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Dielectric elastomers are highly promising as functional materials for the rapidly developing field of flexible actuator and generator technology. They offer a unique combination of low densities and large reversible deformations of up to more than 100% in area, and consequently have great potential for many new types of application. However, implementation has been impeded by the lack of specialized materials. The elastomers that have so far been investigated suffer from a number of disadvantages, including the need for very high activation voltages and limited service lifetimes. This thesis describes an investigation of the use of elastomeric composites as dielectric elastomers with the aim of optimizing and improving their performance in actuators. The influence of materials properties on actuation was first analyzed on the basis of a simple physical model and materials properties derived from standard test methods. The implications for the actuation performance of three conventional dielectric elastomers were then considered in detail. A preliminary conclusion was that the actuation performance could be improved if the permittivity of the elastomers were to be increased by modification with ceramic or conductive fillers. However, actuation performance was shown to depend not only on the permittivity, but also on the elastic modulus, the electrical breakdown strength, and strain hardening. Thus, although significant increases in permittivity were achieved by this approach, actuation performance was compromised by an increase in modulus in the case of the ceramic fillers, and a dramatic drop in electrical breakdown strength, in the case of the conducting fillers. A more promising approach was therefore suggested to be the use of an organic conducting filler encapsulated in an insulating matrix. It was demonstrated that it is indeed possible to increase the permittivity of a given elastomer while maintaining a high electrical breakdown strength. Different processing routes were investigated in order to control the dispersion of the filler and tailor performance. The optimum filler concentration, i.e. that providing the best compromise between permittivity and stiffness, was determined to be approximately 16 vol%, resulting in an improvement by a factor of 2 in actuation strain for a given applied voltage over that obtained with the unmodified matrix. Higher filler concentrations were also argued to have considerable potential for use in generators, given that the observed increased permittivity was also associated with high electrical breakdown strengths and increased strains at break. A threefold increase in converted energy per working cycle was predicted for a composite containing 25.5 vol% fillers based on a simplified model for a dielectric elastomer generator. Whilst these results are extremely encouraging, it is concluded that the composite approach has, in general, only limited potential as a means of obtaining further increases in actuation performance. The major difficulty remains that the use of a relatively rigid second phase to increase dielectric performance will inevitably also increase the elastic modulus beyond a certain filler concentration. As argued in the final part of the thesis, the way forward may therefore ultimately depend on the development of new types of synthetic elastomeric matrix materials that combine intrinsic improvements in electrical response with reduced moduli.

The search for affordable high performance electrode materials in photoelectrochemical hydrogen production by solar water splitting is an ongoing quest. Hematite is a photoanode material with an electronic band gap suitable for efficient absorption of visible light in a photoelectrochemical cell (PEC). Although its poor electronic structure makes hematite a controversial candidate for PEC, it remains promising because it is an earth abundant, chemically stable and low cost material – necessary prerequisites for PEC to become a competitive cost-efficient solar fuel economy. In addition to reviewing some recent PEC research on hematite and its relevant physical and chemical characteristics, we show how hematite obtained by a low cost synthesis can be refined by hydrothermal treatment and further functionalized by coating with phycocyanin, a light harvesting protein known for photosynthesis in blue-green algae.

Distributed power generation and cogeneration of heat and power is an attractive way toward a more rational conversion of fossil and bio fuels. Solid oxide fuel cell (SOFC) – gas turbine (GT) hybrid systems are emerging as the most promising candidates enabling the achievement of a cleaner and more efficient conversion of a large variety of resources across a broad power range covering from small to medium scale applications. This thesis introduces an innovative concept of SOFC-GT hybrid system that allows reaching efficiencies higher than the state of the art while enabling the carbon dioxide separation and avoiding fuel cell pressurisation technical issues. Several hybrid system design alternatives based on this concept are analysed through a thermodynamic optimisation approach combining process modelling, advanced process integration techniques and multi-objective optimisation. A number of optimal hybrid system configurations are determined for different design targets. The results consistently demonstrate the higher energy conversion performance and flexibility enabled with respect to the state of the art. The innovative concept analysis is extended to two applications for which SOFC-GT hybrid cycles are expected to provide the most significant impact toward sustainability: the small scale distributed generation and the conversion of renewable resources. A simplified version of the new hybrid system layout is especially developed for small scale distributed generation, typical of residential building applications (5-10 kWel). Experimental data are used to prove the technical feasibility of the system and to assess the performance potentially achievable with currently feasible technologies. The results of the analysis underline that energy conversion efficiencies higher than traditional centralised power generation can be achieved even at such a small scale. A systematic process integration and optimisation approach is used to assess the energy conversion performance of the original SOFC-GT hybrid cycle fuelled with hydrothermally gasified wet waste biomass. The analysis highlights the considerable potential of the integrated system that allows for converting wet waste biomass into electricity with First Law efficiency higher than 60% while simultaneously enabling the separation of the biogenic carbon dioxide.

Searching suitable panchromatic QD sensitizers for expanding the light-harvesting range, accelerating charge separation, and retarding charge recombination is an effective way to improve power conversion efficiency (PCE) of quantum-dot-sensitized solar cells (QDSCs). One possible way to obtain a wide absorption range is to use the exciplex state of a type-II core/shell-structured QDs. In addition, this system could also provide a fast charge separation and low charge-recombination rate. Herein, we report on using a CdTe/CdSe type-II core/shell QD sensitizer with an absorption range extending into the infrared region because of its exciplex state, which is covalently linked to TiO2 mesoporous electrodes by dropping a bifunctional linker molecule mercaptopropionic acid (MPA)-capped QD aqueous solution onto the film electrode. High loading and a uniform distribution of QD sensitizer throughout the film electrode thickness have been confirmed by energy dispersive X-ray (EDX) elemental mapping. The accelerated electron injection and retarded charge-recombination pathway in the built CdTe/CdSe QD cells in comparison with reference CdSe QD-based cells have been confirmed by impedance spectroscopy, fluorescence decay, and intensity-modulated photocurrent/photovoltage spectroscopy (IMPS/IMVS) analysis. With the combination of the high QD loading and intrinsically superior optoelectronic properties of type-II core/shell QD (wide absorption range, fast charge separation, and slow charge recombination), the resulting CdTe/CdSe QD-based regenerative sandwich solar cells exhibit a record PCE of 6.76% (J(sc) = 19.59 mA cm(-2), V(oc) = 0.606 V, and FF = 0.569) with a mask around the active film under a full 1 sun illumination (simulated AM 1.5), which is the highest reported to date for liquid-junction QDSCs.

The constituent countries of the MENA region---defined in this thesis in conformity with the regional definition of the International Energy Agency and encompassing 17 Muslim countries in North Africa, in the Levant, on the Arabian Peninsula, and Iran---have developed very rapidly over the past decade. Two figures best exemplify the region's tremendous transformation: Total population has expanded by more than 20% and its aggregate economic output has more than doubled. As much as this development is desirable, said development trends have also dramatically reshaped the energy policy environment in the MENA region and began causing problems of their own---affecting the region's large oil exporters and its energy importers alike. Having traditionally enjoyed high energy security and handsome resource rents by virtue of their abundant and cheap fossil fuels, new realities in the domestic energy systems demand a new policy focus on domestic energy issues. Energy challenges have emerged which threaten security of supply, fiscal stability, and environmental integrity. The challenges differ in magnitude from country-to-country and reflect the specific national conditions and circumstances. However, given the similarity in the underlying drivers and the governing energy policies, the energy challenges resemble each other across borders. More specifically, ballooning domestic energy demand consumes a rising share of national energy production and thus increasingly imperils the constant flow of the much needed proceeds from oil and gas exports. In the MENA countries with less abundant hydrocarbon resources, domestic demand growth has heightened energy dependence and, to make matters worse, the tighter supply situation in the energy exporting neighbors may eventually also lead to a discontinuation of the preferential supply agreements which they have benefitted from in the past. As a further corollary of demand growth, massive capital-intensive infrastructure investments are necessary to keep pace with the growth on the demand side. The regional tradition to sell energy commodities domestically at prices non-competitive prices or even below cost, however, limits the national energy sectors' own capability of mustering the required capital. Finally, the universally observable heavily fossil fuel-dominated national energy mixes in the region render the study countries vulnerable to supply shocks. The virtually complete reliance on the regionally available hydrocarbons for meeting energy demand is also a principal contributor to environmental degradation and at the core of the large carbon footprint of energy consumption in MENA countries. Given current policies in combination with the emerging demographic and economic trends, these challenges must be expected to become more severe in the years to come. Rising living standards, especially in the region's expanding urban population, are likely to boost per capita energy consumption. The projected, continued demographic and economic growth will further drive commodity demand. And the supply side cannot be counted on to mitigate the challenges under given policies. On the contrary. Although no reliable production projections are available, it stands to reason that production from the region's most prolific oil and gas fields---some of which have been producing for several decades now---will increasingly require the use of costly secondary and tertiary recovery methods and that some will eventually [...]

A water-soluble organic redox couple (TT−/DTT) and new organic dyes (D45 and D51) have been developed for aqueous dye-sensitized solar cells (DSCs). An optimal efficiency of 3.5% was obtained using the D51 dye and an optimized electrolyte composition. The highest IPCE value obtained was 68% at 460 nm.

Although mature technologies at competitive prices are largely available, solar thermal is not yet playing the important role it deserves in the reduction of buildings fossil energy consumption. The generally low architectural quality characterizing existing building integrations of solar thermal systems pinpoints the lack of design as one major reason for the low spread of the technology. As confirmed by the example of photovoltaics, the improvement of the architectural quality of building integrated systems can increase the use of a solar technology even more than price and technique. This thesis investigates the possible ways to enhance the architectural quality of building integrated solar thermal systems, and focuses on integration into façade, where the formal constraints are major and have most impact. The architectural integration problematic is structured into functional, constructive and formal issues, so that integration criteria are given for each architectural category. As the functional and constructive criteria are already recognized by the scientific community, the thesis concentrates on the definition of the formal ones, yet underestimated or misunderstood. The results of a large European survey over architects and engineers perception of building integration quality are presented, showing that for architects formal issues are not a matter of personal taste, but that they relate to professional competences, and consequently can be described. The solar system characteristics having an impact on the formal quality of the integration are identified (formal characteristics), the related integration criteria are assessed, and finally integration guidelines to support architect integration design work are given. The limits imposed by the collectors available in the market are pointed out, showing that the lack of appropriate products is nowadays the main barrier to BIST (Building Integrated Solar Thermal) architectural quality. A methodology for the development of new solar thermal collectors systems responding at the same time to energy production needs and building integration requirements is defined. The importance to ensure, within the design team, the due professional competences in both these fields is stressed. Three progressive levels of system "integrability" are defined in the path leading to the concept of "active envelope systems" and the main role of facade manufacturers is highlighted. The methodology is applied to unglazed and glazed flat plate systems, and new façade system designs are proposed that show the relevance of the proposed approach.

Natural gas is defined as a combustible mixture of hydrocarbons coming from ground deposits and it is mainly used as a source of energy for burners and motors. Its consumption is increasing worldwide, as this represents a cheap and abundant source of energy, while releasing less CO2 emissions than other fossil fuels, in addition to low emissions of particulates. The diversification of the supply sources of gas and the increase of international trading through pipelines and liquefied natural gas (LNG) shipments makes the gas quality vary more than before, which is a rising challenge for the natural gas industry, as currently the vast majority of gas appliances and motors are unable to adapt to changes in gas quality. This will even worsen in the upcoming years with the multiplication of biogas sources and power-to-gas systems that will be added to the pipeline networks. In order to accomodate the appliances to changes in gas quality, compact and low cost natural gas quality transducers have to be developped for the natural gas industry. The present Thesis aimed at investigating the existing methods to determine natural gas quality for combustion, focusing on the determination of the Wobbe Index (WI), which is a key parameter to set up the air-fuel ratio of the combustion in burners and motors, and to qualify a new type of dynamic viscosity transducer developped at Laboratoire de Production Microtechnique (LPM) of EPFL for the determination of the combustion properties. Inference transducers are a new kind of transducers that allow determining the combustion parameters of the gas by relating to fundamental thermo-physical parameters, and not through the determination of the concentration of the gas constituents, as in gas chromatographs and spectrometers. Here, the dynamic viscosity is chosen as the most promising thermo-physical property of a natural gas to relate to the WI and the Higher Heating Value (HHV). The viscometer takes measurements proportional to the resistance to flow of a gas through a capillary under the action of pulses of heat, and it can be therefore be described as a thermal pumping gas viscometer. A mathematical model and a finite element model (FEM) are used to predict the behavior of the system and for thermal optimization, which are combined by a thermal characterization of the system. The miniature heater used to generate the heat pulses inside the viscometer is a key element of the transducer, and after reviewing potential technologies, the design choices are reported and the fabrication process is exposed, followed by a mechanical and thermal characterization. In order to determine and validate the conversion of the WI from the dynamic viscosity, theoretical relations are analyzed and empirical characterizations are done with a test and calibration setup allowing to create given mixes of gases. Finally, the degradation of the transducer to contaminants of natural gas is investigated, and the analysis is focused to the characterization of the corrosion by the sulfur compounds of natural gas. Test vehicles are developed to study the effect of sulfur corrosion on metallic parts, electronic substrates, silicone adhesives and wirebonds materials, and experiments are held with the dedicated test setups developed at LPM of EPFL.

This article is about diffusion processes behind the innovation of sub-national energy policy measures in a federal system. Typically for the federal political system in Switzerland, the elements of the energy policy field are shaped by the principle of subsidiarity. The aim is that cantons promote innovative problem solutions and regionally adapted implementation. For this reason, policy differences between cantons are large and create a need for coordination. More concretely, I will analyze the impact of inter-cantonal institutions on different innovations in the field of energy policy. The research question is approached with an event history analysis on three different innovative measures in the Swiss cantons from 1990 to 2007. A more comprehensive picture of diffusion in one policy field is drawn with this approach. The main contribution of this paper is the finding that intergovernmental institutions promote diffusion in one policy field only for measures with certain characteristics. The internal determinants are therefore not a sufficient explanation.