Phosphonsäurehaltige polycyclische aromatische Kohlenwasserstoffe für Anwendungen in Brennstoffzellen

Die vorliegende Arbeit umfasst die Synthese und Charakterisierung phosphonsäurehaltiger, organischer Kristalle als ionenleitende Verbindungen in Brennstoffzellen-Anwendungen. Sie zielt dabei einerseits auf die Darstellung von protonenleitenden Polyphenylenverbindungen und deren Verwendung als Linker für den Aufbau protonenleitender Aluminium-Phosphonat-Netzwerke ab und behandelt andererseits die Einführung stark polarer Phosphonsäuregruppen in einen diskreten Nanographenkern sowie deren Einfluss auf die ionen- und elektronenleitenden Eigenschaften, um diese als gemischt-leitende Kompatibilisatoren an der isolierenden Elektrode/ Membran-Grenzfläche in einer Brennstoffzelle zu verwenden. Am Beispiel eines phosphonsäurefunktionalisierten, phenylenisch-expandierten Hexaphenylbenzols konnte ein solvothermisch stabiler Protonenleiter mit einer Selbstorganisation in kolumnare, supramolekulare Strukturen und hoher, temperaturunabhängiger Leitfähigkeit mit dominierendem Grotthuss-Anteil präsentiert werden. Durch einen Wechsel dieser 1D-radialen Phosphonsäureanordnung in der Molekülhülle hin zu 2D- und 3D-H2PO3-funktionalisierten, dendritischen Stäbchen- bzw. Kugelstrukturen konnte gezeigt werden, dass eine kolumnare Molekülanordnung jedoch kein notwendiges Kriterium für einen Grotthuss-artigen Protonentransport darstellt. Durch die mehrdimensionale Orientierung der Phosphonsäuren in der Außenhülle der Dendrimere garantieren die synthetisierten Strukturen hochaggregierte Phosphonsäurecluster, die als dichtes Säurekontinuum die eigentlichen protonenleitfähigen Kanäle darstellen und somit als entscheidendes Kriterium für das Auftreten eines Grotthuss-artigen Mechanismus definiert werden müssen. Eine signifikante Erhöhung der Leitfähigkeit konnte durch den Aufbau poröser, organisch-anorganischer Netzwerke (Al-HPB-NETs) über Komplexierung einer unterstöchiometrischen Menge an Aluminium-Kationen mit der Polyphosphonsäureverbindung Hexakis(p-phosphonatophenyl)benzol als Linkereinheit erfolgen, die anschließend mit kleinen intrinsischen Protonenleitern wie Phosphonsäure dotiert wurden. Diese dotierten Netzwerke wiesen außergewöhnliche Leitfähigkeit auf, da sie die σ-Werte des Referenzpolymers Nafion® bereits in einem Temperaturbereich oberhalb von 135°C übertrafen, aber gleichzeitig ein sehr gutes Säureretentionsverhalten von einem Gew.-% Säuredesorption über eine Immersionsdauer von 14 h gegenüber wässrigem Medium zeigten. Durch Mischen dieser Aluminiumphosphonate mit einer dotierten Polymermatrix wie PBI konnten synergistische Effekte durch zusätzliche attraktive H-Brückenbindungen zwischen molekular angebundener Phosphonsäure und mobiler H3PO4 an Hand eines signifikanten Leitfähigkeitsanstiegs für die resultierenden Membranen beobachtet werden. Die Protonenleitfähigkeit lag in diesen Materialien in dem gesamten untersuchten Temperaturbereich oberhalb von Nafion®. Durch das Einbringen der NETs in PBI konnte ebenfalls die Säureretention von PBI um etwa 9 % bei kurzen Immersionszeiten (bis 1 min) verbessert werden. Darüber hinaus wurde in der vorliegenden Arbeit die synthetische Kombination eines hydrophoben, elektronenleitenden Nanographenkerns mit einer, durch eine isolierende Peripherie getrennten, stark polaren, protonenleitenden Außenhülle realisiert. Am Beispiel von zwei phosphonsäurefunktionalisierten Triphenylenen, die sich in Länge und Planarität der gewählten Peripheriebausteine unterschieden, sollten polycyclische aromatische Kohlenwasserstoffe mit gemischt protonen- und elektronenleitenden Eigenschaften hergestellt werden, die über Impedanzspektroskopie und Vierpunktmessungen untersucht wurden. Da es sich bei der Anwendung solcher gemischtleitenden Verbindungen um grenz-flächenaktive Substanzen handelt, die das ohne verbesserte Anbindung bestehende Dielektrikum zwischen Elektrode und protonenleitender Membran überbrücken sollen, wurde die Untersuchung eines möglichen Elektronentransportes durch eine Molekülmonolage ebenfalls über kombinatorische STM- und STS-Technik durchgeführt.

End-User Development Success Factors and their Application to Composite Web Development Environments

The Future Internet is expected to be composed of a mesh of interoperable Web services accessed from all over the Web. This approach has not yet caught on since global user-service interaction is still an open issue. Successful composite applications rely on heavyweight service orchestration technologies that raise the bar far above end-user skills. The weakness lies in the abstraction of the underlying service front-end architecture rather than the infrastructure technologies themselves. In our opinion, the best approach is to offer end-to-end composition from user interface to service invocation, as well as an understandable abstraction of both building blocks and a visual composition technique. In this paper we formalize our vision with regard to the next-generation front-end Web technology that will enable integrated access to services, contents and things in the Future Internet. We present a novel reference architecture designed to empower non-technical end users to create and share their own self-service composite applications. A tool implementing this architecture has been developed as part of the European FP7 FAST Project and EzWeb Project, allowing us to validate the rationale behind our approach.

A component- and connector-based approach for end-user composite web applications development

Enabling real end-user development is the next logical stage in the evolution of Internet-wide service-based applications. Successful composite applications rely on heavyweight service orchestration technologies that raise the bar far above end-user skills. This weakness can be attributed to the fact that the composition model does not satisfy end-user needs rather than to the actual infrastructure technologies. In our opinion, the best way to overcome this weakness is to offer end-to-end composition from the user interface to service invocation, plus an understandable abstraction of building blocks and a visual composition technique empowering end users to develop their own applications. In this paper, we present a visual framework for end users, called FAST, which fulfils this objective. FAST implements a novel composition model designed to empower non-programmer end users to create and share their own self-service composite applications in a fully visual fashion. We projected the development environment implementing this model as part of the European FP7 FAST Project, which was used to validate the rationale behind our approach.

Polymer interaction with macroscopic carbon nanotube fibres and fabrication of nanostructured composites

El ensamblado de nanotubos de carbono (CNT) como una fibra macroscópica en la cual están orientados preferentemente paralelos entre sí y al eje de la fibra, ha dado como resultado un nuevo tipo de fibra de altas prestaciones derivadas de la explotación eficiente de las propiedades axiales de los CNTs, y que tiene un gran número de aplicaciones potenciales. Fibras continuas de CNTs se produjeron en el Instituto IMDEA Materiales mediante el proceso de hilado directo durante la reacción de síntesis por deposición química de vapores. Uno de los objetivos de esta tesis es el estudio de la estructura de estas fibras mediante técnicas del estado del arte de difracción de rayos X de sincrotrón y la elaboración de un modelo estructural de dicho material. Mediciones texturales de adsorción de gases, análisis de micrografías de electrones y dispersión de rayos X de ángulo alto y bajo (WAXS/SAXS) indican que el material tiene una estructura mesoporosa con una distribución de tamaño de poros ancha derivada del amplio rango de separaciones entre manojos de CNTs, así como una superficie específica de 170m2/g. Los valores de dimensión fractal obtenidos mediante SAXS y análisis Barrett-Joyner-Halenda (BJH) de mediciones texturales coinciden en 2.4 y 2.5, respectivamente, resaltando el carácter de red de la estructura de dichas fibras. La estructura mesoporosa y tipo hilo de las fibra de CNT es accesible a la infiltración de moléculas externas (líquidos o polímeros). En este trabajo se estudian los cambios en la estructura multiescala de las fibras de CNTs al interactuar con líquidos y polímeros. Los efectos de la densificación en la estructura de fibras secas de CNT son estudiados mediante WAXS/SAXS. El tratamiento de densificación junta los manojos de la fibra (los poros disminuyen de tamaño), resultando en un incremento de la densidad de la fibra. Sin embargo, los dominios estructurales correspondientes a la transferencia de esfuerzo mecánica y carga eléctrica en los nanotubos no son afectados durante este proceso de densificación; como consecuencia no se produce un efecto sustancial en las propiedades mecánicas y eléctricas. Mediciones de SAXS and fibra de CNT antes y después de infiltración de líquidos confirman la penetración de una gran cantidad de líquidos que llena los poros internos de la fibra pero no se intercalan entre capas de nanotubos adyacentes. La infiltración de cadenas poliméricas de bajo peso molecular tiende a expandir los manojos en la fibra e incrementar el ángulo de apertura de los poros. Los resultados de SAXS indican que la estructura interna de la fibra en términos de la organización de las capas de tubos y su orientación no es afectada cuando las muestras consisten en fibras infiltradas con polímeros de alto peso molecular. La cristalización de varios polímeros semicristalinos es acelerada por la presencia de fibras de CNTs alineados y produce el crecimiento de una capa transcristalina normal a la superficie de la fibra. Esto es observado directamente mediante microscopía óptica polarizada, y detectado mediante calorimetría DSC. Las lamelas en la capa transcristalina tienen orientación de la cadena polimérica paralela a la fibra y por lo tanto a los nanotubos, de acuerdo con los patrones de WAXS. Esta orientación preferencial se sugiere como parte de la fuerza impulsora en la nucleación. La nucleación del dominio cristalino polimérico en la superficie de los CNT no es epitaxial. Ocurre sin haber correspondencia entre las estructuras cristalinas del polímero y los nanotubos. Estas observaciones contribuyen a la compresión del fenómeno de nucleación en CNTs y otros nanocarbonos, y sientan las bases para el desarrollo de composites poliméricos de gran escala basados en fibra larga de CNTs alineados. ABSTRACT The assembly of carbon nanotubes into a macroscopic fibre material where they are preferentially aligned parallel to each other and to the fibre axis has resulted in a new class of high-performance fibres, which efficiently exploits the axial properties of the building blocks and has numerous applications. Long, continuous CNT fibres were produced in IMDEA Materials Institute by direct fibre spinning from a chemical vapour deposition reaction. These fibres have a complex hierarchical structure covering multiple length scales. One objective of this thesis is to reveal this structure by means of state-of-the-art techniques such as synchrotron X-ray diffraction, and to build a model to link the fibre structural elements. Texture and gas absorption measurements, using electron microscopy, wide angle and small angle X-ray scattering (WAXS/SAXS), and pore size distribution analysis by Barrett-Joyner-Halenda (BJH), indicate that the material has a mesoporous structure with a wide pore size distribution arising from the range of fibre bundle separation, and a high surface area _170m2/g. Fractal dimension values of 2.4_2.5 obtained from the SAXS and BJH measurements highlight the network structure of the fibre. Mesoporous and yarn-like structure of CNT fibres make them accessible to the infiltration of foreign molecules (liquid or polymer). This work studies multiscale structural changes when CNT fibres interact with liquids and polymers. The effects of densification on the structure of dry CNT fibres were measured by WAXS/SAXS. The densification treatment brings the fibre bundles closer (pores become smaller), leading to an increase in fibre density. However, structural domains made of the load and charge carrying nanotubes are not affected; consequently, it has no substantial effect on mechanical and electrical properties. SAXS measurements on the CNT fibres before and after liquid infiltration imply that most liquids are able to fill the internal pores but not to intercalate between nanotubes. Successful infiltration of low molecular weight polymer chains tends to expand the fibre bundles and increases the pore-opening angle. SAXS results indicate that the inner structure of the fibre, in terms of the nanotube layer arrangement and the fibre alignment, are not largely affected when infiltrated with polymers of relatively high molecular weight. The crystallisation of a variety of semicrystalline polymers is accelerated by the presence of aligned fibres of CNTs and results in the growth of a transcrystalline layer perpendicular to the fibre surface. This can be observed directly under polarised optical microscope, and detected by the exothermic peaks during differential scanning calorimetry. The discussion on the driving forces for the enhanced nucleation points out the preferential chain orientation of polymer lamella with the chain axis parallel to the fibre and thus to the nanotubes, which is confirmed by two-dimensional WAXS patterns. A non-epitaxial polymer crystal growth habit at the CNT-polymer interface is proposed, which is independent of lattice matching between the polymer and nanotubes. These findings contribute to the discussion on polymer nucleation on CNTs and other nanocarbons, and their implication for the development of large polymer composites based on long and aligned fibres of CNTs.

Application of the analytic hierarchy process (AHP) in multi-criteria analysis of the selection of intelligent building systems

The availability of innumerable intelligent building (IB) products, and the current dearth of inclusive building component selection methods suggest that decision makers might be confronted with the quandary of forming a particular combination of components to suit the needs of a specific IB project. Despite this problem, few empirical studies have so far been undertaken to analyse the selection of the IB systems, and to identify key selection criteria for major IB systems. This study is designed to fill these research gaps. Two surveys: a general survey and the analytic hierarchy process (AHP) survey are proposed to achieve these objectives. The first general survey aims to collect general views from IB experts and practitioners to identify the perceived critical selection criteria, while the AHP survey was conducted to prioritize and assign the important weightings for the perceived criteria in the general survey. Results generally suggest that each IB system was determined by a disparate set of selection criteria with different weightings. ‘Work efficiency’ is perceived to be most important core selection criterion for various IB systems, while ‘user comfort’, ‘safety’ and ‘cost effectiveness’ are also considered to be significant. Two sub-criteria, ‘reliability’ and ‘operating and maintenance costs’, are regarded as prime factors to be considered in selecting IB systems. The current study contributes to the industry and IB research in at least two aspects. First, it widens the understanding of the selection criteria, as well as their degree of importance, of the IB systems. It also adopts a multi-criteria AHP approach which is a new method to analyse and select the building systems in IB. Further research would investigate the inter-relationship amongst the selection criteria.

Applying Keller’s brand equity model in a B2B context : limitations and an empirical test

It has been recognised that brands play a role in industrial markets, but to date a comprehensive model of business-to-business (B2B) branding does not exist, nor has there been an empirical study of the applicability of a full brand equity model in a B2B context. This paper is the first to begin to address these issues. The paper introduces the Customer- Based Brand Equity (CBBE) model by Kevin Keller (1993; 2001; 2003), and empirically tests its applicability in the market of electronic tracking systems for waste management. While Keller claims that the CBBE pyramid can be applied in a B2B context, this research highlights challenges of such an application, and suggests changes to the model are required. Assessing the equity of manufacturers’ brand names is more appropriate than measuring the equity of individual product brands as suggested by Keller. Secondly, the building blocks of Keller’s model appear useful in an organisational context, although differences in the subdimensions are required. Brand feelings appear to lack relevance in the industrial market investigated, and the pinnacle of Keller’s pyramid, resonance, needs serious modifications. Finally, company representatives play a role in building brand equity, indicating a need for this human element to be recognised in a B2B model.

Designing for engagement : building IT systems

Context The School of Information Technology at QUT has recently undertaken a major restructuring of their Bachelor of Information Technology (BIT) course. Some of the aims of this restructuring include a reduction in first year attrition and to provide an attractive degree course that meets both student and industry expectations. Emphasis has been placed on the first semester in the context of retaining students by introducing a set of four units that complement one another and provide introductory material on technology, programming and related skills, and generic skills that will aid the students throughout their undergraduate course and in their careers. This discussion relates to one of these four fist semester units, namely Building IT Systems. The aim of this unit is to create small Information Technology (IT) systems that use programming or scripting, databases as either standalone applications or web applications. In the prior history of teaching introductory computer programming at QUT, programming has been taught as a stand alone subject and integration of computer applications with other systems such as databases and networks was not undertaken until students had been given a thorough grounding in those topics as well. Feedback has indicated that students do not believe that working with a database requires programming skills. In fact, the teaching of the building blocks of computer applications have been compartmentalized and taught in isolation from each other. The teaching of introductory computer programming has been an industry requirement of IT degree courses as many jobs require at least some knowledge of the topic. Yet, computer programming is not a skill that all students have equal capabilities of learning (Bruce et al., 2004) and this is clearly shown by the volume of publications dedicated to this topic in the literature over a broad period of time (Eckerdal & Berglund, 2005; Mayer, 1981; Winslow, 1996). The teaching of this introductory material has been done pretty much the same way over the past thirty years. During this period of time that introductory computer programming courses have been taught at QUT, a number of different programming languages and programming paradigms have been used and different approaches to teaching and learning have been attempted in an effort to find the golden thread that would allow students to learn this complex topic. Unfortunately, computer programming is not a skill that can be learnt in one semester. Some basics can be learnt but it can take many years to master (Norvig, 2001). Faculty data typically has shown a bimodal distribution of results for students undertaking introductory programming courses with a high proportion of students receiving a high mark and a high proportion of students receiving a low or failing mark. This indicates that there are students who understand and excel with the introductory material while there is another group who struggle to understand the concepts and practices required to be able to translate a specification or problem statement into a computer program that achieves what is being requested. The consequence of a large group of students failing the introductory programming course has been a high level of attrition amongst first year students. This attrition level does not provide good continuity in student numbers in later years of the degree program and the current approach is not seen as sustainable.

Biomechanical aspects of bone microstructure in vertebrates : potential approach to paleontological investigations

The biomechanical or biophysical principles can be applied to study biological structures in their modern or fossil form. Bone is an important tissue in paleontological studies as it is a commonly preserved element in most fossil vertebrates, and can often allow its microstructures such as lacuna and canaliculi to be studied in detail. In this context, the principles of Fluid Mechanics and Scaling Laws have been previously applied to enhance the understanding of bone microarchitecture and their implications for the evolution of hydraulic structures to transport fluid. It has been shown that the microstructure of bone has evolved to maintain efficient transport between the nutrient supply and cells, the living components of the tissue. Application of the principle of minimal expenditure of energy to this analysis shows that the path distance comprising five or six lamellar regions represents an effective limit for fluid and solute transport between the nutrient supply and cells; beyond this threshold, hydraulic resistance in the network increases and additional energy expenditure is necessary for further transportation. This suggests an optimization of the size of bone’s building blocks (such as osteon or trabecular thickness) to meet the metabolic demand concomitant to minimal expenditure of energy. This biomechanical aspect of bone microstructure is corroborated from the ratio of osteon to Haversian canal diameters and scaling constants of several mammals considered in this study. This aspect of vertebrate bone microstructure and physiology may provide a basis of understanding of the form and function relationship in both extinct and extant taxa.

The use of high dynamic range luminance mapping in the assessment, understanding and defining of visual issues in post occupancy building assessment

The international focus on embracing daylighting for energy efficient lighting purposes and the corporate sector’s indulgence in the perception of workplace and work practice “transparency” has spurned an increase in highly glazed commercial buildings. This in turn has renewed issues of visual comfort and daylight-derived glare for occupants. In order to ascertain evidence, or predict risk, of these events; appraisals of these complex visual environments require detailed information on the luminances present in an occupant’s field of view. Conventional luminance meters are an expensive and time consuming method of achieving these results. To create a luminance map of an occupant’s visual field using such a meter requires too many individual measurements to be a practical measurement technique. The application of digital cameras as luminance measurement devices has solved this problem. With high dynamic range imaging, a single digital image can be created to provide luminances on a pixel-by-pixel level within the broad field of view afforded by a fish-eye lens: virtually replicating an occupant’s visual field and providing rapid yet detailed luminance information for the entire scene. With proper calibration, relatively inexpensive digital cameras can be successfully applied to the task of luminance measurements, placing them in the realm of tools that any lighting professional should own. This paper discusses how a digital camera can become a luminance measurement device and then presents an analysis of results obtained from post occupancy measurements from building assessments conducted by the Mobile Architecture Built Environment Laboratory (MABEL) project. This discussion leads to the important realisation that the placement of such tools in the hands of lighting professionals internationally will provide new opportunities for the lighting community in terms of research on critical issues in lighting such as daylight glare and visual quality and comfort.

Building resilience to prevent mental health problems in young people : The resourceful adolescent programme (RAP)

This chapter describes an evidence-based programme called the Resourceful Adolescent Program (RAP), which has been successful in building resilience in young people to prevent depressive symptoms developing.The programme adopts a strengths-focused approach. It aims to build a range of coping resources that foster teenagers’ abilities to maintain a positive sense of self and regulate emotions in the face of the vicissitudes of everyday struggles and difficult life events.This groupbased programme can be implemented routinely in schools or by counselling professionals as an early intervention or prevention programme. While there is no universal definition, ‘resilience’ generally means the process of avoiding the negative trajectories associated with exposure to risk factors (Fergus and Zimmerman, 2005). Current models of resilience are also very clear that there ‘are many pathways to resilience’ (Bonanno, 2004) and there is no

Analysing strategic alliances in building construction

Building construction is a highly competitive and risky business. This competitiveness is compounded where conflicting objectives amongst contracting and subcontracting firms sets the stage for an adversarial and potentially destructive approach. There is a need for change in the construction industry—not only to a more cooperative approach to build mutual trust, respect and good faith—but also from a confrontationist and adversarial attitude to a harmonious relationship. It is necessary to change the culture to create a win-win situation. “Strategic Alliances” is one such concept. A strategic alliance is a cooperative arrangement between two or more organisations that forms part of their overall strategies, and contributes to achieving their major goals and objectives. This paper begins with an overview of the Australian building construction industry, then reviews the literature and describes an analysis framework comprising six attributes of strategic alliances—trust, commitment, interdependence, cooperation, communication, and joint problem solving. Given the trend towards greater emphasis on broader contracting firm performance criteria, indicators are proposed as a component of the tender evaluation process for public works.

Visual localisation in outdoor industrial building environments

This paper presents a vision-based method of vehicle localisation that has been developed and tested on a large forklift type robotic vehicle which operates in a mainly outdoor industrial setting. The localiser uses a sparse 3D edgemap of the environment and a particle filter to estimate the pose of the vehicle. The vehicle operates in dynamic and non-uniform outdoor lighting conditions, an issue that is addressed by using knowledge of the scene to intelligently adjust the camera exposure and hence improve the quality of the information in the image. Results from the industrial vehicle are shown and compared to another laser-based localiser which acts as a ground truth. An improved likelihood metric, using peredge calculation, is presented and has shown to be 40% more accurate in estimating rotation. Visual localization results from the vehicle driving an arbitrary 1.5km path during a bright sunny period show an average position error of 0.44m and rotation error of 0.62deg.

A penalty-based genetic algorithm for the composite SaaS placement problem in the cloud

Cloud computing is a latest new computing paradigm where applications, data and IT services are provided over the Internet. Cloud computing has become a main medium for Software as a Service (SaaS) providers to host their SaaS as it can provide the scalability a SaaS requires. The challenges in the composite SaaS placement process rely on several factors including the large size of the Cloud network, SaaS competing resource requirements, SaaS interactions between its components and SaaS interactions with its data components. However, existing applications’ placement methods in data centres are not concerned with the placement of the component’s data. In addition, a Cloud network is much larger than data center networks that have been discussed in existing studies. This paper proposes a penalty-based genetic algorithm (GA) to the composite SaaS placement problem in the Cloud. We believe this is the first attempt to the SaaS placement with its data in Cloud provider’s servers. Experimental results demonstrate the feasibility and the scalability of the GA.