Military crisis management in the next decade (2020-2030) : inducing consent or relying on compliance?

The most outstanding conceptual challenge of modern crisis management is the principle of consent. It is not a problem only at the operational level - it challenges the entire decision-making structures of crisis management operations. In post-cold war times and especially in the 21st century, there has been a transition from peacekeeping with limited size and scope towards large and complex peace operations. This shift has presented peace operations with a dilemma. How to balance between maintaining consent for peace operations, whilst being able to use military force to coerce those attempting to wreck peace processes? To address such a dilemma, this research aims to promote understanding, on what can be achieved by military crisis management operations (peace support operations) in the next decade. The research concentrates on the focal research question: Should military components induce consent or rely on the compliance of conflicting parties in crisis management operations of the next decade (2020 – 2030)? The focus is on military – political strategic level considerations, and especially on the time before political decisions to commit to a crisis management operation. This study does not focus on which actor or organisation should intervene. The framework of this thesis derives from the so called ‘peacebuilding space’, the scope of peace operations and spoiler theory. Feasibility of both peace enforcement and peacekeeping in countering future risk conditions are analysed in this framework. This future-orientated qualitative research uses the Delphi-method with a panel of national and international experts. Citation analysis supports identification of relevant reference material, which consists of contemporary literature, the Delphi-questionnaires and interviews. The research process followed three main stages. In the first stage, plausible future scenarios and risk conditions were identified with the Delphi-panel. In the second stage, operating environments for peace support operations were described and consequent hypotheses formulated. In the third stage, these hypotheses were tested on the Delphi-panel. The Delphi-panel is sufficiently wide and diverse to produce plausible yet different insights. The research design utilised specifically military crisis management and peace operations theories. This produced various and relevant normative considerations. Therefore, one may argue that this research; which is based on accepted contemporary theory, hypotheses derived thereof and utilising an expert panel, contributes to the realm of peace support operations. This research finds that some degree of peace enforcement will be feasible and necessary in at least the following risk conditions: failed governance; potential spillover of ethnic, religious, ideological conflict; vulnerability of strategic chokepoints and infrastructures in ungoverned spaces; as well as in territorial and extra-territorial border disputes. In addition, some form of peace enforcement is probably necessary in risk conditions pertaining to: extremism of marginalised groups; potential disputes over previously uninhabited and resource-rich territories; and interstate rivalry. Furthermore, this research finds that peacekeeping measures will be feasible and necessary in at least risk conditions pertaining to: potential spillover of ethnic, religious, ideological conflict; uncontrolled migration; consequences from environmental catastrophes or changes; territorial and extra-territorial border disputes; and potential disputes over previously uninhabited and resource-rich territories. These findings are all subject to both generic and case specific preconditions that must exist for a peace support operation. Some deductions could be derived from the research findings. Although some risk conditions may appear illogical, understanding the underlying logic of a conflict is fundamental to understanding transition in crisis management. Practitioners of crisis management should possess cognizance of such transition. They must understand how transition should occur from threat to safety, from conflict to stability – and so forth. Understanding transition is imperative for managing the dynamic evolution of preconditions, which begins at the outset of a peace support operation. Furthermore, it is pertinent that spoilers are defined from a peace process point of view. If spoilers are defined otherwise, it changes the nature of an operation towards war, where the logic is breaking the will of an enemy - and surrender. In peace support operations, the logic is different: actions towards spoilers are intended to cause transition towards consent - not defeat. Notwithstanding future developments, history continues to provide strategic education. However, the distinction is that the risk conditions occur in novel futures. Hence, lessons learned from the past should be fitted to the case at hand. This research shows compelling evidence that swaying between intervention optimism and pessimism is not substantiated. Both peace enforcement and peacekeeping are sine qua non for successful military crisis management in the next decade.

Evaluation of Bubble Formation and Break Up in Suppression Pools by Using Pattern Recognition Methods

During a possible loss of coolant accident in BWRs, a large amount of steam will be released from the reactor pressure vessel to the suppression pool. Steam will be condensed into the suppression pool causing dynamic and structural loads to the pool. The formation and break up of bubbles can be measured by visual observation using a suitable pattern recognition algorithm. The aim of this study was to improve the preliminary pattern recognition algorithm, developed by Vesa Tanskanen in his doctoral dissertation, by using MATLAB. Video material from the PPOOLEX test facility, recorded during thermal stratification and mixing experiments, was used as a reference in the development of the algorithm. The developed algorithm consists of two parts: the pattern recognition of the bubbles and the analysis of recognized bubble images. The bubble recognition works well, but some errors will appear due to the complex structure of the pool. The results of the image analysis were reasonable. The volume and the surface area of the bubbles were not evaluated. Chugging frequencies calculated by using FFT fitted well into the results of oscillation frequencies measured in the experiments. The pattern recognition algorithm works in the conditions it is designed for. If the measurement configuration will be changed, some modifications have to be done. Numerous improvements are proposed for the future 3D equipment.

Die Beendigung von finnischen und deutschen Telefonaten. Eine interaktionslinguistische, kontrastierende Untersuchung

Suomalaisten ja saksalaisten arkikeskustelujen välillä on sekä yhtäläisyyksiä että eroja. Tässä saksalaisen filologian alaan kuuluvassa tutkimuksessa tarkastellaan yhtä keskeistä arkikeskustelun toimintoa, puhelinkeskustelun lopetusta, suomen- ja saksanpuhujien tuottamana. Aineistona on käytetty suomen- ja saksankielisten äidinkielisten puhujien tätä tutkimusta varten nauhoittamia henkilökohtaisia luonnollisia puhelinkeskusteluja. Aineistoon valikoitui 12 suomalaista ja 12 saksalaista puhelua. Nauhoitteiden käyttöön on saatu asianmukainen lupa kaikilta osapuolilta. Puhelut on litteroitu saksalaisella kielialueella vakiintuneen GAT-litterointisysteemin mukaan. Teoreettis-metodisena kehyksenä on kaksi tutkimusalaa, vuorovaikutuslingvistiikka ja kielten vertailu. Vuorovaikutuslingvistinen tarkastelu keskittyy havaintoihin vuorojen ja puheen sekvenssien rakenteesta. Vuorojen merkitysten tulkinnassa hyödynnetään systemaattisesti prosodian antamia vihjeitä. Tuloksena on yksittäisten lopetusten keskustelunanalyyttinen lähikuvaus, jonka pohjalta määritellään kulloisenkin lopetuksen sekvenssirakenne. Kaikki lopetukset olivat siltä osin yhteneväisiä, että niissä kaikissa havaittiin ainakin aloittava, tulevaan tapaamiseen viittaava sekä lopputervehdyksiin johtava sekvenssi. Sekvenssirakenteen variaatioiden pohjalta aineiston lopetukset voidaan kuitenkin jaotella ryhmiin. Sekä suomen- että saksankielisessä aineistossa havaittiin kolmentyyppisiä lopetuksia: kompakteja, komplekseja ja keskeytettyjä lopetuksia. Ryhmittely kolmeen tyyppiin on avuksi seuraavassa kuvausvaiheessa, jossa verrataan suomen- ja saksankielisiä lopetuksia toisiinsa. Samanaikaisesti kun tutkimus valottaa kohtia, joissa kaksi aineistosettiä yhtenevät ja eroavat, se myös esittää, mitkä vuorovaikutuksen tasot soveltuvat kieltenvälisen vertailun kohteiksi. Pohdintaa siitä, mitä vuorovaikutuksen tasoja kieltenväliseen vertailuun voidaan sisällyttää, onkin toistaiseksi esitetty verrattain vähän. Työ siis rakentaa siltaa vuorovaikutuslingvistisen ja kontrastiivisen kielitieteen välille.

Scheduling dynamic dataflow graphs with model checking

With the shift towards many-core computer architectures, dataflow programming has been proposed as one potential solution for producing software that scales to a varying number of processor cores. Programming for parallel architectures is considered difficult as the current popular programming languages are inherently sequential and introducing parallelism is typically up to the programmer. Dataflow, however, is inherently parallel, describing an application as a directed graph, where nodes represent calculations and edges represent a data dependency in form of a queue. These queues are the only allowed communication between the nodes, making the dependencies between the nodes explicit and thereby also the parallelism. Once a node have the su cient inputs available, the node can, independently of any other node, perform calculations, consume inputs, and produce outputs. Data ow models have existed for several decades and have become popular for describing signal processing applications as the graph representation is a very natural representation within this eld. Digital lters are typically described with boxes and arrows also in textbooks. Data ow is also becoming more interesting in other domains, and in principle, any application working on an information stream ts the dataflow paradigm. Such applications are, among others, network protocols, cryptography, and multimedia applications. As an example, the MPEG group standardized a dataflow language called RVC-CAL to be use within reconfigurable video coding. Describing a video coder as a data ow network instead of with conventional programming languages, makes the coder more readable as it describes how the video dataflows through the different coding tools. While dataflow provides an intuitive representation for many applications, it also introduces some new problems that need to be solved in order for data ow to be more widely used. The explicit parallelism of a dataflow program is descriptive and enables an improved utilization of available processing units, however, the independent nodes also implies that some kind of scheduling is required. The need for efficient scheduling becomes even more evident when the number of nodes is larger than the number of processing units and several nodes are running concurrently on one processor core. There exist several data ow models of computation, with different trade-offs between expressiveness and analyzability. These vary from rather restricted but statically schedulable, with minimal scheduling overhead, to dynamic where each ring requires a ring rule to evaluated. The model used in this work, namely RVC-CAL, is a very expressive language, and in the general case it requires dynamic scheduling, however, the strong encapsulation of dataflow nodes enables analysis and the scheduling overhead can be reduced by using quasi-static, or piecewise static, scheduling techniques. The scheduling problem is concerned with nding the few scheduling decisions that must be run-time, while most decisions are pre-calculated. The result is then an, as small as possible, set of static schedules that are dynamically scheduled. To identify these dynamic decisions and to find the concrete schedules, this thesis shows how quasi-static scheduling can be represented as a model checking problem. This involves identifying the relevant information to generate a minimal but complete model to be used for model checking. The model must describe everything that may affect scheduling of the application while omitting everything else in order to avoid state space explosion. This kind of simplification is necessary to make the state space analysis feasible. For the model checker to nd the actual schedules, a set of scheduling strategies are de ned which are able to produce quasi-static schedulers for a wide range of applications. The results of this work show that actor composition with quasi-static scheduling can be used to transform data ow programs to t many different computer architecture with different type and number of cores. This in turn, enables dataflow to provide a more platform independent representation as one application can be fitted to a specific processor architecture without changing the actual program representation. Instead, the program representation is in the context of design space exploration optimized by the development tools to fit the target platform. This work focuses on representing the dataflow scheduling problem as a model checking problem and is implemented as part of a compiler infrastructure. The thesis also presents experimental results as evidence of the usefulness of the approach.

Thermal reactions of the major hydrocarbon components of biomass gasification gas

Gasification of biomass is an efficient method process to produce liquid fuels, heat and electricity. It is interesting especially for the Nordic countries, where raw material for the processes is readily available. The thermal reactions of light hydrocarbons are a major challenge for industrial applications. At elevated temperatures, light hydrocarbons react spontaneously to form higher molecular weight compounds. In this thesis, this phenomenon was studied by literature survey, experimental work and modeling effort. The literature survey revealed that the change in tar composition is likely caused by the kinetic entropy. The role of the surface material is deemed to be an important factor in the reactivity of the system. The experimental results were in accordance with previous publications on the subject. The novelty of the experimental work lies in the used time interval for measurements combined with an industrially relevant temperature interval. The aspects which are covered in the modeling include screening of possible numerical approaches, testing of optimization methods and kinetic modelling. No significant numerical issues were observed, so the used calculation routines are adequate for the task. Evolutionary algorithms gave a better performance combined with better fit than the conventional iterative methods such as Simplex and Levenberg-Marquardt methods. Three models were fitted on experimental data. The LLNL model was used as a reference model to which two other models were compared. A compact model which included all the observed species was developed. The parameter estimation performed on that model gave slightly impaired fit to experimental data than LLNL model, but the difference was barely significant. The third tested model concentrated on the decomposition of hydrocarbons and included a theoretical description of the formation of carbon layer on the reactor walls. The fit to experimental data was extremely good. Based on the simulation results and literature findings, it is likely that the surface coverage of carbonaceous deposits is a major factor in thermal reactions.

An EDTA-β-cyclodextrin adsorbent for the adsorption of rare earth elements and its application in preconcentration of ultratrace rare earth elements from seawater

The objectives of this work were synthesizing an EDTA-β-CD adsorbent and investigating its adsorption potential and applications in preconcentration of REEs from aqueous phase. The adsorption capacity of EDTA-β-CD was investigated. The adsorption studies were performed by batch techniques both in one- and multi-component systems. The effects of pH, contact time and initial concentration were evaluated. The analytical detection methods and characterization methods were presented. EDTA-β-CD adsorbent was synthesized successfully with high EDTA coverage. The maximum REEs uptake was 0.310 mmol g-1 for La(III), 0.337 mmol g-1 for Ce(III) and 0.353 mmol g-1 for Eu(III), respectively. The kinetics of REEs onto EDTA-β-CD fitted well to pseudo-second-order model and the adsorption rate was affected by intra-particle diffusion. The experimental data of one component studies fitted to Langmuir isotherm model indicating the homogeneous surface of the adsorbent. The extended Sips model was applicable for the isotherm studies in three-component system. The electrostatic interaction, chelation and complexation were all involved in the adsorption mechanism. The preconcentration of RE ions and regeneration of EDTA-β-CD were successful. Overall, EDTA-β-CD is an effective adsorbent in adsorption and preconcentration of REEs.

Maanpuolustustahto asevelvollisen koulutuksen ja palveluksen onnistumista selittävänä tekijänä

Lähtökohta tälle tutkimukselle oli havainto siitä, että varusmiehillä maanpuolustustahto ja taisteluluottamus korreloivat. Tämä huomio oli mahdollista tehdä aikaisemmissa varusmiesaineistoilla tehdyissä tutkimuksissa, joissa olin ollut mukana. Tutkimuksen aineistoina olivat useat puolustusvoimissa kerätyt varusmiesten kyselytutkimusaineistot. Vertailuaineistoina käytin reserviläisille kertausharjoituksissa tehtyjen kyselyiden aineistoja. Olennaista oli selvittää, säilyikö havaittu riippuvuus kun muita mahdollisia tekijöitä otettiin huomioon. Tutkimus oli aikaisemmin kerättyjen aineistojen sekundaarianalyysi ja tutkijana en ollut voinut vaikuttaa kyselyjen sisältöön tai käytettyjen muuttujien ja mittareiden valintaan. Aineistot on kerätty kuvaileviin tarkoituksiin ja tästä syystä tämä tutkimus oli tilastollisesti kuvaileva. Keskeiset käytetyt aineistot olivat varusmiesten kotiuttamiskyselyiden eli loppukyselyiden aineistot kaikista varuskunnista vuosilta 2000 – 2008 sekä vuonna 2010 Siilasmaan työryhmää varten kerätty aineisto kolmesta varuskunnasta. Vuoden 2010 varusmiestutkimus oli toteutettu siten, että kysely tehtiin sekä palveluksen alussa että lopussa. Tässä aineistossa käytettiin monipuolisesti varusmiesten psykososiaalisen toimintakyvyn erilaisia mittareita. Maanpuolustustahto on käsitteellisesti laaja kokonaisuus, kuitenkin tässä tutkimuksessa se oli operationalisoitava käytettävissä olleiden osioiden avulla. Maanpuolustustahtoa tarkasteltiin sekä henkilökohtaisena että yleisenä maanpuolustustahtona sekä niiden yhdistelmänä, josta käytettiin myös nimitystä maanpuolustusajattelu. Käsitteellisesti suppeampi taisteluluottamus operationalisoitiin siten, että muuttujana se kuvasi varusmiehen luottamusta aseisiinsa, saamaansa koulutukseen sekä lähiryhmäänsä. Taisteluluottamuksen mittaamisen taustalla oli ajatus siitä, että tämän yksilökohtaisen mittarin keskiarvo on joukon koulutuksen onnistuneisuuden estimaatti. Taisteluluottamus oli tutkimuksessa varsinainen tulosmuuttuja. Tulosten perusteella yksittäisten varusmiesten psykososiaalisessa toimintakyvyssä on eroja. Erityisesti erottui yksittäisenä tekijänä sosiaalisuus, joka summamuuttujana oli muodostettu varusmiestutkimus 2010:n aineistossa Maanpuolustuskorkeakoulun Käyttäytymistieteen laitoksen laatimista osioista. Sosiaalisuus ennusti voimakkaasti varusmiehen etenemistä koulutuksessa aina johtajakoulutukseen saakka. Sosiaalisuuden kontrollointi tilastollisesti ei poistanut maanpuolustusajattelun ja taisteluluottamuksen välistä riippuvuutta. Varusmiestutkimus 2010 aineistossa oli mahdollista tarkastella maanpuolustusajattelun muutosta palvelusaikana ja muutoksen yhteyttä psykososiaalisen toimintakyvyn kuvaajiin. Stressaantumistaipumus ja neuroottisuus olivat yhteydessä maanpuolustustahdon laskuun. Tunteiden hallinnan kyky tuki varusmiehen maanpuolustustahdon ja taisteluluottamuksen kehittymistä. Tilastollinen kuvaus toteutettiin Mplus-ohjelmistolla lasketulla rakenneyhtälömallilla. Aineistoon sopiva malli oli mahdollista löytää. Mallin mukaan sosiaalinen pääoman yksilökohtaisena resurssina antaa mahdollisuuden kehittää ja säilyttää maanpuolustusajattelua, joka on yhteydessä itseluottamuksen luontoiseen taisteluluottamukseen varusmieskoulutuksen päättyessä. Koulutuksen aikana joukkoon kehittynyt kiinteys ja luottamus tukevat tätä kehitystä. Joukkotuotantomallilla saadaan aikaan joukkoja, joissa taisteluluottamus on yleensä tarvittavalla tasolla ja niitä voidaan käyttää osoitettuihin tehtäviin. Kertausharjoitukset ylläpitävät kiinteyttä, taisteluluottamusta ja sitä kautta joukon suorituskykyä. Tutkimuksessa havaittiin myös, että pysyvissä miehistön ryhmissä, joissa ryhmänjohtaja ja/tai jäseniä ei vaihtunut, koulutuksen tulokset olivat parempia kuin muuttuneissa ryhmissä. Edelleen havaittiin, että 12 kuukautta palvelleiden miehistön jäsenten joukossa palvelusmotivaatio laski enemmän kuin muissa varusmiesryhmissä. Yhdestätoista koulutuksen ja tutkimuksen asiantuntijasta koottu ryhmä arvioi tutkimuksen tuloksia sovelletulla Q-menetelmällä Facilitate Pro -ohjelmistoa käyttäen. Menettely tuotti lisänäkökohtia tulosten arviointiin sekä niiden soveltamiseen.

The role of metal ions in selective and sustainable processes

Sustainability and recycling are core values in today’s industrial operations. New materials, products and processes need to be designed in such a way as to consume fewer of the diminishing resources we have available and to put as little strain on the environment as possible. An integral part of this is cleaning and recycling. New processes are to be designed to improve the efficiency in this aspect. Wastewater, including municipal wastewaters, is treated in several steps including chemical and mechanical cleaning of waters. Well-cleaned water can be recycled and reused. Clean water for everyone is one of the greatest challenges we are facing today. Ferric sulphate, made by oxidation from ferrous sulphate, is used in water purification. The oxidation of ferrous sulphate, FeSO4, to ferric sulphate in acidic aqueous solutions of H2SO4 over finely dispersed active carbon particles was studied in a vigorously stirred batch reactor. Molecular oxygen was used as the oxidation agent and several catalysts were screened: active carbon, active carbon impregnated with Pt, Rh, Pd and Ru. Both active carbon and noble metal-active carbon catalysts enhanced the oxidation rate considerably. The order of the noble metals according to the effect was: Pt >> Rh > Pd, Ru. By the use of catalysts, the production capacities of existing oxidation units can be considerably increased. Good coagulants have a high charge on a long polymer chain effectively capturing dirty particles of the opposite charge. Analysis of the reaction product indicated that it is possible to obtain polymeric iron-based products with good coagulation properties. Systematic kinetic experiments were carried out at the temperature and pressure ranges of 60B100°C and 4B10 bar, respectively. The results revealed that both non-catalytic and catalytic oxidation of Fe2+ to Fe3+ take place simultaneously. The experimental data were fitted to rate equations, which were based on a plausible reaction mechanism: adsorption of dissolved oxygen on active carbon, electron transfer from Fe2+ ions to adsorbed oxygen and formation of surface hydroxyls. A comparison of the Fe2+ concentrations predicted by the kinetic model with the experimentally observed concentrations indicated that the mechanistic rate equations were able to describe the intrinsic oxidation kinetics of Fe2+ over active carbon and active carbon-noble metal catalysts. Engineering aspects were closely considered and effort was directed to utilizing existing equipment in the production of the new coagulant. Ferrous sulphate can be catalytically oxidized to produce a novel long-chained polymeric iron-based flocculent in an easy and affordable way in existing facilities. The results can be used for modelling the reactors and for scale-up. Ferric iron (Fe3+) was successfully applied for the dissolution of sphalerite. Sphalerite contains indium, gallium and germanium, among others, and the application can promote their recovery. The understanding of the reduction process of ferric to ferrous iron can be used to develop further the understanding of the dissolution mechanisms and oxidation of ferrous sulphate. Indium, gallium and germanium face an ever-increasing demand in the electronics industry, among others. The supply is, however, very limited. The fact that most part of the material is obtained through secondary production means that real production quota depends on the primary material production. This also sets the pricing. The primary production material is in most cases zinc and aluminium. Recycling of scrap material and the utilization of industrial waste, containing indium, gallium and geranium, is a necessity without real options. As a part of this study plausible methods for the recovery of indium, gallium and germanium have been studied. The results were encouraging and provided information about the precipitation of these valuables from highly acidic solutions. Indium and gallium were separated from acidic sulphuric acid solutions by precipitation with basic sulphates such as alunite or they were precipitated as basic sulphates of their own as galliunite and indiunite. Germanium may precipitate as a basic sulphate of a mixed composition. The precipitation is rapid and the selectivity is good. When the solutions contain both indium and gallium then the results show that gallium should be separated before indium to achieve a better selectivity. Germanium was separated from highly acidic sulphuric acid solutions containing other metals as well by precipitating with tannic acid. This is a highly selective method. According to the study other commonly found metals in the solution do not affect germanium precipitation. The reduction of ferric iron to ferrous, the precipitation of indium, gallium and germanium, and the dissolution of the raw materials are strongly depending on temperature and pH. The temperature and pH effect were studied and which contributed to the understanding and design of the different process steps. Increased temperature and reduced pH improve the reduction rate. Finally, the gained understanding in the studied areas can be employed to develop better industrial processes not only on a large scale but also increasingly on a smaller scale. The small amounts of indium, gallium and germanium may favour smaller and more locally bound recovery.

Competitive Effects of Non-Controlling Minority Acquisitions – Sufficient to merit further EU merger regulation?

Partial ownership interests are a widespread phenomenon in modern corporate environment. Unless minority shareholding affords the target to exercise control over the target, they do currently not have to be notified to the European Commission under EU merger regime. However, economic research has long suggested that when linking competing or non-horizontally positioned undertakings particularly in industries with few competitors, minority shareholdings even far below the majority of shares or voting rights could lead to higher prices or lower output volumes to the detriment of consumers. The Commission has recognized this issue and proceeded to suggest an extension of the merger regime to catch also certain non-controlling minority acquisitions. Horizontal non-controlling minority shareholdings create a positive correlation between the sales revenues of the partial acquirer and target. Through the equity interest the acquirer will internalise a fraction, proportional to the financial rights attached to the shareholding, of the profit of the target. This will incentivise the acquirer to contribute to increasing the target’s business profits by increasing its own sales price (horizontal unilateral effects). When a minority stake is held in a vertically related or a conglomerate company, the minority acquirer could be allowed to hamper or eliminate the target’s rivals’ access either to inputs (input foreclosure) or customers (customer foreclosure), depending on which level of the supply chain the parties are (vertical unilateral effects). Under certain circumstances minority share acquisitions could also lessen competition because they facilitate collusion between companies active in the market (coordinated effects). Economic theory confirms that non-controlling minority shareholdings may under certain circumstances create anti-competitive effects that are unlikely to be remedies by pro-competitive effects. However, they are likely to be of less significant nature than anticompetitive effects created by full mergers. This derives fore mostly from the fact that a minority share acquirer carries all the costs associated with its unilateral action but will internalise only a fraction of the lost profits. This is likely to limit the acquirer’s incentive to raise price and the profitability of such behavior. Having in mind that the number of potentially problematic cases is expected to be next to negligible, the limited potential competitive effects of non-controlling minority share acquisitions cannot be seen to clearly merit extension of the scope of the EUMR. The system suggested by the Commission is particularly ill-fitted for such purpose given the clear lack of legal certainty and considerable administrative burden associated with it.

Neopentyyliglykolin ja propionihapon välisen esteröintireaktion kinetiikka

Glykolien esterit ovat haluttuja pintareaktiivisia aineita. Niitä voidaan valmistaa esteröintireaktiolla karboksyylihappojen kanssa katalyytin läsnä ollessa, jolloin toivottu reaktiotuote on yleensä muodostuva monoesteri. Monoesterin saannon lisäämiseksi reaktiossa muodostuvaa vettä voidaan poistaa jatkuvasti reaktiosta. Reaktion tasapainotilan tutkiminen on kuitenkin tärkeää, jotta reaktion kinetiikka tunnettaisiin mahdollisimman hyvin. Tällöin reaktiotuotteita ei poisteta reaktioseoksesta reaktion aikana. Glykolit esteröityvät happojen kanssa kahdessa vaiheessa. Ensimmäisessä vaiheessa muodostuu monoesteriä ja vettä ja toisessa vaiheessa diesteriä ja vettä. Kokeiden perusteella ensimmäinen vaihe on selvästi toista vaihetta nopeampi reaktio. Kirjallisuudessa on esitetty myös kaksi sivureaktiota, transesteröityminen ja disproportionaatio. Reaktion kinetiikka voidaan kuvata ilman näitä pieniä sivureaktiota, mutta täydellisen kuvaamisen vuoksi on ne myös otettava huomioon. Reaktion kinetiikan tutkimiseksi suoritettiin viisi laboratoriokoetta eri lämpötiloissa neopentyyliglykolilla ja propionihapolla homogeenisen para-tolueenisulfonihapon toimiessa katalyyttina. Lähtöaineiden ja tuotteiden konsentraatioita seurattiin ajan funktiona ja saatujen tulosten perusteella sovitettiin reaktiomekanismin differentiaaliyhtälöiden reaktionopeusvakiot. Nopeusvakioiden lämpötilariippuvuutta tutkittiin Arrheniuksen yhtälön avulla. Lisäksi määritettiin tasapainovakiot kullekin osareaktiolle.

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.