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

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

Operointialueen huomioiminen risteilylaivan sähkötaseessa

Kiristyvät päästörajoitukset ja muuttuvat säädökset ovat muokanneet laivanrakennusalaa energiatehokkaampaan ja ympäristöystävällisempään suuntaan. Energiatehokkuutta tutkitaan yksittäisistä laiteratkaisuista laivan operointitasolle asti. Tämä työ on tehty osana STX Finland Oy:n laivojen energiatehokkuuden tutkimusta. Työn tarkoituksena oli uudistaa laivojen sähkötaseen laskennassa käytettyjä kuormitustaulukoita ja kehittää operointialueen vaikutuksia huomioiva laskentamenetelmä. Uudistuksen taustalla oli tieto operointialueiden ympäristöolosuhteiden vaikutuksista sähkönkulutukseen ja työn tarkoituksena oli mahdollistaa suunnittelun myöhäisemmässä vaiheessa tehtävä operointialuekohtainen sähkönkulutustarkastelu. Sähkötaseen laskenta haluttiin vastaamaan enemmän todellista sähkönkulutusta. Aikaisemmin käytetystä mitoitusperusteisesta laskennasta haluttiin siirtyä todellisempien kuormien arviointiin laitteiden ja muuntajien turhan ylimitoituksen poistamiseksi. Kuormitustaulukoiden toimintaa yksinkertaistettiin ja taulukoista tehtiin helpommin mukautuvia, jotta erilaisten operointitilanteiden vertailu olisi mahdollista. Perinteisen taselaskennan rinnalle kehitettiin operointialueiden vaikutuksia huomioivat laskentataulukot. Uudet taulukot huomioivat komponenttien sähkönkulutuksen prosentuaalisen muutoksen operointialueittain sekä yksilöllisesti että kulutusryhmittäin. Laskentataulukoiden yhteyteen tehtiin kuvaajat havainnollistamaan alueittaisia kulutuseroja.

Modeling and Control of the Power Conversion Unit in a Solid Oxide Fuel Cell Environment

In this doctoral thesis, a power conversion unit for a 10 kWsolid oxide fuel cell is modeled, and a suitable control system is designed. The need for research was identified based on an observation that there was no information available about the characteristics of the solid oxide fuel cell from the perspective of power electronics and the control system, and suitable control methods had not previously been studied in the literature. In addition, because of the digital implementation of the control system, the inherent characteristics of the digital system had to be taken into account in the characteristics of the solid oxide fuel cell (SOFC). The characteristics of the solid oxide fuel cell as well the methods for the modeling and control of the DC/DC converter and the grid converter are studied by a literature survey. Based on the survey, the characteristics of the SOFC as an electrical power source are identified, and a solution to the interfacing of the SOFC in distributed generation is proposed. A mathematical model of the power conversion unit is provided, and the control design for the DC/DC converter and the grid converter is made based on the proposed interfacing solution. The limit cycling phenomenon is identified as a source of low-frequency current ripple, which is found to be insignificant when connected to a grid-tied converter. A method to mitigate a second harmonic originating from the grid interface is proposed, and practical considerations of the operation with the solid oxide fuel cell plant are presented. At the theoretical level, the thesis discusses and summarizes the methods to successfully derive a model for a DC/DC converter, a grid converter, and a power conversion unit. The results of this doctoral thesis can also be used in other applications, and the models and methods can be adopted to similar applications such as photovoltaic systems. When comparing the results with the objectives of the doctoral thesis, we may conclude that the objectives set for the work are met. In this doctoral thesis, theoretical and practical guidelines are presented for the successful control design to connect a SOFC-based distributed generation plant to the utility grid.

Determination of chlorophenols from water by solid phase microextraction - ion mobility spectrometry (SPME-IMS)

Chlorophenols have been classified as possible carcinogens for humans. Chlorophenols have been used as pesticides and wood preservatives. In Finland, during 1930 – 1980s, saw mills used KY-5 wood preservative that contained 2,4,6-TCP, 2,3,4,6-TeCP and PCP. Especially in Finland chlorophenols have entered the environment by leaking from contaminated grounds of old saw mills. Although chlorophenol concentrations found in environment do not cause acute concern, long term exposure can increase the risk of cancer. SPME is relatively cheap and simple sampling method, in which the sample extraction and concentration are performed in a single step. Solvents are not required in SPME. IMS is based on the detection of sample ion drift times. Based on the drift times, reduced mobilities are calculated, which are comparable despite the measurement conditions. SPME-IMS coupling has not been used earlier in the determination of chlorophenols from water samples. The scope of this work was to study, if SPME-IMS system is suitable for detecting chloro-phenols from water samples. The aim was to determine the most optimal extraction condi-tions, which were then applied to real water samples. Following detection limits were deter-mined: 2,4,6-TCP: 0.33 mg/l; 2,3,4,6-TeCP: 0.63 mg/l and PCP: 1.63 mg/l. Detection limits were high compared to the highest possible chlorophenol concentration that is allowed in Finnish drinking water, 10 μg/l. Detected concentrations from water sample differed from verified concentrations in the case of 2,3,4,6-TeCP by 4.6 % and in the case of 2,4,6-TCP by 48.4 %. Based on the results it can be said that SPME-IMS setup is suitable for preliminary analysis of mg/l chlorophenol concentrations from water samples.

Aktiivisen verkkosillan tuottaman yhteismuotoisen jännitteen vaimentaminen kaksitasoisessa, jännitevälipiirillisessä, taajuusmuuttajatopologiassa

Pulssinleveysmoduloidun vaihtosuuntaajan hyötysuhteen parantaminen ja kytkentätaajuuden suurentaminen ovat johtaneet lähtöjännitteen suuritaajuiseen taajuussisältöön kaksitasoisessa, jännitevälipiirillisessä taajuusmuuttajatopologiassa. Kasvava tarve siirtää tehoa myös verkkoon päin on lisännyt aktiivisen verkkosillan käyttöä. Kaksitasoisen aktiivisen verkkosillan vaikutuksesta DC-välipiirin keskipisteen ja kolmivaiheisen kuorman tähtipisteen välinen jännite on nollasta poikkeava aiheuttaen suurentuneen yhteismuotoisen jännitteen taajuusmuuttajan lähtöön ja verkon puolelle. Lisäksi yhteismuotoisten jännitteiden aiheuttamat kytkentätaajuiset häiriövirrat voivat aiheuttaa vikavirtasuojien tahatonta laukeamista, vaikeuttaa EMC-standardien vaatimusten täyttämistä, lisätä moottorin käämieristyksien rasitusta ja mahdollisuutta moottorin laakerivaurioille. Diplomityössä tutkitaan aktiivisen ja passiivisen verkkosillan tuottamaa yhteismuotoista jännitettä simuloinneilla. Esitellään aikaisempaa tutkimustietoa yhteismuotoisen jännitteen ja virran vaimennusratkaisuista aktiivista verkkosiltaa käytettäessä. Tutkimustiedon pohjalta suunnitellaan koelaitteistolle soveltuva suodin. Suotimen toiminta testataan simuloinnein sekä kokeellisin mittauksin. Tehdyt mittaukset osoittavat, että suunniteltu suodin vaimentaa yhteismuotoista jännitettä noin 20 dB verkkosillan kytkentätaajuudella ja tämän jälkeen yli 20 dB/dekadi taajuuteen 100 kHz asti. Lisäksi yhteismuotoisen virran suuruus syöttökaapelin kautta pieneni ehdotetun suotimen vaikutuksesta.

Enabling Change in Universities: Enhancing Education for Sustainable Development with Tools for Quality Assurance

Enabling Change in Universities: Enhancing Education for Sustainable Development with Tools for Quality Assurance This thesis deals with enabling change in universities, more explicitly enhancing education for sustainable development with tools for quality assurance. Change management is a discipline within management that was developed in the 1980s because business changed from being predictable to unpredictable. The PEST mnemonic is a method to categorize factors enabling change; such as political, economic, socio-cultural and technological factors, which all affect higher education. A classification of a change, in either hard or soft, can help understanding the type of change that an organization is facing. Hard changes are more applied to problems that have clear objectives and indicators, with a known cause of the problem. Soft changes are applied to larger problems that affect the entire organization or beyond it. The basic definition for sustainable development is: the future generations should have similar opportunities as the previous. The UN has set as a global goal an integration of education for sustainable development (ESD) at all levels of education during 2005- 2014. The goal is set also in universities, the graduates of which are future leaders for all labor markets. The objective for ESD in higher education is that graduates obtain the competence to take economic, social and environmental costs and benefits into account when making decisions. Knowledge outcomes should aim for systematic and holistic thinking, which requires cross disciplinary education. So far, the development of ESD has not achieved its goals. The UN has identified a need for more transdisclipnary research in ESD. A joint global requirement for universities is quality assurance, the aim of which is to secure and improve teaching and learning. Quality, environmental and integrated management systems are used by some universities for filling the quality assurance requirements. The goal of this thesis is to open up new ways for enhancing ESD in universities, beyond the forerunners; by exploring how management systems could be used as tools for promoting ESD. The thesis is based on five studies. In the first study, I focus on if and how tools for quality assurance could be benefitted for promoting ESD. It is written from a new perspective, the memetic, for reaching a diversity of faculty. A meme is an idea that diffuses from brain to brain. It can be applied for cultural evolution. It is a theory that is based on the evolutionary theory by Darwin, applied for social sciences. In the second Paper, I present the results from the development of the pilot process model for enhancing ESD with management systems. The development of the model is based on a study that includes earlier studies, a survey in academia and an analysis of the practice in 11 universities in the Nordic countries. In the third study, I explore if the change depends on national culture or if it is global. It is a comparative study on both policy and implementation level, between the Nordic countries and China. The fourth study is a single case study based on change management. In this study, I identify what to consider in order to enable the change: enhancing ESD with tools for quality assurance in universities. In the fifth Paper, I present the results of the process model for enhancing ESD with management systems. The model was compared with identified drivers and barriers for enhancing ESD and for implementing management systems. Finally, the process model was piloted and applied for identifying sustainability aspects in curricula. Action research was chosen as methodology because there are not already implemented approaches using quality management for promoting ESD, why the only way to study this is to make it happen. Another reason for choosing action research is since it is essential to involve students and faculty for enhancing ESD. Action based research consists of the following phases: a) diagnosing, b) planning action, c) taking action and d) evaluating action. This research was made possible by a project called Education for Sustainable Development in Academia in the Nordic countries, ESDAN, in which activities were divided into these four phases. Each phase ended with an open seminar, where the results of the study were presented. The objective for the research project was to develop a process for including knowledge in sustainable development in curricula, which could be used in the quality assurance work. Eleven universities from the Nordic countries cooperated in the project. The aim was, by applying the process, to identify and publish examples of relevant sustainability aspects in different degree programs in universities in the Nordic countries. The project was partly financed by the Nordic Council of Ministers and partly by the participating pilot universities. Based on the results of my studies, I consider that quality, environmental and integrated management systems can be used for promoting ESD in universities. Relevant sustainability aspects have been identified in different fields of studies by applying the final process model. The final process model was compared with drivers and barriers for enhancing ESD and for implementing management systems in universities and with succeeding with management systems in industry. It corresponds with these, meaning that drivers are taken into account and barriers tackled. Both ESD and management systems in universities could be considered successful memes, which can reflect an effective way of communication among individuals. I have identified that management systems could be used as tools for hard changes and to support the soft change of enhancing ESD in universities with management system. Based on the change management study I have summarized recommendations on what to consider in order to enable the studied change. The main practical implications of the results are that the process model could be applied for assessment, benchmarking and communication of ESD, connected to quality assurance, when applied. This is possible because the information can be assembled in one picture, which facilitates comparison. The memetic approach can be applied for structuring. It is viable to make comparative studies between cultures, for getting insight in special characteristics of the own culture. Action based research is suitable for involving faculty. Change management can be applied for planning a change, which both enhancing ESD and developing management systems are identified to be.

Dynamic capabilities as enablers of value co-creation between an MBA school and its students

This study presents an understanding of how a U.S. based, international MBA school has been able to achieve competitive advantage within a relatively short period of time. A framework is built to comprehend how the dynamic capability and value co-creation theories are connected and to understand how the dynamic capabilities have enabled value co-creation to happen between the school and its students, leading to such competitive advantage for the school. The data collection method followed a qualitative single-case study with a process perspective. Seven semi-structured interviews were made in September and October of 2015; one current employee of the MBA school was interviewed, with the other six being graduates and/or former employees of the MBA school. In addition, the researcher has worked as a recruiter at the MBA school, enabling to build bridges and a coherent whole of the empirical findings. Data analysis was conducted by first identifying themes from interviews, after which a narrative was written and a causal network model was built. Thus, a combination of thematic analysis, narrative and grounded theory were used as data analysis methods. This study finds that value co-creation is enabled by the dynamic capabilities of the MBA school; also capabilities would not be dynamic if value co-creation did not take place. Thus, this study presents that even though the two theories represent different level analyses, they are intertwined and together they can help to explain competitive advantage. The MBA case school’s dynamic capabilities are identified to be the sales & marketing capabilities and international market creation capabilities, thus the study finds that the MBA school does not only co-create value with existing students (customers) in the school setting, but instead, most of the value co-creation happens between the school and the student cohorts (network) already in the recruiting phase. Therefore, as a theoretical implication, the network should be considered as part of the context. The main value created seem to lie in the MBA case school’s international setting & networks. MBA schools around the world can learn from this study; schools should try to find their own niche and specialize, based on their own values and capabilities. With a differentiating focus and a unique and practical content, the schools can and should be well-marketed and proactively sold in order to receive more student applications and enhance competitive advantage. Even though an MBA school can effectively be treated as a business, as the study shows, the main emphasis should still be on providing quality education. Good content with efficient marketing can be the winning combination for an MBA school.

Mass transfer and reaction kinetics in single droplet systems

As reactive extraction grown more and more popular in a variety of technological applications, optimizing its performance becomes more and more important. The process of complex formation is affected by a great number of both physical and chemical properties of all the components involved, and sometimes their interference with one another makes improving the effectiveness of such processes very difficult. In this Master’s Theses, the processes of complex formation between the aqueous phase - represented by copper sulfate water solution, and organic phase – represented by Acorga M5640 solvent extractor, were studied in order to establish the effect these components have on reactive extraction performance and to determine which step is bottlenecking the process the most.

Scanning the future of Single Euro Payment Area – towards cashless payment methods

The future of paying in the age of digitalization is a topic that includes varied visions. This master’s thesis explores images of the future of paying in the Single Euro Payment Area (SEPA) up to 2020 and 2025 through the views of experts specialized in paying. This study was commissioned by a credit management company in order to obtain more detailed information about the future of paying. Specifically, this thesis investigates what could be the most used payment methods in the future, what items could work as a medium of exchange in 2020 and how will they evolve towards the year 2025. Changing consumer behavior, trends connected to payment methods, security and private issues of new cashless payment methods were also part of this study. In the empirical part of the study the experts’ ideas about probable and preferable future images of paying were investigated through a two-round Disaggregative Delphi method. The questionnaire included numeric statements and open questions. Three alternative future images were created with the help of cluster analysis: “Unsurprising Future”, “Technology Driven Future” and “The Age of the Customer”. The plausible images had similarities and differences, which were reflected to the previous studies in the literature review. The study’s findings were formed based on the images of futures’ similarities and to the open questions answers that were received from the questionnaire. The main conclusion of the study was that development of technology will unify and diversify SEPA; the trend in 2020 seems to be towards more cashless payment methods but their usage depends on the countries’ financial possibilities and customer preferences. Mobile payments, cards and cash will be the main payment methods but the banks will have competitors from outside the financial sector. Wearable payment methods and NFC technology are seen as widely growing trends but subcutaneous payment devices will likely keep their niche position until 2025. In the meantime, security and private issues are seen to increase because of identity thefts and various frauds. Simultaneously, privacy will lose its meaning to younger consumers who are used to sharing their transaction and personal data with third parties in order to get access to attractive services. Easier access to consumers’ transaction data will probably open the door for hackers and cause new risks in paying processes. There exist many roads to future, and this study was not an attempt to give any complete answers about it even if some plausible assumptions about the future’s course were provided.