I takt med att behovet av att minska utsläppen av växthusgasen ökar, ökar även intresset för negativa utsläpp. En lovande teknik för att uppnå negativa utsläpp är koldioxidlagring från biomassa, även kallad BECCS (Bio-Energy Carbon Capture and Storage). Trots teknologins mognad är de stora energibehoven vid lösningsmedelsregenerering ett hinder för storskalig implementering. I den här studien utforskas den relativt okända kinetiken för lösningsmedelsregenerering av kaliumkarbonat i ett steg för att optimera processen. Dessutom undersöks möjligheten att använda vanadin(V)oxid som katalysator för att förbättra desorptionshastigheten. Experimentella analyser utfördes i en sats-reaktor och gick ut på att undersöka förändringen av lösningsmedlets loading över tid genom regelbundna titreringar. Utöver detta undersöks den påverkan som temperatur och omrörning har på desorptionshastigheten. Experimenten utförs vid atmosfärstryck och temperaturer från 80°C till 100°C. Resultaten visade på god repeterbarhet trots svårigheter med temperaturöverskridningar. Desorptionshastigheten var lägre vid 80°C och 90°C än vid 100°C, men de logaritmiska hastighetskonstanterna följde inte en linjär relation mot temperaturinverserna vilket antyder att reaktionen är begränsad av massöverföring. Vidare påverkade inte användandet av en katalysator desorptionskinetiken märkbart, vilket än en gång antyder ett massöverföringsberoende. Slutligen visades ingen märkbar skillnad i desorptionshastighet trots olika omrörningshastigheter. Detta beror troligen på den redan höga massöverföringen som sker vid kokpunkten. Sammanfattningsvis bidrar denna studie med insikter för att förbättra effektiviteten hos regenereringen av lösningsmedel vid BECCS, vilket är avgörande för att motverka utsläppen och möta utmaningarna med klimatförändringarna.

Diese Dissertation untersucht Quantensysteme in kondensierter Phase, welche mit ihrer Umgebung wechselwirken und durch ultrakurze Laserpulse angeregt werden. Die Zeitskalen der verschiedenen beteiligten Prozessen lassen sich bei solchen Problemen nicht separieren, weshalb die Standardmethoden zur Behandlung offener Quantensysteme nicht angewandt werden können. Die Methode des Surrogate Hamiltonian stellt ein Beispiel neuer Herangehensweisen an dissipative Quantendynamik dar. Die Weiterentwicklung der Methode und ihre Anwendung auf Phänomene, die zur Zeit experimentell untersucht werden, stehen im Mittelpunkt dieser Arbeit. Im ersten Teil der Arbeit werden die einzelnen dissipativen Prozesse klassifiziert und diskutiert. Insbesondere wird ein Modell der Dephasierung in die Methode des Surrogate Hamiltonian eingeführt. Dies ist wichtig für zukünftige Anwendungen der Methode, z.b. auf kohärente Kontrolle oder Quantencomputing. Diesbezüglich hat der Surrogate Hamiltonian einen großen Vorteil gegenüber anderen zur Verfügung stehenden Methoden dadurch, daß er auf dem Spin-Bad, d.h. auf einer vollständig quantenmechanischen Beschreibung der Umgebung, beruht. Im nächsten Schritt wird der Surrogate Hamiltonian auf ein Standardproblem für Ladungstransfer in kondensierter Phase angewandt, zwei nichtadiabatisch gekoppelte harmonische Oszillatoren, die in ein Bad eingebettet sind. Dieses Modell stellt eine große Vereinfachung von z.B. einem Molekül in Lösung dar, es dient hier jedoch als Testbeispiel für die theoretische Beschreibung eines prototypischen Ladungstransferereignisses. Alle qualitativen Merkmale eines solchen Experimentes können wiedergegeben und Defizite früherer Behandlungen identifiziert werden. Ultraschnelle Experimente beobachten Reaktionsdynamik auf der Zeitskala von Femtosekunden. Dies kann besonders gut durch den Surrogate Hamiltonian als einer Methode, die auf einer zeitabhängigen Beschreibung beruht, erfaßt werden. Die Kombination der numerischen Lösung der zeitabhängigen Schrödingergleichung mit der Wignerfunktion, die die Visualisierung eines Quantenzustands im Phasenraum ermöglicht, gestattet es, dem Ladungstransferzyklus intuitiv Schritt für Schritt zu folgen. Der Nutzen des Surrogate Hamiltonian wird weiterhin durch die Verbindung mit der Methode der Filterdiagonalisierung erhöht. Dies gestattet es, aus mit dem Surrogate Hamiltonian nur für relative kurze Zeite konvergierte Erwartungswerten Ergebnisse in der Frequenzdomäne zu erhalten. Der zweite Teil der Arbeit beschäftigt sich mit der theoretischen Beschreibung der laserinduzierten Desorption kleiner Moleküle von Metalloxidoberflächen. Dieses Problem stellt ein Beispiel dar, in dem alle Aspekte mit derselben methodischen Genauigkeit beschrieben werden, d.h. ab initio Potentialflächen werden mit einem mikroskopischen Modell für die Anregungs- und Relaxationsprozesse verbunden. Das Modell für die Wechselwirkung zwischen angeregtem Adsorbat-Substrat-System und Elektron-Loch-Paaren des Substrats beruht auf einer vereinfachten Darstellung der Elektron-Loch-Paare als ein Bad aus Dipolen und auf einer Dipol-Dipol-Wechselwirkung zwischen System und Bad. Alle Parameter können aus Rechnungen zur elektronischen Struktur abgeschätzt werden. Desorptionswahrscheinlichkeiten und Desorptionsgeschwindigkeiten werden unabhängig voneinander im experimentell gefundenen Bereich erhalten. Damit erlaubt der Surrogate Hamiltonian erstmalig eine vollständige Beschreibung der Photodesorptionsdynamik auf ab initio-Basis. / This thesis investigates condensed phase quantum systems which interact with their environment and which are subject to ultrashort laser pulses. For such systems the timescales of the involved processes cannot be separated, and standard approaches to treat open quantum systems fail. The Surrogate Hamiltonian method represents one example of a number of new approaches to address quantum dissipative dynamics. Its further development and application to phenomena under current experimental investigation are presented. The single dissipative processes are classified and discussed in the first part of this thesis. In particular, a model of dephasing is introduced into the Surrogate Hamiltonian method. This is of importance for future work in fields such as coherent control and quantum computing. In regard to these subjects, it is a great advantage of the Surrogate Hamiltonian over other available methods that it relies on a spin, i.e. a fully quantum mechanical description of the bath. The Surrogate Hamiltonian method is applied to a standard model of charge transfer in condensed phase, two nonadiabatically coupled harmonic oscillators immersed in a bath. This model is still an oversimplification of, for example, a molecule in solution, but it serves as testing ground for the theoretical description of a prototypical ultrafast pump-probe experiment. All qualitative features of such an experiment are reproduced and shortcomings of previous treatments are identified. Ultrafast experiments attempt to monitor reaction dynamics on a femtosecond timescale. This can be captured particularly well by the Surrogate Hamiltonian as a method based on a time-dependent picture. The combination of the numerical solution of the time-dependent Schrödinger equation with the phase space visualization given by the Wigner function allows for a step by step following of the sequence of events in a charge transfer cycle in a very intuitive way. The utility of the Surrogate Hamiltonian is furthermore significantly enhanced by the incorporation of the Filter Diagonalization method. This allows to obtain frequency domain results from the dynamics which can be converged within the Surrogate Hamiltonian approach only for comparatively short times. The second part of this thesis is concerned with the theoretical treatment of laser induced desorption of small molecules from oxide surfaces. This is an example which allows for a description of all aspects of the problem with the same level of rigor, i.e. ab initio potential energy surfaces are combined with a microscopic model for the excitation and relaxation processes. This model of the interaction between the excited adsorbate-substrate complex and substrate electron-hole pairs relies on a simplified description of the electron-hole pairs as a bath of dipoles, and a dipole-dipole interaction between system and bath. All parameters are connected to results from electronic structure calculations. The obtained desorption probabilities and desorption velocities are simultaneously found to be in the right range as compared to the experimental results. The Surrogate Hamiltonian approach therefore allows for a complete description of the photodesorption dynamics on an ab initio basis for the first time.

Kam, Kin Ting. / Thesis (M.Phil.)--Chinese University of Hong Kong, 2008. / Includes bibliographical references (leaves 169-192). / Abstracts in English and Chinese. / Chapter 1. --- Abstract --- p.ii / English --- p.ii / Chinese --- p.v / Chapter 2. --- Acknowledgments --- p.vii / Chapter 3. --- Abbreviations and N-glycan representation --- p.viii / Chapter 4. --- Introduction --- p.1 / Chapter 5. --- Review of Literatures --- p.2 / Chapter 5.1. --- Introduction to Liver Fibrosis --- p.2 / Chapter 5.1.1. --- Pathogenesis of Liver Fibrosis --- p.2 / Chapter 5.1.2. --- Changes of liver architecture - basis of liver fibrosis diagnosis --- p.4 / Chapter 5.2. --- Current Diagnosis of Liver Fibrosis - from Biopsy Examination to Serum Test --- p.5 / Chapter 5.3. --- Glycomics and its Potential as Biomarkers --- p.9 / Chapter 5.3.1. --- Overview of Biochemical and Functional Characteristics of Glycan --- p.13 / Chapter 5.3.2. --- N-linked and O-linked Glycosylations - A Valuable Source of Biomarkers --- p.15 / Chapter 5.3.3. --- Glycomics 一 An Uprising Approach for Biomarker Discovery --- p.17 / Chapter 5.3.4. --- Human Proteome Organisation Human Disease Glycomics/Proteome Initiative --- p.19 / Chapter 5.3.5. --- Recent Applications of Glycomics to Biomarker Discovery --- p.20 / Chapter 5.4. --- Current Technologies for Glycomic Study --- p.22 / Chapter 5.4.1. --- MALDI-TOF MS --- p.22 / Chapter 5.4.2. --- Lectin Microarray --- p.25 / Chapter 5.4.3. --- Liquid Chromatography --- p.27 / Chapter 5.4.4. --- Capillary Electrophoresis --- p.29 / Chapter 5.4.5. --- Quantitative Profiling of Tissue Glycome --- p.31 / Chapter 6 --- Project Rationales and Objectives --- p.36 / Chapter 7 --- Section 1: Methodology Development of Quantitative N- glycomic Profiling --- p.37 / Chapter 1. --- Introduction --- p.37 / Chapter 2. --- Method and Materials --- p.39 / Chapter 3. --- Results --- p.46 / Chapter 4. --- Discussion --- p.65 / Chapter 5. --- Conclusion --- p.71 / Chapter 8. --- Section 2: Serum N-glycomic Profile as Biomarker for Liver Fibrosis 一 Pilot Study --- p.73 / Chapter 1. --- Introduction --- p.73 / Chapter 2. --- Method and Materials --- p.75 / Chapter 3. --- Results --- p.79 / Chapter 4. --- Discussion --- p.86 / Chapter 5. --- Conclusion --- p.94 / Chapter 9. --- Section 3: Serum N-glycomic Profile as Biomarker for Liver Fibrosis -Verification Study --- p.96 / Chapter 1. --- Introduction --- p.96 / Chapter 2. --- Method and Materials --- p.98 / Chapter 3. --- Results --- p.104 / Chapter 4. --- Discussion --- p.137 / Chapter 5. --- Conclusion --- p.152 / Chapter 10. --- General Discussion --- p.153 / Chapter 11. --- Conclusion --- p.167 / Chapter 12. --- Original Data --- p.168 / Chapter 13. --- References --- p.169 / Chapter 14. --- Publications --- p.196

This thesis is part of a joint thermochemical heat storage (TCS) research project named Neutrons for Heat Storage (NHS), involving three Nordic research institutes. The project isfunded by Nordforsk and KTH Royal Institute of Technology for the project partner KTH. KTH´s objective in the NHS project is to design, build and operate a bench-scale TCS system using strontium chloride (SrCl2) and ammonia (NH3) as a solid-gas reaction system for low temperature heat storage (40-100 ℃). Here, absorption of NH3 into SrCl2⋅NH3 (monoammine) to form SrCl2⋅8NH3 (octaammine) is used for heat release, and desorption (of NH3 from SrCl2⋅8NH3 to form SrCl2⋅NH3) for heat storage. This thesis initially aimed to conduct commissioning, operation and experimental data acquisition, and performance evaluation of the bench-scale TCS system. However, due to various delays in equipment delivery and shortcomings discovered during the project timeline, its objectives were then redefined to partially commission the system with NH3 and carry out the first absorption cycle in one of the reactors. This thesis project was partly a joint project, where Hjörtur Brynjarsson performed various tasks in the overarching NHS project as part of his thesis project, alongside the work described in this report. Brynjarsson’s work involved reviewing and adapting the design of this bench-scale TCS system. For further details about the shortcomings discovered and corresponding design adaptations, readers are referred to Brynjarsson’s report. In this thesis project, to understand the design of the TCS system, background research on the current project and the SrCl2-NH3 reaction pair was conducted. This includes comprehending the evolution of the project carried out by the previous students and project researchers to the current thesis project. Following this, the maximum theoretical volume of composites in the reactor-heat exchanger (R-HEX) was determined. This was found to be 5262 cm3, and the corresponding SrCl2 in the R-HEX is 1631 g for an average salt density in the composite of 0.31g/cm3. Thereupon, a literature review was conducted on the performance evaluation of Thermal energy storage (TES) systems. The final report of International Energy Agency (IEA) Annex 30 (on Applications of TES in the Energy Transition: Benchmarks and Developments) presents numerous Key Performance Indicators (KPIs) relevant to TES systems and are classified into technical, economic, and lifetime performance indicators. These KPIs are used as the basis for the current thesis work and are compared to examples from other metalhalide-NH3 TCS systems. Finally, for the current thesis project, it was decided to focus the KPIs on technical performance indicators, such as energy storage capacity [kJ] and reaction advancement [-]. As one of the main tasks within the project, the data acquisition system (for measuring temperature, pressure, and mass flow rate parameters), as well as the system components and many final connections, were commissioned herein. A data acquisition manual is thus provided for future use. It considers all the data measuring instruments and their respective locations in the system and the data logger. Also, explanations are provided for the calibration of these instruments. As the next main task, a thermal homogeneity test of the reactors (to compare the heat transfer similarity of reactors before the first reaction) was performed, to investigate the underlying assumption that the reactors were identical was valid. After conducting the test, it was found that reactor A had slightly better heat transfer than reactor B. However, this inhomogeneity is not significant enough to affect the system’s overall performance. As the final main task, partial commissioning of the system (i.e., for the first absorption reaction in reactor B) with N2 (as a mock-test to troubleshoot the procedure forNH3) and then with NH3 were carried out. During the partial commissioning of the system using NH3, the NH3 was added in short pressure pulses (between 5-8 bar(a)) with idling between each pulse due to some practical reasons. In addition to this, the absorption reaction was carried out under less than ideal (still not unfavourable) absorption conditions by deliberately setting the heat transfer fluid (HTF) at high temperatures (e.g., at 105, 90, and 65 °C) to avoid a drastic pressure drop in the reactor between each NH3 pulse. At the end of the NH3 commissioning (possible completion of absorption), it was found that 1541 g of NH3 passed through the mass flow meter. The most likely scenario is that 1521 g of NH3 reacted with the SrCl2 salt in the reactor (the rest, 20 g, is in the dead space, comprised of, e.g., the voids in composite, voids in the R-HEX, and the volume in the gas lines). The heat released from the absorption reaction, in this case, is 3774 kJ (or 1.05 kWh), considering all eight ammines. The heat released from the absorption reaction of SrCl2∙NH3 (monoammine) to SrCl2∙8NH3 (octaammine) is 3224 kJ (or 0.89 kWh). The discharge power calculation is excluded here due to the special approach used in this first absorption, with long idling steps, making that irrelevant. In addition, the sustainability aspects of this TCS technology (SrCl2-NH3) used in this project were analyzed. Based on the analysis, it was found that this technology is environmentally friendly, economically feasible, and can aid in social development. Hence, this technology is considered sustainable, and the designed TCS system has an overall positive impact on sustainable development. To conclude, within this project, the designed TCS system was successfully operated for the first absorption in one reactor and is found to meet the design storage capacity (0.89 kWh). As this TCS system was mainly operated for data acquisition, and since the first absorption was performed at less-than ideal conditions, better absorption conditions are recommended for the subsequent cycles, accommodating better temperature and pressure conditions for both absorption and desorption reactions. Finally, evaluation of the system's technical performance at different reaction conditions (pressure, temperature) and optimizing the system for energy and economics are some of the key follow-up tasks for future work that will benefit the system. / Detta exjobbsprojekt är en del av ett forskningsprojekt Neutrons for Heat Storage (NHS), som handlar om termokemisk energilagring (TCS) och genomfördes med hjälp av tre nordiska forskningsinstitut. Projektet finansieras av Nordforsk och KTH Kungliga Tekniska Högskolan för KTH. I NHS-projektet, KTH:s mål är att utforma, bygga och driva ett TCS-system i bänkskala med ett fast-gasreaktionssystem som använder reaktionsparet strontiumklorid (SrCl2) och ammoniak (NH3), för värmelagring vid låg temperatur (t.ex. 40-100 ℃). Här används specifikt absorption av NH3 i SrCl2⋅NH3 (monoammin) till SrCl2⋅8NH3 (oktaammin) för värmeavgivning och desorption av NH3 från SrCl2⋅8NH3 till SrCl2⋅NH3 för värmelagring. Detta projekt syftade inledningsvis till att genomföra driftsättning, drift och insamling av experimentella data samt utvärdering av prestanda för TCS-systemet i bänkskala. På grund av olika förseningar i leveransen av flertal utrustningar och brister som upptäcktes under projektets gång, omdefinierades målen till att ta en partiell driftsättning av systemet med NH3 och genomföra den första absorptionscykeln i en av reaktorerna. Detta exjobbsprojekt var delvis ett gemensamt projekt, där Hjörtur Brynjarsson utförde olika uppgifter i det övergripande NHS-projektet som en del av sitt exjobbsprojekt, parallelt med arbetet som beskrivs i denna rapport. Brynjarsson’s arbete bestod i att granska och anpassa utformningen av denna bänkskala i TCS-system. För ytterligare detaljer om de brister som upptäcktes och motsvarande anpassningar av utformningen hänvisas läsarna till Brynjarsson’s rapport. I detta exjobbsprojekt, för att förstå TCS-systemets utformning, genomfördes bakgrundsforskning om det aktuella NHS projektet och reaktionsparet SrCl2-NH3. Detta innefattar att förstå utvecklingen av NHS projektet från tidigare projekt utförda av studenter och projektforskare för att sammanställa detta exjobbsprojekt. Därefter fastställdes i detta projekt den maximala teoretiska volymen kompositer i reaktor-värmeväxlare enheten (RHEX). Den visade sig vara 5262 cm3 och att motsvarande SrCl2 i R-HEX är 1631 g för en genomsnittlig salttäthet i kompositen på 0,31 g/cm3. Därefter gjordes en litteraturstudie om utvärdering av prestanda för system för termisk energilagring (TES). Slutrapporten om bilaga 30 från International Energy Agency (IEA) (om tillämpningar av TES i energiomställningen: Benchmarks och Utvecklingar) presenterar ett flertal nyckelindikatorer (KPI:er) för prestandaanalys som är relevanta för TES-system och som är klassificerade i tekniska, ekonomiska och livslängdsindikatorer. Dessa KPI:er används som grund för den aktuella exjobben och jämförs med exempel från andra metallhalogenid-NH3- TCS-system. För detta exjobbprojektet beslutades slutligen att fokusera KPI:erna på tekniska prestandaindikatorer, t.ex. energilagringskapacitet [kJ] och reaktionsframsteg [-]. Som en av huvuduppgifterna inom detta projekt togs datainsamlingssystemet (för mätning av temperatur, tryck och massflödesparametrar) samt systemkomponenterna och många slutliga anslutningar i drift här. En användarmanual för datainsamling tillhandahålls därför för framtida användning. Den gäller alla instrument för datamätning och deras respektive placering i systemet samt dataloggern. Dessutom ges här förklaringar till kalibreringen av dessa instrument. Som nästa huvuduppgift utfördes ett test av reaktorernas termiska homogenitet (för att jämföra reaktorernas likhet i värmeöverföring före den första reaktionen), för att undersöka om det underliggande antagandet att reaktorerna var identiska var giltigt. Efter att ha utfört testet konstaterades det att reaktor A hade en något bättre värmeöverföring än reaktor B. Denna inhomogenitet är dock inte tillräckligt betydande för att påverka systemets totala prestanda. Som sista huvuduppgift genomfördes en partielldriftsättning av systemet (dvs. för den första absorptionsreaktionen i reaktor B) med N2 (som ett simuleringstest för att felsöka förfarandet för NH3) och sedan med NH3. Under den partiella idrifttagningen av systemet med NH3 tillsattes NH3 i korta tryckpulser (mellan 5-8 bar(a)) med tomgång mellan varje puls av praktiska skäl. Dessutom utfördes absorptionsreaktionen under mindre än ideala (men ändå inte ogynnsamma) absorptionsförhållanden genom att värmeöverföringsvätskan medvetet ställdes in på höga temperaturer (t.ex. 105, 90 och 65 °C) för att undvika en drastisk tryckminskning i reaktorn mellan varje NH3-puls. I slutet av NH3-installationen (eventuellt avslutad absorption) konstaterades att 1541 g NH3 passerade genom massflödesmätaren. Det mest sannolika scenariot är att 1521 g NH3 reagerade med SrCl2-saltet i reaktorn (resten dvs., 20 g, finns i det döda utrymmet, som t.ex.består av hålrummen i kompositen, hålrummen i R-HEX och volymen i gasledningarna). Den värme som frigörs från absorptionsreaktionen är i detta fall 3774 kJ (eller 1,05 kWh), om man beaktar alla åtta aminer. Den värme som frigörs från absorptionsreaktionen av SrCl2∙NH3 (monoammin) till SrCl2∙8NH3 (oktaammin) är 3224 kJ (eller 0,89 kWh). Beräkningen av utmatningseffekten är utesluten här på grund av det speciella tillvägagångssätt som används vid denna första absorption, med långa tomgångssteg, vilket gör att den är irrelevant. Dessutom analyserades hållbarhetsaspekterna av denna TCS-teknik (SrCl2-NH3) som användes i detta projekt. På grundval av analysen konstaterades det att denna teknik är miljövänlig, ekonomiskt genomförbar och kan bidra till social utveckling. Tekniken anses därför vara hållbar och det konstruerade TCS-systemet har en övergripande positiv inverkan på hållbar utveckling. Sammanfattningsvis kan man konstatera att det konstruerade TCS-systemet inom ramen för detta projekt används på ett framgångsrikt sätt för den första absorptionen i en reaktor och att det uppfyller den avsedda lagringskapaciteten (0,89 kWh). Eftersom detta TCS-system huvudsakligen användes för datainsamling och eftersom den första absorptionen utfördes under mindre än ideala förhållanden, rekommenderas bättre absorptionsförhållanden för de efterföljande cyklerna, med bättre temperatur- och tryckförhållanden för både absorptions och desorptionsreaktioner. Slutligen är utvärdering av systemets tekniska prestanda vid olika reaktionsförhållanden (tryck, temperatur) och optimering av systemet med avseende på energi och ekonomi några av de viktigaste uppföljningsuppgifterna för framtida arbete som kommer att gynna systemet.

No description available.

Thermochemical heat storage (TCS) is a thermal energy storage (TES) technology used to store thermal energy for later use. TCS can provide heating or cooling services from intermittently available thermal energy, often low grade waste heat. The system studied here stores and releases the energy in the form of chemical energy by utilizing reversible chemical reactions. TCS has potential to reduce greenhouse gas emissions, increase infrastructure system efficiency, lower society-wide energy system costs and by that contribute to sustainable development. This thesis is part of a joint TCS research project named Neutrons for Heat Storage (NHS), involving three research institutes. The project is funded by Nordforsk and KTH Royal Institute of Technology. KTH´s objective in the NHS project is to design, build and operate a bench-scale TCS system using strontium chloride (SrCl2) and ammonia (NH3) as a solid-gas reaction system for low-temperature heat storage (40-80 ℃). Here, absorption of NH3 into SrCl2⋅NH3 (monoammine) to form SrCl2⋅8NH3 (octaammine) is used for heat release, and desorption (of NH3 from SrCl2⋅8NH3 to form SrCl2⋅NH3) for heat storage. Prior to this thesis project, this TCS system, as well as its reactor+heat exchanger (R-HEX) units, were numerically designed at KTH, and the R-HEX units were manufactured. This system is now being built at the laboratory of Applied Thermodynamics and Refrigeration division at the Department of Energy Technology, KTH. The initial system is comprised of a shared storage tank, expansion valve, ammonia meter and an R-HEX (absorption path); and an R-HEX, ammonia meter, gas cooler, compressor, condenser, and the storage tank (desorption path), to accommodate absorption, desorption, and NH3 storage. This thesis was originally planned to include commissioning, operation and experimental data acquisition, and performance evaluation of this system. However, due to various delays and shortcomings discovered at the beginning of the project, its objectives were then redefined to review the system and its components and propose necessary design adaptations of the initially designed (and partially built) system. This thesis project was partly a joint project, where Harish Seetharaman performed various tasks in the overarching NHS project as part of his own thesis project, performed alongside the work described in this report. For various information and results, referring to Harish´s report therefore will be necessary. A literature review of the research into SrCl2-NH3 systems was conducted, with emphasis on performance evaluation, kinetics, and reaction paths. TES performance evaluation is discussed concerning the TCS key performance indicators, with the 2018 IEA's Annex 30 as a guideline and 2013 IRENA´s E17 technology brief as a comparative reference. Much progress and refinement has been made in the 5-year span between the publications of these documents, but some adaptations and interpretations still need to be made to the Annex 30 approach for a good approach to a TCS system of similar nature as the one studied in this report. Review of the latest research on the kinetics and reaction path of the SrCl2-NH3 reaction pair revealed that the 100-year-old single-line-and-path reaction expression is an oversimplification of the actual chemistry. The reaction path seems to be dependent on the kinetics of the reaction, and varies with heating rate, temperature, and pressure. Various literature was found and compared, which show that the reaction enthalpies and entropies are not settled science. This demonstrates the necessity for further research into the SrCl2-NH3 reaction pair before application-scale product design and commercialization can take place. A comprehensive equipment and system review was conducted, whereby multiple issues were found and addressed, that if gone unnoticed, would have caused difficult setbacks for the project.  Consequently, the previous purchased ammonia flow meters and ammonia compressor, were exchanged for new and better suiting equipment. The original ammonia flow meters were undersized due to miscalculations of converting flow units of NLPH (Normal Liters Per Hour) to the project units of g/s, while wrongly using the density of compressed ammonia to convert to g/s, instead of it at the defined normal conditions. Furthermore, these flow meters were of the wrong type, as they had no digital output for data acquisition. The original compressor was also severely undersized, only capable of evacuating 7-14% of the expected maximum desorption flow. This was due to a similar miscalculation during conversion of NLMP (Normal Liters Per Minute) to g/s, as well as an unrequested compressor stroke reduction. New solutions and additional equipment were then required to accommodate the operational limitations discovered in the final chosen equipment and system configuration. These include limiting the compressor inlet pressure to a maximum of 1.1 bar(a); avoiding risk of NH3 condensation at them inlets of the new mass flow meters and compressor; and maintaining the flow meter and compressor inlet temperatures below 40 °C. The pressure limitations required considerable design adaptations. Firstly, an ammonia by-pass is introduced to keep feeding ammonia into the compressor during low desorption flows. The inlet pressure limitation necessitated active pressure management in the form of pressure reduction valves, which were thus introduced. Secondly, the condensation regulation and temperature management required a new approach, as the cooling and condensation temperatures in the original design were too low, causing risks of far too low temperature and pressure in the desorption path, as well as counter-acting simultaneous heating and cooling between the condenser and the storage tank heating sleeve. As a solution, a shunt pump is proposed, where constant cooling water temperature provides condensation on a tight temperature range using an infinite cold wall approach. Along with reviewing the equipment and the system design, new procedures concerning investigating and confirming homogeneous heat transfer properties of the reactors are proposed. Furthermore, improvements are suggested concerning the commissioning of the experimental rig, that include equipment testing with N2-gas and stepwise changes in temperature in sequential cycles to gain a good understanding of the likely behaviors of the system before it is run at the extremes of the operating range. In conclusion, a new and improved process flow diagram, showing all these adaptations, additions, and changes from the original diagram is presented herein as the final key contribution to the overarching NHS-project. This is complemented with an instruction manual, to allow the next researchers a smooth continuation, in terms of the system build, and later commissioning and operation. Finally, some suitable next steps in the project are suggested. These include a conceptualization of descriptive functions for the performance and behavior of the specific system and reactors. These functions are proposed with temperature and pressure as independent variables, as these are two main variables influencing the kinetics of the reaction in the given system. As no experimental data exists yet, the form of the proposed functions is generic. Furthermore, a suggestion is made for a future adaptation for achieving the phase change from NH3(g) to NH3(l) (which is the storage form of ammonia in the system) by deep cooling at the desorption pressure, resulting in only a liquid pump being required to raise the pressure of the NH3(l) in the storage tank. / Termokemisk energilagring (TCS) är en teknik inom termisk energilagring (TES) som används för att lagra termisk energi för senare bruk. TCS kan tillhandahålla värme och kyla från periodvis tillgänglig termisk energi, ofta lågtemperatur spillvärme. Systemet lagrar energin som kemisk energi genom att använda reversibla kemiska reaktioner och massaseparation av reaktions-produkterna. TCS har potential att minska utsläppet av växthusgaser, öka effektiviteten av system i vår infrastruktur, minska energikostnader i samhället och därmed bidra till hållbar utveckling. Detta exjobbsprojekt är en del av ett gemensamt TCS-forskningsprojekt som heter Neutrons for Heat Storage (NHS), där tre forskningsinstitut deltar. Projektet är finansierat av Nordforsk och Kungliga Tekniska Högskolan. KTH:s mål med NHS-projektet är att projektera, bygga, samt driva ett TCSsystem i bänkskala med strontiumklorid (SrCl2) och ammoniak (NH3) som ett fast-gasreaktionssystem för lågtemperaturvärmelagring (40-80 ℃). Här används absorption av NH3 till SrCl2⋅NH3 (monoammin) för att bilda SrCl2⋅8NH3 (oktaammin) för värmeurladdning och desorption (av NH3 från SrCl2⋅NH3 till SrCl2⋅NH3) för värmelagring. Innan detta exjobbsprojekt började hade detta TCS-system, samt systemets reaktor+värmeväxlare (R-HEX) enheter varit numeriskt projekterad vid KTH, och R-HEX-enheterna hade redan tillverkats. Detta system byggs nu på laboratoriet för Avdelningen för tillämpad termodynamik och kylning vid Institutionen för Energiteknik, KTH. Det initiala systemet består av en gemensam lagringstank, expansionsventil, ammoniakmätare, och en R-HEX (systemets absorptionssida) och en R-HEX, ammoniakmätare, gaskylare, kompressor, en kondensor, och en gemensamma lagringstanken (desorptionssidan), for att rymma absorption, desorption (samtidigt) och NH3-lagring. Exjobbsprojektet var ursprungligen planerat att inkludera driftsättning, drift och experimentdatainsamling samt utvärdering av systemet. På grund av olika förseningar och brister som upptäcktes i projektet, omdefinierades projektets mål och består nu av att granska systemet och, samt att föreslå nödvändiga designanpassningar av det ursprungligen konstruerade systemet och dess komponenter. Projektet var delvis ett gemensamt arbete, där Harish Seetharaman utförde olika uppgifter i det övergripande NHS projektet som en del av sitt eget exjobbssprojekt. För olika uppgifter och resultat kommer det därför att vara nödvändigt att hänvisa till Harishs rapport. Litteraturstudié av forskningen kring SrCl2-NH3 system genomfördes, med betoning på prestandautvärdering, kinetik och reaktionsvägar. Prestandautvärdering av TES system diskuteras angående TCS-nyckelindikatorer, med 2018 års IEA:s Annex 30 som riktlinje och IRENA:s E17 Teknologi-sammandrag från 2013 som en referens. Många framsteg och förbättringar har gjorts under femårsperioden mellan dessa publikationer, men vissa anpassningar och tolkningar måste fortfarande härledas till metoderna i Annex 30 för att få ett bra förhållningssätt till ett TCS-system av liknande karaktär som det som studeras i detta projekt. Granskning av den senaste forskningen avseende reaktionskinetik och reaktionsvägar för SrCl2-NH3 reaktionsparet visade att det hundraåriga enkellinje-och-reaktionsväg-formuleringen är en förenkling av den faktiska kemin. Reaktionsvägen verkar beroende av reaktionens kinetik och varierar med uppvärmnings-takten, temperaturen och även trycket. Olika litteratur jämfördes som visar att reaktionsentalpierna och entropierna inte är fastställd vetenskap. Detta visar behovet av ytterligare forskning avseende SrCl2-NH3 innan produktdesign och kommersialisering i applikations-skala kan utföras. En omfattande granskning av systemet och dess komponenter genomfördes, där flera problem hittades och åtgärdades. Om dessa problem hade gått obemärkt förbi skulle det ha orsakat svåra bakslag för projektet. Följaktligen byttes de tidigare köpta ammoniakflödesmätarna ut till nya och en ammoniakkompressor byttes ut mot en ny, för tillämpningen bättre anpassad. De ursprungliga ammoniak-flödesmätarna var underdimensionerade pga. felberäkningar i omvandling av flödesenheter för NLPH (normal liter per timme) till projektenheterna g/s. Samtidigt var densiteten av komprimerad ammoniak felaktigt använt för omvandling till g/s, istället för densiteten vid de definierade normala förhållandena; 1 bar (a) och 20 ° C. Dessutom var dessa flödesmätare av fel typ, eftersom de inte hade någon digital utgång för datainsamling. Den ursprungliga kompressorn var också kraftigt underdimensionerad, endast kapabel att evakuera 7-14% av det förväntade maximala desorptionsflödet. Detta berodde på en liknande felberäkning vid konvertering av NLPM (normal liter per minute) till g/s, samt en oönskad kompressorslagsminskning. Nya lösningar och ytterligare utrustning krävdes för att tillgodose de operativa begränsningar som upptäcktes i den slutgiltigt valda utrustningen och systemutformningen. Dessa inkluderar: begränsa kompressorns inloppstryck till maximalt 1,1 bar(a); undvika risk för NH3 kondens i de nya massflödesmätarna och kompressorn; samt bibehålla flödesmätarens och kompressorns inloppstemperaturer under 40 °C. Tryckbegränsningarna krävde omfattande projekteringsanpassningar. För det första införs en ammoniak-by-pass för att fortsätta mata ammoniak till kompressorn under låga desorptionsflöden. Inloppstrycksbegränsningen nödvändiggjorde aktiv tryckhantering i form av tryckreduceringsventiler. För det andra krävde kondensregleringen och temperaturhanteringen en ny strategi, eftersom kyl- och kondenseringstemperaturerna i den ursprungliga utformningen var för låga. Detta orsakade risker för alldeles för låg temperatur och tryck på desorptionssidan, samt samtidigt motverkande uppvärmning och kylning av kondensorn och förvaringstankens värmehylsa. Som en lösning föreslås en shunt där konstant kylvattentemperatur ger kondens i ett tätt temperaturintervall med en oändlig kallväggsinriktning. Tillsammans med granskning av utrustningen och systemutformningen föreslås nya tillvägagångssätt för undersökning och bekräftelse av reaktorers förmodade homogena värmeöverförings-egenskaper. Dessutom föreslås förbättringar av idrifttagningen av den experimentella riggen, som inkluderar utrustningstestning med N2-gas och stegvisa temperaturförändringar i sekventiella körningar för att få en god förståelse för systemets troliga beteenden innan det körs i ytterligheterna av systemts arbetsområde. Sammanfattningsvis presenteras ett nytt och förbättrat processflödesdiagram, som visar alla utförda anpassningar, tillägg och ändringar från det ursprungliga diagrammet, som är avhandlingsprojektets huvudbidrag till det övergripande NHS-projektet. Detta kompletteras med en bruksanvisning för att smidigt fasa in kommande forskare avseende systemets konstruktion, driftsättning, och drift. Slutligen föreslås några lämpliga kommande steg i projektet. Dessa inkluderar en konceptualisering av beskrivande funktioner för prestanda och beteende av det specifika systemet och reaktorer. Dessa funktioner föreslås med temperatur och tryck som oberoende variabler, eftersom dessa är två huvudvariabler som påverkar reaktionens kinetik. Eftersom inga experimentella data ännu finns, är formen för de föreslagna funktionerna generisk. Vidare ges förslag om framtida anpassning för att uppnå fasändringen från NH3(g) till NH3(v) (som är lagringsformen för NH3 i systemet) genom djup nedkylning vid desorptionstrycket, vilket resulterar i att endast en vätskepump krävs för att höja trycket för NH3(v) i lagringstanken.

The demand for high performance electronic devices is ever increasing in today's world with advent of digital technology in every field. In order to support this fast paced growth and incursion of digital technology in society, smarter, smaller integrated circuits are required at a lower cost. This primary requirement drives semiconductor industries towards the integration of larger number of smaller transistors on a given circuit area. The past decades have seen a rapid evolution of material processing and fabrication techniques, as focus shifts from submicron to sub-nanometer length scales in device configuration. As the functional feature size of an integrated circuit decreases, the threshold of defect causing impurities rises drastically. Huge amount of resources are spent in downstream and upstream processing in order to restore system from contamination upsets and in the upkeep of Ultra-High-Purity (UHP) process streams to meet these stringent requirements. Contamination once introduced into the system also drastically reduces process yield and throughput resulting in huge losses in revenue. Regular UHP fluid distribution system maintenance as well as restorative operations involve a purging operation typically known as Steady State Purge (SSP). This purge operation involves large amount of expensive UHP gas and time. Depending on the scale of the system and type of process involved this results in significant tool, process downtimes and can have a wide range of environment, health and safety (ESH) ramifications. A novel purge process, referred to as Pressure Cyclic Purge (PCP) was studied for establishing gas phase contamination control in UHP applications. In understanding the basic mechanism of this technique and to analyze its extent of application in aiding purging operations, a coupled approach involving experimental investigation and computational process modelling was used. Representative and generic distribution sections such as main supply lines and sections with laterals were contaminated with a known amount of moisture as impurity. The dynamics of the impurity transport through the system from purging with SSP as well as PCP was captured by a highly sensitive analyzer. The surface interactions between the moisture and EPSS were characterized in terms of adsorption and desorption rate constants and surface site density. A computational process model trained using experimental data was then validated and used to study the steady and cyclic purge mechanisms and predict complex purge scenarios. Industrially relevant and applicable boundary conditions and system definitions were used to increases the utility of the computational tool. Although SSP compared closely with PCP on simple systems without laterals, a drastic difference in dry-down efficiency was noticed in systems with dead volumes in the form of capped laterals. Studies on system design parameters revealed that the disparity in performance was observed to increase with larger number and surface area of dead volumes, opening a path to critical understanding of the differences in process mechanisms. Beneficial transient pressure gradient induced convective flow in the dead volumes during cyclic purge was identified to be the main factor driving the enhanced dry down rate. Similar trends were observed on using surface concentration as the purge metric. Hybrid purge schemes involving a combination of SSP and PCP were found to yield higher benefit in terms of efficient use of purge gas. Removal of strongly interacting contaminant species showed a higher benefit from use of controlled PCP scheme. Although, parametric analysis carried out on the operating factors of cyclic purge suggested that the enhancement in dry down increased with higher pressure range, it was highly conditional towards configurational factors in design and operation such as system dimensions, holding time, cycling pattern, valve loss coefficients and the complex inter coupling between them. The robustness of the process simulator allows the development of optimal purge scenarios for a given set of system parameters in order to perform a controlled purge. The benefit of using a hybrid PCP scheme was evaluated in terms of UHP purge gas and process time as a function of purity baseline required. Apart from UHP gas distribution systems, process vessels, chambers and components along the process stream are also prone to molecular contamination and pose a threat to product integrity. The dead volumes acting as areas of contaminant accumulation represent cavities or dead spaces in flow control elements such as mass flow controllers (MFCs), gauges, valves or dead spaces in process chambers. Steady purge has very little effect in cleanup of such areas and more efficient methods are necessitated to raise purge efficiency. The analysis of application of PCP is extended to such components through the development of a robust and comprehensive process simulator. The computational model applies a three dimensional physical model to analyze purge scenarios with steady and cyclic purge. The results presented pertain to any generic gas phase contaminant and electronic grade steel surfaces. Close investigation of the purge process helped elaborate the cleaning mechanism. Critical steps driving the purge process were identified as - dilution of chamber by introduction of fresh gas during re-pressurization and chamber venting during depressurization. Surface and gas phase purging of chambers with dead spaces using steady and cyclic purge were studied and compared. Cyclic purge exhibited a higher rate of dry down. The effect of system, design and purge operating parameters on surface cleaning were studied. Although higher frequency cycles and larger operating pressure ranges optimized for a given geometry are found to deliver better pressure cyclic purge (PCP) performances, the benefit is found to be contingent to a strong interplay between system parameters. PCP is found to be advantageous than steady state purge (SSP) in terms of purge gas usage and operation time in reaching a certain purity baseline. Specialty process gases supplied to the fabrication facility are typically stored in the form of liquids in enormous tanks outside the fab. Ammonia is a widely used in UHP concentrations for a variety of process including epitaxial growth, MOCVD, etching and wet processes in the semiconductor industry. The recent development in LED research has risen the demand and supply for Ammonia based compounds. Stringent baselines are maintained for the impurities associated with the manufacturing of such gases (e.g. Moisture in Ammonia). Apart from the difference in the rates of evaporation of the individual species from the storage cylinder causing accumulation of slower evaporating species, external temperature fluctuations also generate unsteady flux of desired species. When concentrations rise above this threshold additional purification or in most cases discarding large volumes of unused gas is warranted, causing loss of resources and causing ESH issues. Bulk gases are usually delivered over long lengths of large diameter pipes which produce large density of adsorption sites for contaminants to accumulate and eventually release into the gas stream. In order to establish contamination control in the gas delivery system, the surface interactions of the multispecies system with the delivery line surface was characterized. Desired concentrations of moisture in ammonia and UHP nitrogen mixtures were produced in a gas mixing section capable of delivering controlled mass flow rates to an EPSS test bed. Transient moisture profiles during adsorption and desorption tests at various test bed temperatures, mass flow rates and moisture concentration were captured by a highly sensitive analyzer. A mathematical model for single and multi-species adsorption was used in conjunction with experimental data to determinate kinetics parameters for moisture, ammonia system in EPSS surface. The results indicate competitive site binding on EPSS between ammonia and water molecules. Also, the concentration distribution of each species between surface, gas phase is interdependent and in accordance to the kinetic parameters evaluated. Back diffusion of impurity is a major source of contaminant introduction into UHP streams. Back diffusion refers to the transport of contaminants against the flow of bulk process stream. Molecular species can back diffuse from dead volumes, during mixing operations etc., simply when there is a gradient of concentration. A steady state approach was used to analyze the mechanism and effects of various geometrical and operational parameters on back diffusion. High sensitivity moisture detectors were used to capture the dynamics of contamination in a section of a generic distribution system. Results showed that back diffusion can occur through VCR fittings, joints and valves under constant purge. General trends on the effect of design parameters on back diffusion were derived from studies on various orifice sizes, system dimensions, flow rates and test moisture concentrations. Coupled parametric studies helped identify critical variable groups to perform dimensionless analysis on back diffusion of moisture. Crucial points where back diffusion can be minimized or completely eliminated are identified to help set up guidelines for cyclic and steady purge parameters without excessive use of expensive UHP gas or installation of unnecessarily large factors of safety. Wet cleaning of micro/nano sized features is a highly frequent process step in the semiconductor industry. The operation is a huge consumer of ultra-pure water and one of the main areas where process time minimization is focused. Comprehensive process model is developed to simulate the mechanism and capture the dynamics of rinsing high aspect ratio Silicon features in the nanometer scale. Rinsing of model trench, post etch contaminated with ammonium residue is studied. Mass transport mechanisms such as convection, diffusion are coupled with surface processes like adsorption and desorption. The effect of charged species on the trench surface and in the bulk, the resultant induced electric field on the rinse dynamics and decay of surface species concentration is studied. General rinsing trends and critical points in change in mechanisms were identified with critical groups such as mass transfer coefficient and desorption coefficient. The model is useful in evaluating process efficiency in terms of rinse time and DI water consumption under varying process temperature, contaminant concentration, and rinse fluid flow rate. The generic build of the model allows extension of its functionality to other impurity-substrate material couples.

Thesis (MSc)--Stellenbosch University, 2004. / ENGLISH ABSTRACT: The choice of the sample preparation technique used in combination with a chromatographic technique in environmental analysis strongly influences the performance of the method as a whole. The main aim of this work was to evaluate methods like: micro liquid-liquid extraction (цLLE)and solid phase micro extraction (SPME) in combination with gas chromatography-electron capture detector (GCECD) and a recently developed technique named stir bar sorptive extraction (SBSE) combined with thermal desorption system-programmable temperature vaporizationgas chromatography-mass spectrometer (TDS-PTV-GC-MS) for the analysis of organochloro-pesticides (OCPs) in natural water and to make a comparison between them. The most suitable method was then selected for the analysis of water samples collected from Eritrea. An additional goal was to develop a sensitive method for the analysis ofOCPs in soil and sediment samples. цLLE-GC-ECD and SPME-GC-ECD methods were evaluated for the analysis of OCPs in water. The former allowed achieving a sensitivity of less than 100 ppt and the latter was able to detect down to the 1 ppt level. Both methods were found to be repeatable with %RSD of3% to 19% and 5% to 12% as well as linear with a range of 1:103 and 1:5x103 respectivey. SBSE-TDS-GC-MS was also investigated for the analysis of OCPs in water samples. With this technique a good sensitivity down to 1 ppt was also obtained. The less sensitive nature of the MS compared to ECD was hereby compensated for by the large amount of polydimethylsiloxane (PDMS) phase on the stir bar. The method was repeatable and linear with a range of 1:5000, which is similar to the one obtained for the SPME-GC-ECD method. All three methods were also tested with real contaminated water samples and a comparison of the three techniques in terms of sensitivity, linearity, repeatability, availability and cost effectiveness was done. As a method of choice in terms of the above criteria, SPMEGC- ECD was applied to the water samples collected from Eritrea. The presence of some oePs such as a-BBC (benzenehexachloride), heptachlor, heptachlor epoxide, endosulfan I, p,p'-DDE (dichlorodiphenylchloroethylene), endosulfan II, p,p'-DDD (dichlorodiphenyldichloroethane), endosu!fan sulfate and p,p'-DDT (dichlorodiphenyltrichloroethane) in some of the Eritrean water samples was demonstrated The SPME-GC-ECD technique for the analysis OCPs in soil and sediment samples was investigated. It was shown to be able to detect down to 1 pg/g (lppt) with good linearity and repeatability. The method was also evaluated for authentic soil samples. Due to a lack of time the method could not be applied for the analysis of the soil and sediment samples collected from Eritrea. / AFRIKAANSE OPSOMMING: Die keuse van 'n gepaste monster-voorbereidingsmetode wat gebruik word tesame met 'n chromatografiese skeidingtegniek in omgewings-analise het 'n beduidende effek op die algehele metode. Die doel van hierdie werk was om metodes soos mikrovloeistof- vloeistof ekstraksie (цLLE) en soliede fase mikro ekstraksie (SPME) in kombinasie met gaschromatografie met elektronvangs deteksie (GC-ECD) te ontwikkel vir die analise van organochloor-pestisiede (OCPs) in natuurlike water. Vervolgens is hierdie metodes vergelyk met die onlangs-ontwikkelde roerstaaf sorptiewe ekstraksie tegniek (SBSE) in kombinasie met termiese desorbsie-GCmassaspektrometriese deteksie (TDS-GC-MSD). Die mees geskikte metode is vervolgens gebruik vir die analise van Eritreaanse watermonsters. Daarbenewens was die doelook om 'n sensitiewe metode te ontwikkel vir die analise van OCPs in gronden sedimentmonsters. Beide цLLE en SPME-GC-ECD metodes is gekarakteriseer deur goeie herhaalbaarheid en lineariteit. Die sensitiwiteit van bogenoemde metodes was minder as 100 dele per triljoen (ppt) en 1 ppt, respektiewelik. Ook met SBSE-TDS-GC-MSD kon 'n deteksielimiet van 1 ppt bereik word. In hierdie geval is vir die verlies van sensitiwiteit van die MSD in vergelyking met die ECD, gekompenseer deur die groter hoeveelheid PDMS op die roerstaaf in vergelyking met 'n SPME apparaat. Die herhaalbaarheid en lineariteit van die metode is vergelykbaar met dié van die SPMEGC- ECD metode. Al drie metodes is vergelyk vir die analise van gekontamineerde watermonsters in terme van sensitiwiteit, liniêre bereik, herhaalbaarheid, toeganklikheid en kosteeffektiwiteit. SPME-GC-ECD is vervolgens gekies as metode van voorkeur vir die analise van Eritreaanse watermonsters. Die teenwoordigheid van sekere OCPs soos a-BHC, heptachloor, heptachloorepoksied, endosulfan I, p,p'-DDE, endosulfan II, p,p' -DDD, endosulfan sulfaat en p,p' -DDT in die monsters is gedemonstreer. Die toepasbaarheid van die SPME-GC-ECD metode vir die analise van OCPs in grond-en sedimentmonsters is ook geëvalueer, en dit was moontlik om so min as 1 pg/g waar te neem. Weens tydbeperkings was dit nie moontlik om Eritreaanse grondmonsters met die ontwikkelde metode te analiseer nie.

This thesis presents experimental studies of three different chemical reaction steps relevant for heterogeneous catalysis: dissociation, desorption, and oxidation. CO on single-crystal metal surfaces was chosen as the model systems. X-ray absorption spectroscopy (XAS) and x-ray emission spectroscopy (XES) provide information about the electronic structure, and were performed on CO/Fe to measure both a non-dissociative, and a pre-dissociative state. The measurement on the pre-dissociative state showed a π →  π* excitation, which implies a partly broken internal π bond in the molecule. Ultrafast laser-induced reactions were used to examine the dynamic properties of desorption and oxidation. Here CO/Ru and CO/O/Ru were used as model systems. Desorption of CO from a Ru surface involve both hot electrons and phonons. In the case of CO oxidation from CO/O/Ru a pronounced wavelength dependence of the branching ratio between desorption and oxidation was observed. Excitation with 400 nm showed a factor of 3-4 higher selectivity towards oxidation than 800 nm. This was attributed to coupling to transiently excited, non-thermalized electrons. Finally, by performing optical pump/x-ray probe XAS and XES changes in the electronic structure during the reaction could be followed, both for desorption and oxidation. In the CO/Ru experiment, two different transient excitation paths were observed, one leading to a precursor state, and one where CO moves into a more highly coordinated site. Using selective excitation in XES, these were shown to coexist on the surface. In the oxidation experiment, probing the reacting species located near the transition state region in an associative catalytic surface reaction was demonstrated for the very first time.

Sterilization of tissue engineered scaffolds is an important regulatory issue and is at the heart of patient safety. With the introduction of new biomaterials and micro/nano structured scaffolds, it is critical that the mode of sterilization preserve these built-in features. Conventional sterilization methods are not optimal for engineered polymeric systems and hence alternate systems need to be identified and validated. PCL is polyester with a low melting point (heat labile), susceptible to hydrolysis and is popular in tissue engineering. Electrospinning generates some nanoscale features within the scaffold, the integrity of which can be affected by sterilization method. Chapter 1 explores the possibility of using Peracetic acid (PAA) to sterilize polymeric scaffolds that are sensitive to heat or moisture. PAA is a strong oxidizing agent that has been approved for sterilizing catheters and endoscopes. The ability of PAA to sterilize at room temperature, its breakdown into non-toxic end products and effectiveness at low concentrations are major advantages. Chapter 2 evaluates the ability of PAA-sterilized PCL scaffolds (PAA-PCL) to support survival and proliferation of mouse calvarial osteoblast cell line, MC3T3. While Ctrl-PCL scaffolds (ethanol-disinfected) showed robust cell survival, PAA-PCL scaffolds induced massive cell death. Following interrelated hypotheses are tested: the observed cytotoxicity was due adsorption of PAA and/or hydrogen peroxide onto PCL fibers during sterilization; and elimination of adsorbed residues will restore scaffold cytocompatibility. Neither extensive aeration nor chemical neutralization with sodium thiosulfate and catalase were effective in improving cell survival. However, quenching PAA-PCL scaffolds in 70% ethanol for 30 minutes effectively removed adsorbed PAA residues and completely restored cell viability and proliferation over a 7 day period. In order to test if PAA-induced toxicity was limited to electrospun PCL scaffolds, commercially available, porous polystyrene scaffolds (Alvetex®) was treated with PAA. Interestingly, a statistically significant increase in cell survival and proliferation resulted with PAA treatment and this was abolished by ethanol quenching. Combined, these results illustrate that PAA treatment can produce diametrically opposite effects on cell survival depending on substrate chemistry and that PAA can be used to effectively sterilize tissue engineering scaffolds without compromising cell viability.