurement method based on a 3-2-1 wire-based pose estimation system is proposed and implemented in a Solidworks environment to simulate the real experimental validations. Numerical simulations and Solidworks prototype-model validations are carried out on the hybrid robot to verify the effectiveness, accuracy and robustness of the calibration algorithms.

Dental Health in Preschool and Schoolchildren in Relation to Dental Fear and Some Fear-Related Factors, and the Outcome of a Caries Prevention Program in Offspring of Fearful Mothers

Dental caries and dental fear and anxiety (DFA) are common interrelated problems but so far little is known about these problems in Estonia. The aim was to study dental health in relation to DFA, some fear-related factors, and to study the effect of a caries prevention program in children of fearful mothers. Dental health and DFA were assessed in two Estonian [2-4-year-olds (n=472) and 8-10-year-olds (n=344)], and the effect of some medical conditions on DFA in one Finnish child group [3-year-olds (n=148)]. 120 mother-child-pairs participated in the xylitol-based prevention program. Dental health was examined using the WHO or the ICDAS criteria and expressed as dmft/DMFT-indices. The modified children’s fear survey schedule dental subscale (MCFSS-DS) was used to assess DFA of schoolchildren, one single question to assess parental DFA, and the Corah’s dental anxiety scale (DAS) to assess DFA of mothers in the prevention study. Dentine caries was diagnosed in 42% of the 2-4-year-old and in 93% of the 8-10-year-old Estonian children. DFA of 8-10-year-olds (17%) was associated with experience of dental treatment, and maternal and paternal DFA. Dental apprehension at 9 years of age was associated with frequent exposure to invasive medical care. The xylitol-based prevention was successful irrespective of poor dental hygiene habits and maternal severe DFA. In conclusion, experience of operative dental treatment and DFA of Estonian children were closely associated. Invasive medical care and parental DFA were also linked to children’s DFA. Habitual use of xylitol by mothers was effective in preventing caries even in children of severely fearful mothers.

Assessment of Young Learners’ English Proficiency in Bilingual Content Instruction CLIL

This applied linguistic study in the field of second language acquisition investigated the assessment practices of class teachers as well as the challenges and visions of language assessment in bilingual content instruction (CLIL) at primary level in Finnish basic education. Furthermore, pupils’ and their parents’ perceptions of language assessment and LangPerform computer simulations as an alternative, modern assessment method in CLIL contexts were examined. The study was conducted for descriptive and developmental purposes in three phases: 1) a CLIL assessment survey; 2) simulation 1; and 3) simulation 2. All phases had a varying number of participants. The population of this mixed methods study were CLIL class teachers, their pupils and the pupils’ parents. The sampling was multi-staged and based on probability and random sampling. The data were triangulated. Altogether 42 CLIL class teachers nationwide, 109 pupils from the 3rd, 4th and 5th grade as well as 99 parents from two research schools in South-Western Finland participated in the CLIL assessment survey followed by an audio-recorded theme interview of volunteers (10 teachers, 20 pupils and 7 parents). The simulation experimentations 1 and 2 produced 146 pupil and 39 parental questionnaires as well as video interviews of volunteered pupils. The data were analysed both quantitatively using percentages and numerical frequencies and qualitatively employing thematic content analysis. Based on the data, language assessment in primary CLIL is not an established practice. It largely appears to be infrequent, incidental, implicit and based on impressions rather than evidence or the curriculum. The most used assessment methods were teacher observation, bilingual tests and dialogic interaction, and the least used were portfolios, simulations and peer assessment. Although language assessment was generally perceived as important by teachers, a fifth of them did not gather assessment information systematically, and 38% scarcely gave linguistic feedback to pupils. Both pupils and parents wished to receive more information on CLIL language issues; 91% of pupils claimed to receive feedback rarely or occasionally, and 63% of them wished to get more information on their linguistic coping in CLIL subjects. Of the parents, 76% wished to receive more information on the English proficiency of their children and their linguistic development. This may be a response to indirect feedback practices identified in this study. There are several challenges related to assessment; the most notable is the lack of a CLIL curriculum, language objectives and common ground principles of assessment. Three diverse approaches to language in CLIL that appear to affect teachers’ views on language assessment were identified: instrumental (language as a tool), dual (language as a tool and object of learning) and eclectic (miscellaneous views, e.g. affective factors prioritised). LangPerform computer simulations seem to be perceived as an appropriate alternative assessment method in CLIL. It is strongly recommended that the fundamentals for assessment (curricula and language objectives) and a mutual assessment scheme should be determined and stakeholders’ knowledge base of CLIL strengthened. The principles of adequate assessment in primary CLIL are identified as well as several appropriate assessment methods suggested.

Flexible multibody dynamics and intelligent control of a hydraulically driven hybrid redundant robot machine

The assembly and maintenance of the International Thermonuclear Experimental Reactor (ITER) vacuum vessel (VV) is highly challenging since the tasks performed by the robot involve welding, material handling, and machine cutting from inside the VV. The VV is made of stainless steel, which has poor machinability and tends to work harden very rapidly, and all the machining operations need to be carried out from inside of the ITER VV. A general industrial robot cannot be used due to its poor stiffness in the heavy duty machining process, and this will cause many problems, such as poor surface quality, tool damage, low accuracy. Therefore, one of the most suitable options should be a light weight mobile robot which is able to move around inside of the VV and perform different machining tasks by replacing different cutting tools. Reducing the mass of the robot manipulators offers many advantages: reduced material costs, reduced power consumption, the possibility of using smaller actuators, and a higher payload-to-robot weight ratio. Offsetting these advantages, the lighter weight robot is more flexible, which makes it more difficult to control. To achieve good machining surface quality, the tracking of the end effector must be accurate, and an accurate model for a more flexible robot must be constructed. This thesis studies the dynamics and control of a 10 degree-of-freedom (DOF) redundant hybrid robot (4-DOF serial mechanism and 6-DOF 6-UPS hexapod parallel mechanisms) hydraulically driven with flexible rods under the influence of machining forces. Firstly, the flexibility of the bodies is described using the floating frame of reference method (FFRF). A finite element model (FEM) provided the Craig-Bampton (CB) modes needed for the FFRF. A dynamic model of the system of six closed loop mechanisms was assembled using the constrained Lagrange equations and the Lagrange multiplier method. Subsequently, the reaction forces between the parallel and serial parts were used to study the dynamics of the serial robot. A PID control based on position predictions was implemented independently to control the hydraulic cylinders of the robot. Secondly, in machining, to achieve greater end effector trajectory tracking accuracy for surface quality, a robust control of the actuators for the flexible link has to be deduced. This thesis investigates the intelligent control of a hydraulically driven parallel robot part based on the dynamic model and two schemes of intelligent control for a hydraulically driven parallel mechanism based on the dynamic model: (1) a fuzzy-PID self-tuning controller composed of the conventional PID control and with fuzzy logic, and (2) adaptive neuro-fuzzy inference system-PID (ANFIS-PID) self-tuning of the gains of the PID controller, which are implemented independently to control each hydraulic cylinder of the parallel mechanism based on rod length predictions. The serial component of the hybrid robot can be analyzed using the equilibrium of reaction forces at the universal joint connections of the hexa-element. To achieve precise positional control of the end effector for maximum precision machining, the hydraulic cylinder should be controlled to hold the hexa-element. Thirdly, a finite element approach of multibody systems using the Special Euclidean group SE(3) framework is presented for a parallel mechanism with flexible piston rods under the influence of machining forces. The flexibility of the bodies is described using the nonlinear interpolation method with an exponential map. The equations of motion take the form of a differential algebraic equation on a Lie group, which is solved using a Lie group time integration scheme. The method relies on the local description of motions, so that it provides a singularity-free formulation, and no parameterization of the nodal variables needs to be introduced. The flexible slider constraint is formulated using a Lie group and used for modeling a flexible rod sliding inside a cylinder. The dynamic model of the system of six closed loop mechanisms was assembled using Hamilton’s principle and the Lagrange multiplier method. A linearized hydraulic control system based on rod length predictions was implemented independently to control the hydraulic cylinders. Consequently, the results of the simulations demonstrating the behavior of the robot machine are presented for each case study. In conclusion, this thesis studies the dynamic analysis of a special hybrid (serialparallel) robot for the above-mentioned special task involving the ITER and investigates different control algorithms that can significantly improve machining performance. These analyses and results provide valuable insight into the design and control of the parallel robot with flexible rods.

Narrow Gap flux-cored arc welding of high strength shipbuilding steels

This thesis is part of the Arctic Materials Technologies Development –project. The research of the thesis was done in cooperation with Arctech Helsinki Shipyard, Lappeenranta University of Technology and Kemppi Oy. Focus of the thesis was to study narrow gap flux-cored arc welding of two high strength steels with three different groove angles of 20°, 10° and 5°. Welding of the 25 mm thick E500 TMCP and 10 mm thick EH36 steels was mechanized and Kemppi WisePenetration and WiseFusion processes were tested with E500 TMCP steel. EH36 steel test pieces were welded without Wise processes. Shielding gases chosen were carbon dioxide and a mixture of argon and carbon dioxide. Welds were tested with non-destructive and destructive testing methods. Radiographic, visual, magnetic particle and liquid penetrant testing proved that welds were free from imperfections. After non-destructive testing, welds were tested with various destructive testing methods. Impact strength, bending, tensile strength and hardess tests proved that mechanized welding and Wise processes produced quality welds with narrower gap. More inconsistent results were achieved with test pieces welded without Wise processes. Impact test results of E500 TMCP exceeded the 50 J limit on weld, set by Russian Maritime Register of Shipping. EH36 impact test results were much closer to the limiting values of 34 J on weld and 47 on HAZ. Hardness values of all test specimens were below the limiting values. Bend testing and tensile testing results fulfilled the the Register requirements. No cracking or failing occurred on bend test specimens and tensile test results exceeded the Register limits of 610 MPa for E500 TMCP and 490 MPa for EH36.

Continuous Counter-current Solvent Extraction of Magnesium and Calcium from Lithium-rich Brine

Solvent extraction of calcium and magnesium impurities from a lithium-rich brine (Ca ~ 2,000 ppm, Mg ~ 50 ppm, Li ~ 30,000 ppm) was investigated using a continuous counter-current solvent extraction mixer-settler set-up. The literature review includes a general review about resources, demands and production methods of Li followed by basics of solvent extraction. Experimental section includes batch experiments for investigation of pH isotherms of three extractants; D2EHPA, Versatic 10 and LIX 984 with concentrations of 0.52, 0.53 and 0.50 M in kerosene respectively. Based on pH isotherms LIX 984 showed no affinity for solvent extraction of Mg and Ca at pH ≤ 8 while D2EHPA and Versatic 10 were effective in extraction of Ca and Mg. Based on constructed pH isotherms, loading isotherms of D2EHPA (at pH 3.5 and 3.9) and Versatic 10 (at pH 7 and 8) were further investigated. Furthermore based on McCabe-Thiele method, two extraction stages and one stripping stage (using HCl acid with concentration of 2 M for Versatic 10 and 3 M for D2EHPA) was practiced in continuous runs. Merits of Versatic 10 in comparison to D2EHPA are higher selectivity for Ca and Mg, faster phase disengagement, no detrimental change in viscosity due to shear amount of metal extraction and lower acidity in stripping. On the other hand D2EHPA has less aqueous solubility and is capable of removing Mg and Ca simultaneously even at higher Ca loading (A/O in continuous runs > 1). In general, shorter residence time (~ 2 min), lower temperature (~23 °C), lower pH values (6.5-7.0 for Versatic 10 and 3.5-3.7 for D2EHPA) and a moderately low A/O value (< 1:1) would cause removal of 100% of Ca and nearly 100% of Mg while keeping Li loss less than 4%, much lower than the conventional precipitation in which 20% of Li is lost.

Green diesel synthesis by hydrodeoxygenation of lipids extracted from Chlorella algae in supercritical hexane

Lipids were extracted from Chlorella algae with supercritical hexane. The high lipids yield of approximately 10% was obtained at optimum conditions of 300 rpm stirring speed and 2 h duration compared to the total contents of lipids being 12%. Furthermore, an easiness of hexane recovery may be considered as economically and ecologically attractive. For the first time, in the current work catalytic hydrodeoxygenation (HDO) of Chlorella algal lipids was studied over 5 wt% Ni/H-Y-80 and 5 wt% Ni/SiO2 at 300 C and under 30 bar total pressure in H2. A comparative HDO of stearic acid was carried out under similar conditions. The conversion of lipids was about 35% over 5 wt% Ni/H-Y-80 after 6h, whereas, 5 wt% Ni/SiO2 was totally deactivated after 60 min. The selectivity to hydrocarbons (C15-C18) is 6%. As a comparison, complete conversion of stearic acid over 5 wt% Ni/H-Y-80 was achieved in 6 h. The transformation of lipids proceeded mostly via hydrogenation and hydrolysis with formation of free fatty acid (FFA). The lower activity might be attributed to deactivation of catalysts caused by chlorophylls and carotenoids. Even though the conversion is low, future studies in HDO of lipids extracted from other algae species having higher lipid content could be proposed. Coke resistant catalyst might be considered to improve catalytic activity.